WO2016098870A1

WO2016098870A1 - Process for treating keratin fibers technical field

Info

Publication number: WO2016098870A1
Application number: PCT/JP2015/085427
Authority: WO
Inventors: Kenichi KANEOKA; Natsumi Komure
Original assignee: L'oreal
Priority date: 2014-12-18
Filing date: 2015-12-11
Publication date: 2016-06-23
Also published as: JP2017537952A; JP6914837B2

Abstract

The present invention relates to composition for reshaping keratin fibers, preferably hair, comprising: (a) at least one fatty material, preferably in the form of liquid at ambient temperature and under atmospheric pressure, (b) at least one surfactant, preferably at least one nonionic surfactant, and (c) at least one alkaline agent, wherein the amount of the (a) fatty material is 30% by weight or more, preferably 50% by weight or more, relative to the total weight of the composition. The composition according to the present invention is an oil-rich composition comprising an alkaline agent which enables to achieve excellent perm performance with reduced or no malodor due to a reducing agent.

Description

DESCRIPTION

PROCESS FOR TREATING KERATIN FIBERS

TECHNICAL FIELD

The present invention relates to a composition for treating keratin fibers such as hair, as well as a process using the composition.

BACKGROUND ART

Many hair care products are marketed nowadays to easily style, texturize and add some weight to the hair, and especially to thin hair, amongst which foams and styling gels or hair lacquers may be mentioned as an example. 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 long-lasting shape modification 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 (an oxidizing step, also called a fixing step) , so as to give the hair the desired form in the end. The modified shape that is imposed to the hair by means of a chemical treatment, such as explained above, is relatively long-lasting and is particularly 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 shape modification of keratin fibers have been proposed. Generally, they offer good performances on the day of treatment.

For example, WO2011155076 discloses a perm process comprising the steps of: applying onto the keratin fibers a composition comprising one or several alkaline agents; placing the keratin fibers in an occlusive space; and heating the keratin fibers, JP-A-2008-081471 discloses a hair deformation agent which comprises oily material in an amount of 85-99.9% by weight and an oil-soluble reducing agent, and JP-A-1993-306212 discloses a hair deformation method characterized by applying to the hair a composition containing 20 to 100% by weight of the polyol, and allowed to deform at a temperature of 50 to 250 °C.

Furthermore, WO2013098332 discloses a composition for reducing curl and/or frizziness of hair comprising 20% by weight of olive oil, 2.0% by weight of monoethanolamine and 10.0% by weight of urea.

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:

- Short lastingness against environmental stress (e.g., mechanical constraints from

brushings, frequent shampoos, light exposure),

- Insufficient perm efficiency on natural hair,

- Hair degradation, especially in repeated applications or in combination with other

chemical treatments such as oxidative coloration, - Malodor of thiol-compounds during and after the perm process,

- Long and complicated application process.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide a composition, preferably a cosmetic composition for reshaping keratin fibers comprising alkaline agent, which enables to achieve excellent perm performance with reduced or no malodor due to a reducing agent. An objective of the present invention is also to provide a process for reshaping keratin fibers using the above composition.

The above objective can be achieved by a composition for reshaping keratin fibers, preferably hair, comprising:

(a)at least one fatty material, preferably in the form of liquid at ambient temperature and under atmospheric pressure,

(b) at least one surfactant, preferably at least one nonionic surfactant, and

(c) at least one alkaline agent, wherein the amount of the (a) fatty material is 30% by weight or more, preferably 50% by weight or more, relative to the total weight of the composition.

The (a) fatty material may be selected from the group consisting of hydrocarbon oils, silicone oils, plant or animal oils, ester or ether oils, fatty alcohols and mixtures thereof.

Preferably, the (a) fatty material may be selected from the group consisting of mineral oil, octyldodecanol, petrolatum, isododecane, hydrogenated polyisobutene, isopropyl myristate, dimethicone, cyclohexasiloxane, C₂o_-22 alcohol, cetyl palmitate, oleyl alcohol, cetyl alcohol and mixtures thereof.

The amount of the (a) fatty material may be 90% by weight or less, preferably 84.9 % by weight or less, more preferably 65 % by weight or less, relative to the total weight of the composition. In a preferred embodiment, the (b) surfactant may consist only of one or more nonionic surfactant(s).

The nonionic surfactant may be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants, preferably from

polyoxyalkylenated nonionic surfactants, and even preferably chosen from

polyoxyethylenated fatty alcohol and polyoxyethylenated fatty ester.

In a preferred embodiment, the (b) surfactant may be selected from the group consisting of Oleth-20, Oleth-10, Deceth-5 and mixtures thereof.

Preferably, the amount of the (b) at least one surfactant may be from 4% to 30 % by weight, preferably from 6% to 22 % by weight, and even preferably from 6% to 12% by weight, relative to the total weight of the composition. The (c) alkaline agent may be selected from the group consisting of an inorganic alkaline agent, an organic alkaline agent and mixtures thereof.

Preferably, the (c) alkaline agent may be selected from the group consisting of ammonia; alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal phosphates;

monohydrogen phosphates; monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof;

oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof; and mixtures thereof.

In a preferred embodiment, the amount of the alkaline agent may be from 0.1% to 10.0% by weight, preferably 1% to 7% by weight, and more preferably 2% to 5% by weight, relative to the total weight of the composition.

In a preferred embodiment, the amount of the inorganic alkaline agent may be from 0.1% to 9.9% by weight, preferably 1% to 7% by weight, and more preferably 2% to 5% by weight, or the amount of the organic alkaline agent may be from 1.1% to 10% by weight, preferably 1.5% to 7% by weight, and more preferably 2% to 5% by weight, relative to the total weight of the composition.

Preferably, the composition of the present invention do not comprise any reducing agent or comprises less than 1% by weight, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight of a reducing agent, relative to the total weight of the composition.

The composition according to the present invention may further comprise (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5. The (d) organic acidic agent having a pKa value of from 0.5 to 3.5(s) may be chosen from amino acids, aminosulfonic acids and mixtures thereof. Due to the presence of the (d) organic acidic agent having a pKa value of from 0.5 to 3.5, reshaping efficiency such as strong wave intensity of the curled keratin fibers can be further enhanced and damage to the keratin fibers can be further reduced.

In a preferred embodiment, the (a) fatty material, the (b) at least one surfactant and the (c) at least one alkaline agent and (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5 (when it is present) may be comprised in two or more separate compositions, preferably the (a) at least one fatty material and the (b) at least one surfactant may be comprised in one composition, and the (c) at least one alkaline agent and (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5 (when it is present) may be comprised in another composition.

The present invention also relates to a kit comprising a composition of the present invention and instructions for use.

The above objective can also be achieved by a process for reshaping keratin fibers, preferably hair, comprising the steps of:

applying a composition according to the present invention to keratin fibers

heating the keratin fibers to a temperature between 45°C to 250°C (step (1)),

optionally further heating the keratin fibers to a temperature between 70°C to 250°C (heating step (2))

rinsing and drying the keratin fibers.

The process may further comprise the step of rinsing the keratin fibers after the step of applying the composition onto the keratin fibers and before heating the keratin fibers.

The process may further comprise the step of providing the keratin fibers with mechanical tension, preferably by using a reshaping means selected from the group consisting of a curler, a roller, a clip, a plate and an iron.

The process may not comprise a step of placing the keratin fibers in an occlusive space.

In a preferred embodiment, the keratin fibers may be heated at a temperature ranging from 60°C to 150°C, preferably ranging from 60°C to 90°C during the step of heating the keratin fibers.

The composition of the present invention can eliminate thiol-odor and heavy hair damage caused by a reducing agent. The conventional formulation contains thioglycolic acid (e.g. lOwt %). Less hair damage will encourage customers for repeated applications or treatment combinations, perm and coloration, for example.

BRIEF DESCRIPTION OF DRAWINGS

Figure 1 shows the results of a test for perm efficiency between a composition with 35% by weight of fatty material and a composition with 20% by weight of the fatty material.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to an oil-rich composition for reshaping keratin fibers comprising an alkaline agent with a large amount of fatty material, and surfactant, which enables to achieve excellent perm performance even without any reducing agent.

The composition according to the present invention comprises:

(a) at least one fatty material, preferably in the form of liquid at ambient temperature and under atmospheric pressure,

(b) at least one surfactant, preferably at least one nonionic surfactant,

(c) at least one alkaline agent,

wherein the amount of the (a) fatty material is 30% by weight or more, preferably 50% by weight or more, relative to the total weight of the composition.

The composition according to the present invention may further comprises (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5

(Fatty Material)

The composition according to the present invention comprises (a) at least one fatty material. Here, "fatty material" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at ambient temperature (25°C) under atmospheric pressure (760 ramHg). As the fatty material(s), those generally used in cosmetics can be used alone or in combination thereof. These oil(s) may be volatile or non-volatile, preferably non-volatile. The (a) fatty material may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof. The (a) fatty material may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils and hydrocarbon oils.

As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil,¹ corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

As examples of animal oils, mention may be made of, for example, squalene and squalane. As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C₁-C₂₆ aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C C₂6 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, cetyl palmitate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of CrC₂₂ alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C₄-C₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used. Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate;

diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; - triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C -C₃₀ and preferably C₁₂-C₂₂ fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates. An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyri state, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).

As examples of silicone oils, mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane,

decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, cyclohexasiloxane, and the like; and mixtures thereof.

Preferably, silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid

polydimethylsiloxanes (PDMS) and liquid cyclohexasiloxane.

These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non- volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms.

These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as

dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula:

CH,

CH_Q

with D" : — Si - O with D' : - Si - O—

^C8^H17

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and

tetratrimethylsilylpentaerythritol (50/50) and the mixture of

octamethylcyclotetrasiloxane and

oxy-1 , 1 '-bis(2,2,2',2',3,3 '-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5><10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25 °C according to ASTM standard 445 Appendix C.

Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:

the Silbione^® oils of the 47 and 70 047 series or the Mirasil^® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

the oils of the Mirasil^® series sold by the company Rhodia;

the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm²/s;

the Viscasil^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia. Among the silicones containing aryl groups are polydiarylsiloxanes, especially

polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that may be mentioned include the products sold under the following names:

the Silbione® oils of the 70 641 series from Rhodia;

- the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;

the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;

the silicones of the PK series from Bayer, such as the product PK20;

certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide. Hydrocarbon oils may be chosen from:

linear or branched, optionally cyclic, C₆-C₁₆ lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; and

linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as

Parleam®, and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosane, and decene/butene copolymer; and mixtures thereof.

The (a) fatty material may be a fatty alcohol. The term "fatty alcohol" here means any saturated or unsaturated, linear or branched C₈-C₃₀ alcohol, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or non-conjugated carbon-carbon double bonds.

Among the C₈-C₃₀ fatty alcohols, C₁₂-C₃₀ fatty alcohols, for example, may be used. Mention may be made, among these, of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, linoleyl alcohol, undecylenyl alcohol, palmitoleyl alcohol, linolenyl alcohol, myristyl alcohol, arachidonyl alcohol, erucyl alcohol, octyldodecanol, and mixtures thereof. It is also preferable that the (a) fatty material be chosen from oils with molecular weight below 600 g/mol.

Preferably, the (a) fatty material has a low molecular weight such as below 600 g/mol, chosen among ester or ether oils with a short hydrocarbon chain or chains (CrC₁₂, e.g., isopropyl myristate, isopropyl palmitate, isononyl isononanoate, dicaprylyl carbonate, ethyl hexyl palmitate, dicaprylyl ether, and isopropyl lauroyl sarcosinate), hydrocarbon oils with a short alkyl chain or chains (Q-C^, e.g., isododecane, isohexadecane, and squalane), and short alcohol type oils such as octyldodecanol. It is also preferable that the (a) fatty material be selected from the group consisting of hydrocarbon oils, esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C_!-C₂₂ alcohols, and esters of C₄-C₂₂ monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C₄-C₂₆ dihydroxy, C4-C₁₅ trihydroxy, tetrahydroxy or pentahydroxy alcohols. It is preferable that the (a) fatty material be chosen from hydrocarbon oils, silicone oils, ester or ether oils, fatty alcohols and mixtures thereof, which are in the form of a liquid at ambient temperature.

More preferably, (a) fatty material be chosen from the group consisting of mineral oil, octyldodecanol, petrolatum, isododecane, hydrogenated polyisobutene, isopropyl myristate, dimethicone, cyclohexasiloxane, C_20-22 alcohol (i.e. C_20-22 fatty alcohol),, cetyl palmitate, oleyl alcohol, cetyl alcohol and mixtures thereof.

It is also preferable that the (a) fatty material be selected from the group consisting of mineral oil, C_20-22 alcohol, cetyl palmitate and mixtures thereof.

The amount in the composition according to the present invention of the (a) fatty material may range from 30% by weight or more, preferably 50% by weight or more, and preferably 90% by weight or less, more preferably 84.9% by weight or less, and even more preferably from 50% by weight or more and 65% by weight or less, relative to the total weight of the composition.

According to our experiment, a composition with 35% by weight of the fatty material exhibited good perm efficiency (number of curls: 6) whereas a composition with 20% by weight exhibited low perm efficiency (number of curls: 4) (Figure 1).

(Surfactant) The composition according to the present invention comprises (b) at least one surfactant.

Any surfactant may be used for the present invention. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

The (b) surfactant used in the present invention may be selected from the group consisting of (bl) anionic surfactants, (b2) amphoteric surfactants, (b3) cationic surfactants, and (b4) nonionic surfactants. (b 1 ) Anionic Surfactants

According to the present invention, the type of anionic surfactant is not limited. It is preferable that the anionic surfactant be selected from the group consisting of (C₆-C₃o) alkyl sulfates, (C₆-C₃₀) alkyl ether sulfates, (C₆-C3o) alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C₆-C₃₀) alkylsulfonates, (C₆-C₃o) alkylamide sulfonates, (C₆-C₃o) alkylaryl sulfonates, a-olefin sulfonates, paraffin sulfonates; (C -C₃₀) alkyl phosphates; (C₆-C₃₀) alkyl sulfosuccinates, (C₆-C₃₀) alkyl ether sulfosuccinates, (C₆-C₃₀) alkylamide sulfosuccinates; (C₆-C₃₀) alkyl sulfoacetates; (C₆-C₂₄) acyl sarcosinates; (C₆-C₂₄) acyl glutamates; (C₆-C3₀) alkylpolyglycoside carboxylic ethers; (C₆-C₃₀) alkylpolyglycoside sulfosuccinates; (C₆-C₃₀) alkyl sulfosuccinamates; (C₆-C₂₄) acyl isethionates; N-(C₆-C₂₄) acyl taurates; C₆-C₃₀ fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C₈-C₂₀) acyl lactylates; (C₆-C₃₀) alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C₆-C₃o) alkyl ether carboxylic acid salts; polyoxyalkylenated (C₆-C₃₀) alkylaryl ether carboxylic acid salts; and polyoxyalkylenated (C6-C30) alkylamido ether carboxylic acid salts.

It is more preferable that the anionic surfactant be selected from salts of (C₆-C₃o) alkyl sulfate or polyoxyalkylenated (C₆-C₃₀) alkyl ether carboxylic acid salts.

In at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.

(b2) Amphoteric Surfactants

According to the present invention, the type of amphoteric surfactant is not limited. The amphoteric or zwitterionic surfactants can be, for example (nonlimiting list), amine derivatives such as aliphatic secondary or tertiary amines, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain comprising 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate or phosphonate).

The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoaminecarboxylated derivatives.

The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and

alkylamidoalkylsulfobetaines, in particular, (C₈-C2₄) alkylbetaines, (C₈-C₂₄) alkylamido (Q-Q) alkylbetaines, sulphobetaines, and (C₈-C₂₄) alkylamido (Ci.Cg) alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are chosen from (C₈-C₂₄) alkylbetaines, (C -C₂₄) alkylamido(C₁-C₈) alkylsulphobetaines, sulphobetaines, and phosphobetaines.

Non-limiting examples that may be mentioned include the compounds classified in the CTFA dictionary, 9th edition, 2002, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/ oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine,

stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine,

oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and

cocosultaine, alone or as mixtures.

The betaine-type amphoteric surfactant is preferably an alkylbetaine and an

alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

Among the amidoaminecarboxylated derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and

Amphocarboxypropionates, with the respective structures:

R₁-CONHCH₂CH₂-N⁺(R₂)(R₃)(CH₂COO^") in which:

Ri denotes an alkyl radical of an acid RrCOOH present in hydrolysed coconut oil, a heptyl, nonyl or undecyl radical,

R₂ denotes a beta-hydroxyethyl group, and

R₃ denotes a carboxymethyl group; and

R -CONHCH^CHz-NCBXQ in which:

B represents -CH₂CH₂OX',

C represents -(CH₂)_Z-Y', with z~l or 2,

X' denotes a -CH₂CH₂-COOH group, -CH₂-COOZ', -CH₂CH₂-COOH, -CH₂CH₂-COOZ' or a hydrogen atom,

Y' denotes -COOH, -COOZ', -CH₂-CHOH-S0₃Z' or a -CH₂-CHOH-S0₃H radical,

Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ammonium ion or an ion issued from an organic amine, and

Ri' denotes an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C₇, C₉, Cn or CB alkyl radical, a C₁₇ alkyl radical and its iso form, or an unsaturated C₁₇ radical.

It is preferable that the amphoteric surfactant be selected from (C₈-C₂4) alkyl

amphomonoacetates, (C₈-C₂4) alkyl amphodiacetates, (Q-C24) alkyl amphomonopropionates, and (C₈-C₂4) alkyl amphodipropionates.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium

Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium

Caprylamphodipropionate, Lauroamphodipropionic acid and Cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie. (b3) Cationic Surfactants

According to the present invention, the type of cationic surfactant is not limited. The cationic surfactant may be selected from the group consisting of optionally

polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:

those of general formula (I) below:

wherein Ri, R₂, R₃, and R₄, which may be identical or different, are chosen from linear and branched aliphatic radicals comprising from 1 to 30 carbon atoms and optionally comprising

heteroatoms such as oxygen, nitrogen, sulfur and halogens. The aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C₂-C₆ polyoxyalkylene, alkylamide, (C₁₂-C₂₂) alkylamido (C₂-C₆) alkyl, (C₁₂-C₂₂) alkylacetate and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X^" is chosen from halides, phosphates, acetates, lactates, (C₂-C₆) alkyl sulfates and alkyl- or alkylaryl-sulfonates;

quaternary ammonium salts of imidazoline, for instance those of formula (II) below:

(Π)

wherein:

R₅ is chosen from alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;

R^ is chosen from hydrogen, C C₄ alkyl radicals, and alkenyl and alkyl radicals comprising from 8 to 30 carbon atoms;

R₇ is chosen from Ci-G} alkyl radicals;

R₈ is chosen from hydrogen and C]-C₄ alkyl radicals; and

X^" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R₅ and Rg are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals comprising from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R₇ is methyl and R₈ is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG and W75HPG by the company Witco;

diquaternary ammonium salts of formula (III):

(III)

wherein:

R₉ is chosen from aliphatic radicals comprising from 16 to 30 carbon atoms;

R₁₀ is chosen from hydrogen or alkyl radicals comprising from 1 to 4 carbon atoms or a group

(Rl6a)(Rl7a)(Rl8a)N⁺(CH₂)₃;

Rn, R₁₂, R₁₃, R₁₄, R_16a, R_17a, and R_18a, which may be identical or different, are chosen from hydrogen and alkyl radicals comprising from 1 to 4 carbon atoms; and

X^" is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates. An example of one such diquaternary ammonium salt is FINQUAT CT-P of

FINETEX(Quaternium-89) or FINQUAT CT of FINETEX (Quaternium-75); and

quaternary ammonium salts comprising at least one ester function, such as those of formula (IV) below:

wherein:

R₂₂ is chosen from C_\-C alkyl radicals and Q-Q hydroxyalkyl and dihydroxyalkyl radicals; R₂3 is chosen from:

the radical below:

linear and branched, saturated and unsaturated C1-C22 hydrocarbon-based radicals R₂₇, and hydrogen,

R₂₅ is chosen from:

the radical below:

O

R "2,8

linear and branched, saturated and unsaturated Ci-C^ hydrocarbon-based radicals R₂₉, and hydrogen,

R₂₄, R₂₆, and R₂₈, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C -C₂₁, hydrocarbon-based radicals;

r, s, and t, which may be identical or different, are chosen from integers ranging from 2 to 6; each of rl and tl, which may be identical or different, is 0 or 1, and r2+rl=2r and tl+2t=2t; y is chosen from integers ranging from 1 to 10;

x and z, which may be identical or different, are chosen from integers ranging from 0 to 10; X^" is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R₂₃ denotes R₂₇, and that when z is 0, R₂₅ denotes R₂₉. R₂₂ may be chosen from linear and branched alkyl radicals. In one embodiment, R₂₂ is chosen from linear alkyl radicals. In another embodiment, R₂₂ is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R₂₃ is a hydrocarbon-based radical R₂₇, it may be long and comprise from 12 to 22 carbon atoms, or short and comprise from 1 to 3 carbon atoms. When R₂₅ is a hydrocarbon-based radical R₂₉, it may comprise, for example, from 1 to 3 carbon atoms. By way of a non-limiting example, in one embodiment, R₂₄, R₂₆, and R₂₈, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, Cn-C₂₁ hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated Cn-C₂₁ alkyl and alkenyl radicals. In another embodiment, x and z, which may be identical or different, are 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s and t, which may be identical or different, are equal to 2 or 3, for example equal to 2. The anion X^" may be chosen from, for example, halides, such as chloride, bromide, and iodide; and C1-C4 alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion that is compatible with the ammonium comprising an ester function, are other non-limiting examples of anions that may be used according to the invention. In one embodiment, the anion X^" is chosen from chloride and methyl sulfate.

In another embodiment, the ammonium salts of formula (IV) may be used, wherein:

R₂₂ is chosen from methyl and ethyl radicals,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R₂3 is chosen from:

the radical below:

methyl, ethyl, and C₁₄-C₂₂ hydrocarbon-based radicals, hydrogen;

R₂₅ is chosen from:

the radical below:

O

^R28 ^C

and hydrogen;

R24, R26, an R₂₈, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, Co-Cn hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C₁₃-C₁₇ alkyl and alkenyl radicals. In one embodiment, the hydrocarbon-based radicals are linear.

Non-limiting examples of compounds of formula (IV) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyethyl-dimethylammonium, of

diacyloxyethyl-hydroxyethyl-methylamm- onium, of

monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethyl- ammonium, and mixtures thereof. In one embodiment, the acyl radicals may comprise from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound comprises several acyl radicals, these radicals may be identical or different.

These products may be obtained, for example, by direct esterification of optionally

oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine or

alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification may be followed by a quatemization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin; and glycerol

chlorohydrin. Such compounds are sold, for example, under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca, and "Rewoquat® WE 18" by the company Rewo-Goldschmidt.

Other non-limiting examples of ammonium salts that may be used in the compositions according to the invention include the ammonium salts comprising at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180.

Among the quaternary ammonium salts mentioned above that may be used in compositions according to the invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for instance dialkyldimethylammonium and alkyltrimethylammonium chlorides in which the alkyl radical comprises from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium,

cetyltrimethylammonium and benzyldimethylstearylammonium chloride;

palmitylamidopropyltrimethylammonium chloride; cetrimonium chloride; behentrimonium chrolide (docosyltrimethylammonium chloride); and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.

According to one embodiment, the cationic surfactant that may be used in the compositions of the invention is chosen from cetrimonium chloride, behentrimonium chrolide, and mixtures thereof.

(b4) Nonionic Surfactants

According to the present invention, the type of nonionic surfactant is not limited. According to the present invention, it is preferable that the (b) surfactant be a nonionic surfactant.

The nonionic surfactants are compounds well known in themselves (see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991, pp. 116-178). Thus, they can, for example, be chosen from alcohols, alpha-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non-limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C -C₂₄)alkylpolyglycosides; N-(C6-C₂₄)alkylglucamine derivatives; amine oxides such as (C₁o-C₁₄)alkylamine oxides or N-^io-Ci^acylaminopropylmorpholine oxides; silicone surfactants; and mixtures thereof. The nonionic surfactants may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units. Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include:

monooxyalkylenated or polyoxyalkylenated (C₈-C₂₄)alkylphenols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C₈-C₃₀ alcohols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C₈-C₃₀ amides,

esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of polyalkylene glycols,

monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of sorbitol,

saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated plant oils,

condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100 and most preferably between 2 and 50. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.

According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).

Examples of polyoxyethylenated fatty alcohol (or C₈-C₃₀ alcohols) that may be mentioned include the adducts of ethylene oxide with decyl alcohol, especially those containing from 3 to 10 oxyethylene units and more particularly those containing from 5 to 7 oxyethylene units (Deceth-5 to Deceth-7, as the CTFA names); the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units and more particularly those containing from 10 to 12 oxyethylene units (Laureth-10 to Laureth-12, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 9 to 50 oxyethylene units (Beheneth-9 to Beheneth-50, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 50 oxyethylene units (Ceteareth-10 to Ceteareth-50, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 10 to 30 oxyethylene units (Ceteth-10 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 2 to 20 oxyethylene units (Steareth-2 to Steareth-20, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 10 to 50 oxyethylene units (Isosteareth-10 to Isosteareth-50, as the CTFA names); the adducts of ethylene oxide with oleyl alcohol, especially those containing from 10 to 30 oxyethylene units (Oleth-10 to Oleth-30, as the CTFA names); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C -C₄₀ alcohols are preferably used. In particular, the monoglycerolated or polyglycerolated C₈-C₄o alcohols correspond to the following formula:

RO-[CH₂-CH(CH₂OH)-0]_m-H or RO-[CH(CH₂OH)-CH₂0]_m-H in which R represents a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

As examples of compounds that are suitable in the context of the present invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture. Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use the Cg/C₁₀ alcohol containing 1 mol of glycerol, the C₁₀/C₁₂ alcohol containing 1 mol of glycerol and the C₁₂ alcohol containing 1.5 mol of glycerol.

The monoglycerolated or polyglycerolated C₈-C₄o fatty esters may correspond to the following formula:

RO-[CH₂-CH(CH₂OR'")-0]_m-R" or R'0-[CH(CH20R'")-CH₂0]_m-R" in which each of R', R" and R'" independently represents a hydrogen atom, or a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkyl-CO- or alkenyl-CO-radical, with the proviso that at least one of R', R" and R'" is not a hydrogen atom, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

Examples of polyoxyethylenated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (as the CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (as the CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (as the CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (as the CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG- 100 stearate); and mixtures thereof.

According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units, such as glyceryl esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sorbitol esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sugar (sucrose, maltose, glucose, fructose, and/or alkylglycose) esters of a C₈-C₂₄, preferably C₁₂-C₂₂, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugar and a C₈-C₂₄, preferably C₁₂-C₂₂, fatty alcohol or alcohols; and mixtures thereof.

As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name: glyceryl stearate) or glyceryl ricinoleate and mixtures thereof can be cited, and as polyoxyalkylenated derivatives thereof, mono-, di- or triester of fatty acids with a polyoxyalkylenated glycerol (mono-, di- or triester of fatty acids with a polyalkylene glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di- and/or tristearate) can be cited.

Mixtures of these surfactants, such as for example the product containing glyceryl stearate and PEG- 100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE), can also be used.

The sorbitol esters of C8-C₂₄ fatty acids and polyoxyalkylenated derivatives thereof can be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and esters of fatty acids and alkoxylated sorbitan containing for example from 20 to 100 EO, such as for example sorbitan monostearate (CTFA name: sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65), sold by the company ICI under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Uniqema.

As esters of fatty acids and glucose or alkylglucose, glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture of oleic acid/hydroxy stearic acid (CTFA name: Methyl glucose dioleate/hydroxystearate), the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can for example be cited.

As sucrose esters, saccharose palmito-stearate, saccharose stearate and saccharose monolaurate can for example be cited.

As sugar ethers, alkylpolyglucosides can be used, and for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818 UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Mixtures of glycerides of alkoxylated plant oils such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides can also be cited.

The nonionic surfactant according to the present invention preferably contains alkenyl or branched C₁₂-C₂₂ acyl chain such as oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate. According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from copolymers of ethylene oxide and of propylene oxide, in particular copolymers of the following formula:

HO(C₂H₄0)a(C₃H₆0)_b(C₂H₄0)_cH in which a, b and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60, and mixtures thereof.

According to one of the embodiments according to the present invention, the nonionic surfactant may be selected from silicone surfactants. Non-limiting mention may be made of those disclosed in documents US-A-5364633 and US-A-5411744.

The silicone surfactant ma preferably be a compound of formula (V):

in which:

Ri, R₂ and R₃, independently of each other, represent a Q-C6 alkyl radical or a radical -(CH₂)_x-(OCH₂CH₂)_y-(OCH₂CH₂CH₂)_z-OR4, at least one radical ¾, R₂ or R₃ not being an alkyl radical; R4 being a hydrogen, an alkyl radical or an acyl radical;

A is an integer ranging from 0 to 200;

B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero;

x is an integer ranging from 1 to 6;

y is an integer ranging from 1 to 30;

z is an integer ranging from 0 to 5. According to one preferred embodiment of the present invention, in the compound of formula (V), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30. As examples of silicone surfactants of formula (V), mention may be made of the compounds of formula (VI):

(CH₃)₃SiO - [(CH₃)₂SiO]_A - (CH₃SiO)_B - Si(CH₃)₃

I (VI)

(CH₂)_r{OCH₂CH₂)_y-OH

in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20.

As examples of silicone surfactants of formula (V), mention may also be made of the compounds of formula (VII):

H-(OCH₂CH₂)_y-(CH₂)₃-[(CH₃)₂SiO]A'-(CH₂)₃-(OCH₂CH₂)_y-OH (VII) in which A' and y are integers ranging from 10 to 20.

Compounds of the present invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667. The compounds DC 5329, DC 7439-146 and DC 2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12.

The compound Q4-3667 is a compound of formula (VII) in which A is 15 and y is 13.

The HLB of the nonionic surfactant(s) may be more than 8, preferably more than 9, more preferably more than 10. If two or more nonionic surfactants are used, the HLB value is determined by the weight average of the HLB values of all the nonionic surfactants. The HLB is the ratio between the hydrophilic part and the lipophilic part in the molecule. This term HLB is well known to those skilled in the art and is described in "The HLB system. A time-saving guide to emulsifier selection" (published by ICI Americas Inc., 1984). If the HLB of the nonionic surfactant(s) is lower than 8, the oily feeling after rinsing-off would remain. If the HLB of the nonionic surfactant(s) is higher than 13, the removability of the composition would be worse.

Preferred nonionic surfactants which can be used in the composition of the invention of the present application can be selected from polyethylene glycol ethers of C₈-C₂₄ fatty alcohol or alcohols, fatty acid or acids, and polyoxyalkylenated derivatives thereof and polypropylene glycol ethers of C₄-C₂₄ fatty alcohol or alcohols such as PPG- 14 butyl ether and PPG- 15 stearyl ether..

In a preferred embodiment, the (b) surfactant may consist only of one or more nonionic surfactant(s).

In a preferred embodiment, the (b) surfactant may comprise at least one nonionic surfactant and at least one cationic surfactant. Preferred nonionic surfactants which can be used in the composition of the invention of the present application can be selected from Oleth-20, Oleth-10, Deceth-5, Steareth-2, Steareth-20, Ceteareth-33, PPG- 14 butyl ether, PPG- 15 stearyl ether, and mixtures thereof, more preferably, from Oleth-20, Oleth-10, Deceth-5 and mixtures thereof.

Preferably, the (b) surfactant may be selected from the group consisting of Oleth-20, Oleth-10, Deceth-5 and mixtures thereof. The amount of the (b) at least one surfactant may be from 4% to 30 % by weight, preferably from 6% to 22 % by weight, and more preferably from 6% to 12 % by weight, relative to the total weight of the composition.

(Alkaline Agent)

The composition according to the present invention comprises (c) at least one alkaline agent.

The alkaline agent may be an inorganic alkaline agent. It is preferable that the inorganic alkaline agent be selected from the group consisting of ammonia; alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal phosphates and monohydrogen phosphates such as sodium phosphate or sodium monohydrogen phosphate; ammonium hydroxide; and ammonium bicarbonate.

As examples of the inorganic alkaline metal hydroxides, mention may be made of sodium hydroxide and potassium hydroxide. As examples of the alkaline earth metal hydroxides, mention may be made of calcium hydroxide and magnesium hydroxide. As the inorganic alkaline agent, sodium hydroxide, ammonium hydroxide and ammonium bicarbonate are preferable. The alkaline agent may be an organic alkaline agent. It is preferable that the organic alkaline agent be selected from the group consisting of monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof.

As examples of the organic alkaline agents, mention may be made of alkanolamines such as mono-, di- and tri-ethanolamine, and isopropanolamine; urea, guanidine and their derivatives; basic amino acids such as lysine, ornithine 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 Q-C4 alkyl radical, and R_l5 R₂, R₃ and R4 independently denote a hydrogen atom, an alkyl radical or a C₁-C₄ hydroxyalkyl radical, which may be exemplified by 1,3-propanediamine and

derivatives thereof. It is preferable that the (c) alkaline agent be selected from non- volatile alkaline agents, and more preferably be selected from organic amines, inorganic bases, organic amine salts and ammonium salts. The non-volatile alkaline agent may be an inorganic alkaline agent selected among the alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal

(hydrogeno)carbonates; alkaline earth metal (hydrogeno)carbonates; ammonium

(hydrogeno)carbonates; alkaline metal metasilicates; ammonium metasilicates; and mixtures thereof.

The non-volatile alkaline agent may be an organic alkaline agent selected among monoamines, and derivatives and salts of monoamines; diamines, and derivatives and salts of diamines; polyamines, and derivatives and salts of polyamines; amino acids and derivatives thereof; oligomers of amino acids and derivatives thereof; polymers of amino acids and derivatives thereof; urea and derivatives thereof; guanidine and derivatives thereof; and mixtures thereof.

Preferably, the (c) alkaline agent may be selected from the group consisting of an inorganic alkaline agent, an organic alkaline agent and mixtures thereof. Preferably, the (c) alkaline agent may be selected from the group consisting of ammonia; alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal phosphates; monohydrogen phosphates; monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof; and mixtures thereof.

It is preferable that the non- volatile alkaline agent be selected from alkaline metal hydroxides and alkanolamines, more preferably sodium hydroxide, monoethanolamine and

monoisopropanolamine.

The amount of the inorganic alkaline agent be from 0.1% to 9.9% by weight, preferably 1% to 7% by weight, more preferably 2% to 5%, or the amount of the organic alkaline agent be from 1.1% tol0% by weight, preferably 1.5% to 7% by weight, more preferably 2% to 5%, by weight relative to the total weight of the composition.

(Organic Acidic Agent having pKa Value of less than 3.5)

The composition according to the present invention may further comprise (d) at least one organic acidic agent having pKa value of less than 3.5. Two or more (d) organic acidic agent having pKa value of less than 3.5 may be used in combination. Thus, a single type of organic acidic agent having pKa value of less than 3.5 or a combination of different types of organic acidic agent having pKa value of less than 3.5 may be used. The pKa value may be measured at 25°C.

The (d) organic acidic agent having a pKa value of less than 3.5 has at least one pKa value less than 3.5, and may have two or more pKa values. If the (d) organic acidic agent has two or more pKa values, at least one of the pKa values must be in a range less.than 3.5. One should recall that the term "organic" means that the acidic agent has at least one carbon atom in its chemical structure.

It is preferable that the (d) organic acidic agent having pKa value of less than 3.5 be non- volatile. One should recall that the term "non- volatile" means that the acidic agent has a vapor pressure generally lower than 0.02 mmHg (2.66Pa) at room temperature.

The (d) organic acidic agent having pKa value of less than 3.5 may be selected from the group consisting of carboxylic acids, aminosulfonic acids, amino acids such as glycine, alanine, glutamic acid, aspartic acid, phenyl alanine, β-alanine, isoleucine, leucine, proline, glutamine, serine, threonine, valine, tryptophane, tyrosine, oligomers of amino acids such as

glycylglycine, and mixtures thereof.

The carboxylic acids having pKa value of less than 3.5 may be selected from the group consisting of oxalic acid, malonic acid, maleic acid, salicylic acid, phthalic acid, and mixtures thereof.

The aminosulfonic acid having pKa value of less than 3.5 may be selected from the group consisting of taurine, 2-(cyclohexylamino)ethanesulfonic acid, and mixtures thereof.

It is preferable that the (d) organic acidic agent having pKa value of less than 3.5 be selected from taurine, 2-(cyclohexylamino)ethanesulfonic acid, amino acids having a pKa value of less than 3.5, and mixtures thereof. The amino acids that may be used according to the present invention may be a-amino acids, β-amino acids, or γ-amino acids. Preferably, the amino acids used in the present invention are a-amino acids, i.e., they comprise an amine function and an acid function at the same carbon atom. The a-amino acids may be represented by the following formula (I):

R— CH— eooH

(I)

in which:

when p=2, R represents a hydrogen atom, an aliphatic group optionally containing one or several nitrogen atoms, a heterocyclic portion, or an aromatic group, or

when p=l, R can form a heterocycle with the nitrogen atom of -N(H)_P. This heterocycle is preferably a saturated 5-membered ring, optionally substituted with one or more C1-C₄ alkyl or hydroxyl groups. Preferably, the aliphatic group is a linear or branched Q-C₄ alkyl group; a linear or branched CrC₄ hydroxyalkyl group; a linear or branched CrC₄ aminoalkyl group; a linear or branched (Q-Q alkyl)thio(C₁-C₄)alkyl group; a linear or branched C₂-C₄ carboxyalkyl group; a linear or branched ureidoalkyl group, a linear or branched guanidinoalkyl group, a linear or branched imidazoloalkyl group or a linear or branched indolylalkyl group, the alkyl portions of these last four groups comprising from one to four carbon atoms.

Preferably, the aromatic group is a C₆ aryl or C₇-C₁₀ aralkyl group, the aromatic nucleus optionally being substituted with one or more Q-C4 alkyl or hydroxyl groups.

It is preferable that the amino acids be selected from acidic amino acids and neutral amino acids. The term "neutral amino acids" is intended to mean amino acids which have a pH, at ambient temperature (25°C), in water of inclusively between 5 and 7. The term "acidic amino acids" is intended to mean amino acids which have a pH, at ambient temperature, in water of less than 5.

As acidic amino acids and neutral amino acids that may be used in the present invention, mention may be made especially of aspartic acid, glutamic acid, alanine, asparagine, carnitine, glutamine, glycine, isoleucine, leucine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine.

The (d) organic acidic agent having pKa value of less than 3.5 may have two or more carboxylic acids, such as aspartic acid and glutamic acid.

It is preferable that the (d) organic acidic agent has a pKa value of from 0.5 to 3.5, more preferably from 1.0 to 3.0, and even more preferably from 1.5 to 2.8. It is preferable that the (d) organic acidic agent having pKa value of less than 3.5 be selected from the group consisting of glycine, taurine, alanine, proline,

2-(cyclohexylamino)ethanesulfonic acid and mixtures thereof.

The amount of the (d) organic acidic agent having pKa value of less than 3.5 in the

composition according to the present invention may be from 0.1 to 25% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 17% by weight, relative to the total weight of the composition.

(Other Ingredient)

(Ingredients which are common in cosmetic compositions)

The composition according to the present invention may also comprise an effective amount of other ingredients which are common in cosmetic compositions, such as various common adjuvants, vitamins such as Vitamin C, anti-ageing agents, whitening agents, anti-greasy skin agents, chelating agents such as EDTA and pentasodium pentetate, UV screening agents, anti-oxidating agents such as Vitamin C and sodium metabisulfite, preserving agents such as phenoxyethanol, vitamins or provitamins, for instance, panthenol, opacifiers, fragrances, plant extracts, cationic polymers and so on.

The thickener may be chosen, for example, from cellulose-based thickeners such as hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose; guar gum and derivatives thereof, for example, hydroxypropyl guar, marketed by RHODIA under the reference JAGUAR HP 105, and microbial gums such as xanthan gum and scleroglucan gum; and synthetic thickeners such as cetyl stearyl alcohol, acrylic and acrylamidopropane sulfonic acid crosslinked homopolymers, for example Carbomer, associative non ionic, anionic, cationic, and amphoteric polymers, such as polymers marketed under the names PEMULEN TR1 and TR2 by GOODRICH, SALCARE SC90 by ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, and 46 by ROHM & HAAS and ELFACOS T210 and T212 by AKZO. (Reducing Agent)

The composition according to the present invention may comprise a reducing agent; however, it is preferable that the composition according to the present invention comprises a reduced amount of a reducing agent, preferably no reducing agent.

The reducing agent may be a thiol reducing agent or a non-thiol reducing agent.

The term "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; di thioglycolic acid and derivatives thereof in particular esters thereof such as glycerol or glycol dithioglycolate; 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 C_1-4 acyl derivatives thereof such as N-acetylcysteamine and N-propionylcysteamine; thioglycerol, for example 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; glutathione in the reduced form; mercaptosuccinic acid; 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, monoethanolamine,

di-isopropanolamine or triethanolamine, 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 and N-mono- or

Ν,Ν-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. 0 432 000 and alkylaminomercaptoalkylamides such as those described in European Patent Application No. 0 514 282; (2/3) hydroxy-2 propyl thioglycolate; and the hydroxy-2 methyl-1 ethyl thioglycolate-based mixture (67/33) described in French Patent Application No. 2 679 448.

The thiol-based reducing agent may be a compound represented by the following chemical formula (VIII):

wherein

X is a structure selected from the group consisting of -0-, -S-, -NH- and -NR¹-;

R¹ is an alkyl group of 1 to 6 carbon atoms;

R² is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; Y is an oxygen atom or a sulfur atom; and

R is a divalent organic residue optionally having a mercapto group.

X is preferably -0-, -NH-, -NCH₃- or -S- in view of preparation of a perm solution, in which case the compound shows relatively high solubility in the perm aqueous solution.

Y is an oxygen atom or a sulfur atom, and is more preferably an oxygen atom in view of industrial availability and handling properties. R² may be a hydrogen atom, a methyl group, an ethyl group or a propyl group, and is preferably a hydrogen atom, a methyl group or an ethyl group.

R is a divalent organic residue optionally having a mercapto (-SH) group. R is not particularly limited as long as it is a divalent organic group, and can be an alkylene group. The main chain of the alkylene group may have 2 to 6 carbon atoms. The divalent organic residue may have a branch or a side chain. Examples of the side chains include alkyl groups and alkenyl groups.

If R is substituted with a mercapto group, one or more mercapto groups may be present.

The term "non-thiol reducing agent" here means a reducing agent with no thiol group. The non-thiol reducing agent may be chosen from the group consisting of sulfites, bisulfites, sulfinates, phosphines, sugars, reductones and hydrides. 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 (IX) below:

in which

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

R³¹, R³² and R³³, 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 heteroatoms 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-alkylamino 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, sulfinate, 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=l , m=0 and p=l ;

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 R³¹, R³² and R³³,

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

dihydroxyalkylamino and carboxyl. For example, the radical p-methoxyphenyl is a substituted aryl radical. The radicals R , R and R may not simultaneously represent a hydrogen atom.

Optionally, at least one of the radicals R , R and R denotes, as a hydrocarbon-based radical, an optionally substituted alkyl radical. For example, 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 dialkylaminoalkyl radical, a haloalkyl radical, a hydroxyl radical, a carboxyl radical, a halogen atom, and an aryl radical substituted with a mono- or dialkylaminoalkyl 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; a trifluoromethyl radical; a chloromethyl radical; an allyl radical; a vinyl radical; a dimethylamino radical; a diethylamino radical; a

di(isopropyl)amino 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 trimethoxyphenyl radical; an o-(dimethylamino)phenyl radical; an m-(dimethylamino)phenyl radical; a p-(dimethylamino)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-(diethylaminomethyl)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-diethylaminomethyl-phenyl)phenyl radical; a 5-methyl-2-isopropylcyclohexyl radical; an N-methyl-N-phenylaminomethyl radical; and a carboxyphenyl radical.

Non-thiol-based reducing agents may be chosen from sulfites, bisulfites and phosphines.

The sulfur-containing reducing agent may be selected from the group consisting of

2-mercapto-4-butanolide, glutathione, thioglycolic acid, 3-mercaptopropionic acid, thiolactic acid, L-cysteine, cysteamine, thioglycerol, L-cysteine methyl ester, L-cysteine ethyl ester, mercaptosuccinic acid, glycerol monothioglyclate, N-acetyl-L-cysteine and mixtures thereof.

In a preferred embodiment, the composition according to the present invention may comprise less than 1%, for example, less than 0.5%, or less than 0.1% by weight of a reducing agent, relative to the total weight of the composition.

In another preferred embodiment, the composition according to the present invention does not comprise any reducing agent.

The composition according to the invention may comprise one or several polyols. In a preferred embodiment, the composition according to the present invention comprise less than 20%, preferably less than 10%, more preferably less than 5% by weight of polyol which may be low molecular weight water-soluble compound having two or more hydroxyl groups such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butylene glycol, triethylene glycol, polyols for use in the present invention, hexylene glycol.

[Preparation]

The composition can be prepared by mixing (a) at least one fatty material; (b) at least one surfactant; (c) at least one alkaline agent and preferably (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5 , as essential ingredients, as well as optional

ingredient(s) as explained above.

The method and means to mix the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the composition according to the present invention.

The composition according to the present invention is preferably a ready-to-use composition. For the purposes of the present invention, the expression "ready-to-use composition" is defined herein as a composition to be applied immediately to keratin fibers such as hair.

Said "ready-to-use composition" may be stored in unmodified form before use, or may result from the extemporaneous mixing of two or more separate compositions. In one embodiment, one of the separate compositions may comprise (a) at least one fatty material and (b) at least one surfactant, and another of the separate compositions may comprise (c) at least one alkaline agent and preferably (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5. In this embodiment, it is preferable that the composition according to the present invention be obtained prior to use by mixing a first composition comprising (a) at least one fatty material and (b) at least one surfactant, and a second composition comprising (c) at least one alkaline agent and preferably (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5, preferably under a temperature of about 70 °C, and cool the mixture to ambient temperature.

[Kits]

In some embodiments, the present invention provides for kits comprising a composition of the invention and instructions for use.

Preferably the instructions comprise an explanation that the composition according to the present invention be used to a process for reshaping keratin fibers, comprising at least the step of heating the keratin fibers to a temperature between 45°C to 250°C, preferably 60°C to 200°C, more preferably 60°C to 150°C, more preferably 60°C to 90°C (heating step (1)). In some embodiments, after Step (1) of heating the keratin fibers, a step of heating the keratin fibers to a temperature between 70°C to 250°C, preferably 80°C to 200°C, more preferably 90°C to 150°C, more preferably 100°C to 130°C, may be performed (heating step (2)). In particular, when the (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5 is present, preferably the heating step (2) may be performed. In some embodiments, the kit may contain, for example, gloves or a conditioning rinse.

In some other embodiments, the developer bottle may contain a solution comprising hydrogen peroxide.

In yet other embodiments, one or more components (a) to (c) of the composition of the present invention are packaged separately from other components. [Keratin Fiber Reshaping Process]

The present invention also relates to a process using the composition according to the present invention. Preferably, the process according to the present invention be intended for reshaping keratin fibers such as hair.

The process for treating keratin fibers according to the present invention can be performed by applying a composition according to the present invention to keratin fibers,

heating the keratin fibers to a temperature between 45°C to 250°C (heating step (1)), optionally further heating the keratin fibers to a temperature between 70°C to 250°C

(heating step (2)),

rinsing and drying the keratin fibers.

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

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.

According to the present invention, the keratin fibers will be heated at 45°C to 250°C, preferably 60°C to 200°C, more preferably 60°C to 150°C, and more preferably 60°C to 90°C, during heating step (1) of heating the keratin fibers. In some embodiments, after heating step (1) of heating the keratin fibers, the keratin fibers will be further heated at 70°C to 250°C, preferably 80°C to 20G°C, more preferably 90°C to 150°C, more preferably 100°C to 130°C, during heating step (2) of heating the keratin fibers.

Therefore, the composition according to the present invention can be used to a process for reshaping keratin fibers, comprising at least the step of heating the keratin fibers to a temperature between 45°C to 250°C, preferably 60°C to 200°C, more preferably 60°C to 150°C, and more preferably 60°C to 90°C (heating step (1)). Preferably, after heating step (1) of heating the keratin fibers, a step of heating the keratin fibers to a temperature between 70°C to 250°C, preferably 80°C to 200°C, more preferably 90°C to 150°C, more preferably 100°C to 130°C, may be performed (heating step (2)).

The heating steps (1) and (2) may be performed independently for an appropriate time which is required to treat keratin fibers. The time length for each of the heating steps (1) and (2) is not limited, but it may be from 1 minute to 2 hours, preferably 1 minute to 1 hour, and more preferably 1 minute to 30 minutes. For example, the time for heating step (1) may be from 5 to 20 minutes, and preferably from 10 to 15 minutes. The time for heating step (2) may be from 10 to 25 minutes, and preferably from 15 to 20 minutes.

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

According to the present invention relating to the reshaping process for keratin fibers, the keratin fibers may be subjected to mechanical tension which is typically used for permanent deformation. The reshaping 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 composition is applied to the keratin fibers. The application of the 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

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 step(s) is(are) performed.

This reshaping process for 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.

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

In one embodiment, the process according to the present invention may not comprise a step of placing one or more means for covering the keratin fibers to which the composition according to the present invention has been applied to form one or more closed spaces (occlusive spaces) above the keratin fibers, before the heating step. Therefore, the process according to the present invention may not comprise a step of placing the keratin fibers in an occlusive space.

The occlusive space can be formed by at least one coating means in order to restrict the evaporation of evaporable components such as water in the above-described composition from keratin fibers and keep a predetermined temperature in the heating device throughout the process.

EXAMPLES The present invention will be described in a more detailed manner by way of examples.

However, these examples should not be construed as limiting the scope of the present invention.

Examples 1, 2 and Comparative Examples 1 to 3

[Preparation]

Each of the compositions according to Examples 1, 2 and Comparative Examples 1 to 3 was respectively prepared by mixing the ingredients shown in Table 1 according to the following manner.

Table 1. Ingredients of the com ositions of Exam le 1, 2 and Com arative Examples 1 to 3

(unit: % by weight)

Tab e 2. Product information of the in redients used in the Exam les

Preparation procedure for the compositions (Ex. Composition of Example 1)

1) C_20-22 alcohols, cetyl palmitate, Oleth-20, Oleth-10, and Deceth-5 were dissolved in

mineral oil at 70 °C to obtain a mineral oil phase.

2) Ethanolamine was dissolved in water at 70 °C to obtain a water phase.

3) The water phase was poured into mineral oil phase and the mixture was agitated at 70 °C. 4) Carbomer was added to the mixture.

5) The mixture was cooled to the ambient temperature.

Similarly, the compositions of Example 2 and Comparative Examples 1 to 3 were also prepared.

[Evaluation of Perm efficiency]

(Evaluation protocol) 1) Each composition (1 g) of Examples 1 and 2 and Comparative Examples 1 to 3 was applied on of Chinese hair swatch (1 g).

2) The hair swatch was rolled on a 1.6 cm diameter perm-roller.

3) The perm-roller was plugged on a Digital Perm Machine (Oohiro, model ODIS-2) and heat at 90 °C for 15 minutes.

4) The hair swatch was rinsed and dried.

5) The perm efficiency was evaluated based on the number of curls on the hair swatch. The results are shown in Table 3.

[Results of Perm Efficiency]

Table 3. Results of the evaluation of erm efficiency

++: very good perm efficiency, number of curls more than 8

+: good perm efficiency, number of curls 6~7

-: low perm efficiency, number of curls 4~5

--: weak perm efficiency, number of curls less than 3 As shown in Table 3, the compositions of Examples 1 and 2 exhibited very high perm efficiency.

It can be recognized from the result of Example 1 in comparison with that of Comparative Example 1 , the alkaline agent would have brought the good perm efficiency for Example 1. In addition, upon considering the result of Example 1 in comparison with that of Comparative Example 2, or Example 2 in comparison with that of Comparative Example 3, it can be understood that the fatty material and surfactant would also have contributed to the good perm efficiency for Examples 1 and 2. Accordingly, it has been demonstrated that the oil-rich composition comprising an alkaline agent of the invention enables to achieve excellent perm performance without any reducing agent.

In addition, the perm efficiency of Example 1 was even better than the perm efficiency of another experiment where the composition of Example 1 was used but the perm-roller was left at ambient temperature during step 3) of the above-described Evaluation protocol.

Furthermore, upon comparing the perm efficiency of modified compositions of Example 1 where only the total amount of (a) fatty material was changed to 35% by weight or 20% by weight, a composition with 35% by weight of the fatty material (B) exhibited good perm efficiency (number of curls: 6) whereas a composition with 20% by weight (A) exhibited low perm efficiency (number of curls: 4) (Figure 1).

Examples 3 to 5

[Preparation] Each of the compositions according to Examples 3 to 5 was respectively prepared by mixing the ingredients shown in Table 4 according to the following manner.

Table 4. Ingredients of the compositions of Exam les 3 to 5

(unit: % by wei;

Tab e 5. Product information of the in redients used in the Exam les

Preparation procedure for the compositions (Ex. Composition of Example 3)

1) Steareth-2 and Steareth-20 were dissolved in Dimethicone at 70 °C to obtain a mineral oil phase.

2) Sodium hydroxide and glycine were dissolved in water at 70 °C to obtain a water phase.

3) The water phase was poured into mineral oil phase and the mixture was agitated at 70 °C.

4) Hydroxyethylcellulose was added to the mixture.

5) The mixture was cooled to the ambient temperature.

Similarly, the compositions of Examples 4 and 5 were also prepared.

Perm efficiency was evaluated by the above-mentioned Evaluation protocol for Examples 1, 2 and Comparative Examples 1 to 3 except that the perm-roller in step 3) was plugged on another Digital Perm Machine (ASIA Electronics, model PHC) and heated at 80 degrees for 10 minutes and 120 degrees for 15 minutes. The results are shown in Table 6.

[Results of Perm Efficiency]

Table 6. Results of the evaluation of perm efficiency

Examples

3 4 5 pH 10.5 10.5 N.A. (very high)

Perm Efficiency ++ ++ ++

Hair damage ++ ++ Perm Efficiency

++: very good perm efficiency, number of curls more

+: good perm efficiency, number of curls 6~7

-: low perm efficiency, number of curls 4-5

— : weak perm efficiency, number of curls less than 3

Hair damage

++: Very low damage level: no hair breakage, good touch

+: Low damage level: no hair breakage, slight lack of bounce

-: Slightly damaged: Some hair breakage obsearved, lack of bounce

— : Heavily damaged: Hair breakage frequently observed, unnatural softness

As shown in Table 6, due to the presence of Glycine (Example 3) and Taurine (Example 4), the pH of the compositions of Examples 3 and 4 was controlled to a relatively low value (10.5). Furthermore, the compositions of Examples 3 and 4 not only exhibited very high perm efficiency on the same level with Example 5 but also caused less damage to the keratin fibers.

Claims

1. A composition for reshaping keratin fibers, preferably hair, comprising:

(b) at least one surfactant, preferably at least one nonionic surfactant, and

(c) at least one alkaline agent,

2. The composition according to claim 1 , wherein the (a) fatty material is selected from the group consisting of hydrocarbon oils, silicone oils, plant or animal oils, ester or ether oils, fatty alcohols, and mixtures thereof.

3. The composition according to claim 1 or 2, wherein the fatty material (a) is selected from the group consisting of mineral oil, octyldodecanol, petrolatum, isododecane,

hydrogenated polyisobutene, isopropyl myristate, dimethicone, cyclohexasiloxane, C₂₀-₂₂ alcohol, cetyl palmitate, oleyl alcohol, cetyl alcohol, and mixtures thereof.

4. The composition according to any one of claims 1-3, wherein the amount of the (a) fatty material is 90% by weight or less, preferably 84.9 % by weight or less, more preferably 65 % by weight or less, relative to the total weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein the (b) surfactant

consists of one or more nonionic surfactant(s).

6. The composition according to any one of claims 1 to 5, wherein the nonionic surfactant is chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or

polyglycerolated nonionic surfactants, preferably from polyoxyalkylenated nonionic surfactants, and even preferably chosen from polyoxyethylenated fatty alcohol and polyoxyethylenated fatty ester.

7. The composition according to claim 6, wherein the (b) surfactant is selected from the

group consisting of Oleth-20, Oleth-10, Deceth-5 and mixtures thereof.

8. The composition according to any one of claims 1 to 7, wherein the amount of the (b) at least one surfactant is from 4% to 30 % by weight, preferably from 6% to 22 % by weight, and even preferably from 6% to 12% by weight, relative to the total weight of the composition.

9. The composition according to any one of claims 1 to 8, wherein the (c) alkaline agent is selected from the group consisting of an inorganic alkaline agent, an organic alkaline agent and mixtures thereof.

10. The composition according to claim 9, wherein the (c) alkaline agent is selected from the group consisting of ammonia; alkaline metal hydroxides; alkaline earth metal hydroxides; alkaline metal phosphates; monohydrogen phosphates; monoamines and derivatives thereof; diamines and derivatives thereof; polyamines and derivatives thereof; basic amino acids and derivatives thereof; oligomers of basic amino acids and derivatives thereof; polymers of basic amino acids and derivatives thereof; urea and derivatives thereof; and guanidine and derivatives thereof; and mixtures thereof.

11. The composition according to any one of claims 1 to 10 , wherein the amount of the

alkaline agent is from 0.1% to 10.0% by weight, preferably 1% to 7% by weight, and more preferably 2% to 5% by weight, relative to the total weight of the composition.

12. The composition according to any one of claims 1 to 11, wherein the amount of the

inorganic alkaline agent is from 0.1 % to 9.9% by weight, preferably 1% to 7% by weight, and more preferably 2% to 5% by weight, or the amount of the organic alkaline agent is from 1.1% to 10% by weight, preferably 1.5% to 7% by weight, and more preferably 2% to 5% by weight, relative to the total weight of the composition.

13. The composition according to any one of claims 1 to 12, which does not comprise any reducing agent or comprises less than 1% by weight, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight of a reducing agent, relative to the total weight of the composition.

14. The composition according to any one of claims 1 to 13, wherein the composition further comprises (d) at least one organic acidic agent having a pKa value of from 0.5 to 3.5, preferably selected from amino acids, aminosulfonic acids and mixtures thereof.

15. The composition according to any one of claims 1 to 14, wherein the (a) fatty material, the (b) at least one surfactant and the (c) at least one alkaline agent are comprised in two or more separate compositions, preferably the (a) at least one fatty material and the (b) at least one surfactant are comprised in one composition, and the (c) at least one alkaline agent is comprised in another composition.

16. A kit comprising a composition according to any one of claims 1 to 15 and instructions for use.

17. A process for reshaping keratin fibers, preferably hair, comprising the steps of:

applying a composition according to any one of claims 1 to 15 to keratin fibers, heating the keratin fibers to a temperature between 45°C to 250°C

rinsing and drying the keratin fibers.

18. The process according to Claim 17, further comprising the step of rinsing the keratin

fibers after the step of applying the composition onto the keratin fibers and before heating the keratin fibers.

19. The process according to Claim 17 or 18, further comprising the step of providing the keratin fibers with mechanical tension, preferably by using a reshaping means selected from the group consisting of a curler, a roller, a clip, a plate and an iron.

20. The process according to any one of Claims 17 to 19, wherein the process does not

comprise a step of placing the keratin fibers in an occlusive space.

21. The process according to any one of Claims 17 to 20, wherein the keratin fibers are

heated at a temperature ranging from 60°C to 150°C, preferably ranging from 60°C to 90°C during the step of heating the keratin fibers.