FR2874380A1 - New amphoteric polysaccharide compound containing sulfonate function(s) useful in cosmetics as conditioning agent; for caring and for protecting the hair; and for making up the skin, lips and the nails - Google Patents

Abstract

An amphoteric polysaccharide compound containing sulfonate function(s) is new. An amphoteric polysaccharide compound containing sulfonate function(s) of formula (An-X-O) n-P(O-Z-Sulfo) p-(O-(Y) r-CAT) m(I) is new. P : a polysaccharide chain; X, Y and Z : a linear or branched, optionally saturated, optionally hydroxylated divalent 1-12C hydrocarbon-based group optionally comprising at least one ether and/or amine function in the hydrocarbon-based chain; or a group of formula -Si(R) 2-(O-Si(R) 2) q-A- (where the Si is attached to the O in the group An-X-O-, CAT-(Y) r-O- or Sulfo-Z-O-); R : R 1or OR 1; R 1linear or branched, optionally saturated, optionally hydroxylated 1-8C monovalent hydrocarbon-based group optionally comprising at least one ether and/or amine function in the hydrocarbon-based chain; q : 0 - 10; A : a linear or branched, optionally saturated, optionally hydroxylated 1-12C divalent hydrocarbon-based group optionally comprising at least one ether and/or amine function in the hydrocarbon-based chain; r : 0 or 1; An : anionic group of formula -C(O)-O-V or -P(O)(O-V) 2; V : H or alkali metal or alkaline-earth metal; CAT : an ammonium group of formula -N +>(R 2)(R 3)(R 4) Q ->, or a cationic polymer chain obtained by grafting and polymerization of ethylenic monomers bearing an ammonium group (a); R 2- R 4H or linear or branched, optionally saturated, optionally hydroxylated 1-22C monovalent hydrocarbon-based group optionally comprising at least one ether and/or amine function in the hydrocarbon-based chain; Q ->mineral or organic anion; Sulfo : sulfonic or sulfonate group; n : an integer such that the degree of substitution of the polysaccharide compound with anionic group CO 2V and/or PO 3V 2is 0.01 - 1.5; m : an integer such that the degree of substitution of the polysaccharide compound with cationic group is 0.01 - 1.5; p : integer such that the degree of substitution of the polysaccharide compound with sulfonic or sulfonate group is 0.01 - 1.5 The oxygen atoms belong to at least one saccharide unit of P. Provided that when CAT is a cationic polymer chain obtained by grafting and polymerization of ethylene monomers bearing an ammonium group then r is 0. An independent claim is included for a cosmetic composition (C1) comprising: (I) in a medium.

Description

(M_x_o) P (o- (YcAT) n m (I) o o

He He -C-O-V, -P-0-V,

O I V

  The present invention relates to novel amphoteric polysaccharide compounds with sulfonate function (s), their use in cosmetics and the compositions comprising them. BACKGROUND OF THE INVENTION The present invention relates to novel amphoteric polysaccharide compounds having a sulfonate function (s).

  In the field of cosmetics, one seeks in particular to improve the cosmetic properties of keratin materials, such as hair and skin, and more particularly sensitized hair, ie hair that is damaged or weakened, especially under the chemical action atmospheric agents and / or hair treatments such as permanent dyes or discolorations.

  For this purpose, it is usual to use complementary cosmetic agents known as conditioning agents, for example cationic polymers or silicones, intended mainly to repair or limit the harmful or undesirable effects induced by the various treatments or aggressions that are undergone, more or less repeated, the hair fibers. These conditioning agents also improve the cosmetic behavior of natural hair.

  Other conditioning agents, such as the amphoteric polysaccharides described in US 4,803,071, US 4,464,523, WO 90/03779 and FR 2,883,599, can be used in hair cosmetic compositions. However, these polysaccharides are not very effective in terms of conditioning and remanence.

  After several uses, the Applicant found that the hair was loaded and lacked lightness.

  She then surprisingly and unexpectedly found novel amphoteric polysaccharide compounds with sulfonate function (s) which, used in cosmetics, made it possible to overcome the disadvantages described above and to obtain excellent cosmetic properties such as an excellent effect. conditioner and hair protector, good hair disentangling, good posture and good hair discipline. In addition, the use of these amphoteric polysaccharide compounds with sulfonate function (s) leads to a good remanence of these properties, even after several washes of the hair, without observing too much deposit which would lead to hair loaded, non-malleable and non-flexible.

  These conditioning agents also give the skin cosmetic properties such as good hydration.

  The present invention therefore relates to novel amphoteric polysaccharide compounds with sulfonate function (s) as described below.

  A second subject of the invention consists of a use of such a polysaccharide compound in cosmetics and in particular for the cosmetic treatment of keratinous substances, such as the care and protection of the hair, the styling, the permanent, the straightening, the coloring. or discoloration, or cleaning and care of the skin, or make-up of the skin, lips or nails.

  It also relates to a cosmetic composition comprising at least one polysaccharide compound according to the invention, in a cosmetically acceptable medium.

  Other objects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the various examples which follow.

  The amphoteric polysaccharide compounds with sulfonate function (s) according to the invention have, as other substituents, only the sulphonate functional groups, at least one anionic group and at least one cationic group, said groups being linked to the polysaccharide chain via the dicarboxylic acid atoms. oxygen of the saccharide units.

  The amphoteric polysaccharide compounds with sulfonate function (s) according to the invention may be represented by the following formula (I): ## STR2 ## in which: the atoms of oxygen belong to one or more saccharide units of P, P represents a polysaccharide chain, X, Y and Z each represent, independently of one another: a linear or branched, saturated or unsaturated C1-C12 divalent hydrocarbon group optionally hydroxylated and optionally comprising at least one ether and / or amine function in the hydrocarbon chain, or - a group

R R 1 1

   If Si Si 1 RR q the silicon atom is attached to the oxygen atom in the group An-XO-, CAT- (Y), -O- or Sulfo ZO, where each R, identical or different, represents R1 or OR1, R, represents a monovalent C1-C8, preferably C1-C4, linear or branched hydrocarbon group, saturated or unsaturated, optionally hydroxylated and optionally comprising at least one ether and / or amine function in the hydrocarbon chain; , q represents an integer ranging from 0 to 10, preferably from 0 to 5, q = 0 being particularly preferred, and A represents a linear or branched, saturated or unsaturated, optionally hydroxylated C1-C12 hydrocarbon-based hydrocarbon group and comprising optionally at least one ether and / or amine function in the hydrocarbon chain, r is equal to 0 or 1, r being 0 when CAT represents a cationic polymer chain obtained by grafting and polymerization of ethylenic monomers carrying an amine group. monium, An represents an anionic group selected from

O O

  With V representing a hydrogen atom or an alkali or alkaline earth metal, for example, a sodium or potassium atom, CAT represents: - an ammonium group

Q R4

  wherein R2, R3 and R4 each independently represent a hydrogen atom or a C1-C22, preferably C1-C18, linear or branched, saturated or unsaturated, optionally hydroxylated monovalent hydrocarbon group; and optionally comprising at least one ether and / or amine function in the hydrocarbon chain, and Q- represents an inorganic or organic anion, for example a halogen atom such as a chlorine or bromine atom, the atom of chlorine being particularly preferred, or an acetate, a citrate, a lactate, an oleate or a behenate, or a cationic polymer chain obtained by grafting and polymerization of ethylenic monomers bearing an ammonium group, for example of the formula: R 5 R 6 R 7 in which R 5 R6 and R5 are each, independently of each other, a hydrogen atom, a C1-C22, preferably C1-C18, linear or branched alkyl group, or a C2-C22 alkenyl group; preferably in C 2-C18, linear or branched, Sulfo represents a sulphonate or sulphonate group, such as SO3V, V having the same meaning as above, n is such that the degree of substitution of the polysaccharide compound by an anionic group CO2V and / or PO3V2 (DS (-) 1), is in the range from 0.01 to 1.5, preferably from 0.05 to 1, m is such that the degree of substitution of the polysaccharide compound by a cationic group (DS (+)), is in the range from 0.01 to 1.5, preferably from 0.05 to 1, P is such that the degree of substitution of the polysaccharide compound by a sulfonic or sulfonate group (DS ( -) 2), is in the range from 0.01 to 1.5, preferably from 0.02 to 1, the total degree of substitution of the polysaccharide compound not exceeding 3, and preferably it is included in the range from 0.05 to 2.5.

  By degree of substitution DS (-) 1 of the amphoteric polysaccharide compounds according to the invention is meant the ratio of the number of hydroxyl groups substituted by an anionic group CO2V and / or PO 3 V 2 in the repeating unit to the number of elemental monosaccharides constituting the reason.

  By degree of substitution DS (-) 2 of the amphoteric polysaccharide compounds according to the invention is meant the ratio of the number of hydroxyl groups substituted by a sulfonic or sulphonate group in the repeating unit to the number of elemental monosaccharides constituting the unit.

  By degree of substitution DS (+) of the amphoteric polysaccharide compounds according to the invention is meant the ratio of the number of hydroxyl groups substituted by a cationic group in the repeating unit to the number of elemental monosaccharides constituting the unit.

  The polysaccharide chain represented by P is preferably a cellulose, a starch, an inulin, a guar gum, a xanthan gum, a pullulan, an agar-agar, a sodium, potassium or ammonium alginate, a carrageenan, dextran, furcellaran, gellan gum, acacia, tragacanth, hyaluronic acid, konjac mannan, lignin sulfonate, locust bean gum, partially N-actylated chitin, pectin, a polydextrose, a rhamsane gum or a welan gum.

  More preferably, the polysaccharide chain is a cellulose, a carboxymethylcellulose, a hydroxyethylcellulose, a hydroxypropylcellulose, a hydroxypropylmethylcellulose, a methylcellulose, a starch, a starch acetate, a hydroxyethylstarch, a hydroxypropylamidon, an inulin, a guar gum, a gum carboxymethylguar, carboxymethylhydroxypropyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, or xanthan gum.

  The sulfonate-functional polysaccharide chain preferably has a weight average molecular weight in the range of 500 to 15,000,000, more preferably 1,000 to 10,000,000.

  As examples of linear, branched, saturated or unsaturated C 1 -C 12, preferably C 1 -C 8 divalent hydrocarbon group X, Y, Z or A, there may be mentioned especially linear or branched C 1 -C 8 alkylene groups, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, hexylene or octylene; linear or branched C2-C8 alkenylene groups, such as vinylene, allylene, crotonylene, butenylene, isobutenylene, tert-butenylene, hexenylene or octenylene. These groups may also carry at least one hydroxy substituent and / or comprise at least one ether and / or amine function in the alkylene or alkenylene chain.

  As examples of linear or branched, saturated or unsaturated, C1-C8, preferably C1-C4, C1-C4 monovalent hydrocarbon radical, mention may especially be made of linear or branched C1-C4 alkyl groups, such as methyl or ethyl n-propyl, isopropyl, n-butyl or tert-butyl; linear or branched C2-C4 alkenyl groups, such as vinyl, allyl, crotonyl, butenyl, isobutenyl or tert-butenyl; said groups may carry at least one hydroxy substituent and include at least one ether and / or amine function in the alkyl or alkenyl chain.

  By way of examples of R 2 to R 7 there may be mentioned linear or branched C 1 -C 4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl groups, and alkyl groups. linear or branched C12-C18, such as lauryl, myristyl, cetyl or stearyl groups. As an example of a C2-C18 alkenyl group, preferably a C2-C6, linear or branched, there may be mentioned vinyl, allyl, crotonyl or butenyl groups.

  The amphoteric polysaccharide compounds most particularly preferred in the invention are those corresponding to the formula (I) in which: P represents a cellulose, a carboxymethylcellulose, a hydroxyethylcellulose, a hydroxypropylcellulose, a hydroxypropylmethylcellulose, a methylcellulose, a starch, an acetate of starch, hydroxyethyl starch, hydroxypropyl starch, inulin, guar gum, carboxymethylguar gum, carboxymethylhydroxypropyl guar gum, hydroxyethylguar gum, hydroxypropyl guar gum or xanthan gum, X, Y and Z represent each, independently of one another, a linear or branched C 1 -C 8 alkylene group, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, hexylene or octylene; or a linear or branched C2-C8 alkenylene group, such as vinylene, allylene, crotonylene, butenylene, isobutenylene, tert-butenylene, hexenylene or octenylene, or

R R

 If 0 - If A

R

  where each R, identical or different, represents R 1 or OR 1, R 1 represents a linear or branched C 1 -C 4 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl; or a linear or branched C2C4 alkenyl group, such as vinyl, allyl, crotonyl, butenyl, isobutenyl or tert-butenyl; q represents an integer ranging from 0 to 5, A represents a linear or branched C1-C8 alkylene group, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, tertbutylene, hexylene or octylene; or a linear or branched C2-C8 alkenylene group, such as vinylene, allylene, crotonylene, butenylene, isobutenylene, tert-butenylene, hexenylene or octenylene, r, An, CAT, Sulfo, m, n and p have the same meanings as those above, and R2 to R4, represent a hydrogen atom, a C1-4 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, or a C12 alkyl group; C18 such as lauryl, myristyl, cetyl or stearyl, or a linear or branched C 2 -C 6 alkenyl group such as vinyl, allyl, crotonyl or butenyl.

  The amphoteric polysaccharide compounds with sulfonate function (s) as described above may be used in cosmetics, as conditioning agents, and in particular for the cosmetic treatment of keratin materials, such as the care and protection of the hair, the maintenance and the discipline of the hair, but still for the cleaning and the care of the skin and the make-up of the skin, the lips and the nails.

  The subject of the present invention is also a cosmetic composition comprising, in a cosmetically acceptable medium, at least one amphoteric polysaccharide compound with sulfonate function (s) according to the invention, preferably in an amount ranging from 0.01 to 50% by weight. more preferably from 0.03 to 25% by weight relative to the total weight of the composition.

  By cosmetically acceptable medium is meant a medium compatible with all keratin materials such as skin, hair, nails, eyelashes and eyebrows, lips and any other area of the body and face.

  The cosmetically acceptable medium may consist solely of water or a mixture of water and a cosmetically acceptable solvent such as a lower alcohol C1-C4, such as ethanol, isopropanol, tertio butanol, n-butanol; alkylene polyols such as propylene glycol; polyol ethers; and their mixtures.

  The composition according to the invention may furthermore comprise one or more conventional additives well known in the art, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, anionic, cationic, nonionic, amphoteric or zwitterionic polymers. , thickening agents, pearlescent agents, opacifiers, UV filters, perfumes, mineral, vegetable and / or synthetic oils, fatty acid esters, dyes, volatile or nonvolatile silicones, organomodified or otherwise, cyclic or acyclic, branched or unbranched, inorganic or organic particles, natural or synthetic, preservatives and pH stabilizers.

  Those skilled in the art will take care to choose the possible additives and their amount so that they do not adversely affect the properties of the compositions of the present invention.

  These additives are generally present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

  The cosmetic compositions in accordance with the invention may be in the form of a mousse, a gel, a spray or a lacquer and may be used in rinsed or non-rinsed application.

  The compositions in accordance with the invention may be used as hair products, in particular rinsed or not rinsed, and in particular for washing, caring and / or conditioning the hair, maintaining the hairstyle, shaping the hair. , coloring, discoloration, permanent deformation or hair straightening.

  The compositions of the invention may also be used as care or hygiene products such as creams for protection, treatment or care for the face, for the hands or for the body, body care or protection milks. , lotions, gels or mousses for caring for or cleaning the skin, or as makeup or makeup removers of the skin, lips, nails and eyelashes.

  The examples given below are given as an illustration of the present application.

EXAMPLES

Example 1

  The sulfonation and the quaternization of a sodium salt of carboxymethylcellulose are carried out.

  Sulfonation 57 g of sodium salt of carboxymethylcellulose having a DS of 0.6 0.95, sold by Fluka, are dispersed with vigorous stirring in 200 ml of anhydrous 1,4-dioxane.

  1.2 g (50 mmol) of sodium hydride are added in small portions. Refluxed (99-100C) for 2 hours.

  The mixture is allowed to cool until the temperature is at 80 ° C., and then 6.1 g (50 mmol) of 1,3-propane-sultone dissolved in 50 ml of anhydrous dioxane are rapidly introduced. Refluxed again for 5 hours.

  After cooling to room temperature, a beige powder is recovered by filtration, which is re-saturated 3 times with dioxane and dried in vacuo at 50 ° C., giving 59.3 g of product.

  Quaternization The whole of the sulfonated product is dispersed in 500 ml of acetonitrile and 0.5 ml of a 50% sodium hydroxide solution.

  9.7 g of a 78% aqueous solution of 2,3-epoxypropyltrimethylammonium chloride (50 mmol) are then introduced.

  The mixture is heated at 50 ° C. for 5 hours. After cooling to room temperature, a light brown powder is collected by filtration and re-sewed twice in 200 ml of acetonitrile: acetonitrile enters the gum and allows extract certain impurities which are then removed by spinning of the eraser, the manipulation is here repeated twice. It is dried under vacuum at C.

  EXAMPLE 2 Shampoo A shampoo was prepared from the following ingredients, the amounts of which are indicated in percent by weight of active ingredient relative to the total weight of the composition: sodium lauryl ether sodium (TEXAPON N702 from COGNIS) 12.5% Cocoylbetaine (DEHYTON AB 30 from GOLDSCHMIDT) 2.5% Dimethicone (DC200FLUID from Dow Corning) 2.0% Compound of Example 1 0.5% Cocamide Monoisopropanolamine 0.4% Carbomer 0.2% Preservative qs Fragrance qs Citric acid Example 3: Conditioner A conditioner was prepared from the following ingredients, the amounts of which are indicated in percent by weight of active ingredient relative to the total weight of the composition. : Behenyltrimethylammonium chloride (GENAMIN 1.2% KDMP from CLARIANT) PEG / PPG Dimethicone (GOLDSCHMIDT ABIL B8851) 0.5% Cyclopentasiloxane (Dow Corning 245 Fluid) 15.0% Compound of Example 1 1.0% Propylene Glycol 2.5% Preservative qs Perfume qs A citric acid / sodium hydroxide qs pH 6.5 Water qs 100

Examples 4-6

  The dyeing compositions were prepared from the following ingredients, the amounts of which are indicated in percent by weight of active ingredient relative to the total weight of the composition: Ex.4 Ex.5 Ex. 6 Paraphenylenediamine 0.240, 24 0.24 Para-aminophenol 0.44 0.44 0.44 2-aminophenol. 0.028 0.028 0.028 1,3-dihydroxybenzene 0.192 0.192 0.192 3-aminophenol 0.019 0.019 0.019 5-N- (3-hydroxyethyl) amino-2-methylphenol 0.021 0.021 0.021 1,3-dihydroxy-2-methylbenzene 0.055 0.055 0.055 Anhydrous sodium metasilicate 2 2 2 Monoethanolamine 5.45 5.45 5.45 Reducer, antioxidant, sequestering, fragrance qs qs qs

  Propylene Glycol Crosslinked Acrylic Acid Polymer 0.4 0.4 0.4 Compound of Example 1 1.5 1.5 2.8 Cationic Polymer: Hexadimethrin 3 3-Chloride (CTFA Name) Mexomer PO sold by CHIMEX Sodium Lauryl Sulfate Powder 3 - - Lauryl alcohol oxyethylenated at 12 moles - 7.5 7.5 ethylene oxide Oleocetyl alcohol oxyethylenated at 30 moles - 4 4 ethylene oxide Decyl alcohol oxyethylenated 3 moles 10 10 10 ethylene oxide Decyl alcohol oxyethylenated at 5 moles 8 - ethylene oxide Lauric acid 2.5 2.5 2.5 Cetyl stearyl alcohol 50/50 11.5 11.5 11.5 Agent pearlescent agent: Hydrophobic fumed silica 1,2 1,2 1, 2 Nacreous agent: Glycerol monostearate 2 2 2 Demineralized water 100 100 100 At the time of use, weight for weight was mixed, each dye composition described above with a solution of hydrogen peroxide at 20 volumes (6% by weight).

  The mixtures thus produced were applied for 30 minutes to locks of natural gray hair or permed with 90% of whites. The locks were then rinsed, washed with a standard shampoo, rinsed again and then dried.

  The hair was dyed in a golden blond shade for each of Examples 4 to 6.

Example 7

  Another dyeing composition was prepared from the following ingredients, the amounts of which are indicated in percent by weight of active ingredient relative to the total weight of the composition. Mixture of C18 to C24 linear alcohols (C18 / C20 / C22 / C24: 7/57/30/6 alcohol content> 95%) Oxyethylenated stearyl alcohol (2 moles of ethylene oxide) 4.5 Oxyethylenated stearyl alcohol (21 moles of ethylene oxide) 1.75 Acid oleic 2,6 Cationic polyurethane obtained by the condensation of 1,3 bis 0,2 (isocyanatomethylcyclohexane), N, N-dimethylethanolamine quaternized with bromododecane, N, N-dimethylethanolamine and polyoxyethylene of molecular weight Polyacid acrylic) crosslinked (product marketed under the trademark Carbopol 980 by the company Novéon) Hydroxypropyl-methylcellulose 0.2 Monoisopropanolamide of coprah acids 3 Merquat 100 in 40% aqueous solution 1.6 Compound of Example 1 2 Metabisulphite odium 0.71 EDTA (ethylenediamine tetraacetic acid) 0.2 Tert-butylhydroquinone 0.3 1,4-diaminobenzene 0.2 Para-aminophenol 1,2 1,3-dihydroxybenzene 0.1 1-hydroxy-3-aminobenzene 0.2 1-methyl-2-hydroxy-4- (3-hydroxyethylaminobenzene) 0.8 Monoethanolamine 1 Ammonia at 20% NH3 11 Parfum qs Demineralized water qs 100 This composition is mixed at the time of use with an oxidizing composition under emulsion form containing 7.5% of hydrogen peroxide as oxidizing agent at a proportion of 1 part by weight of dye composition for 1.5 parts by weight of oxidizing composition. The resulting mixture is applied to strands of natural hair with 90% of whites and left for 30 minutes. After rinsing, washing with shampoo and drying, we obtain dyed hair in a sustained shade light brown red copper.

Example 8

  The following compositions were prepared, the percentages indicated being by weight relative to the total weight of the composition: Oxidizing composition: Fatty alcohol 2.3% Fatty alcohol oxyethylenated 0.6% Fatty amide 0.9% Glycerin 0.5% Peroxide of hydrogen 7.5% perfume qs Demineralized water qs 100% Coloring composition: Mixture of C18 to C24 linear alcohols [C18 / C20 / C22 / C24, 7/58/30/6, content of alcohols> 95%] (NAFOL 20-22) 3% Mixture of C18 to C24 linear alcohols [C18 / C20 / C22 / C24, 7/58/30/6, content of oxyethylenated alcohols> 95%] (30 moles of oxide 1, 35% ethylene) (NAFOLOX 20-22) Oxyethylenated stearyl alcohol (2 moles ethylene oxide) 4% oxyethylenated stearyl alcohol (21 moles oxide 2% ethylene) Oleic acid 2,6% Distearate glycol 2% Propylene glycol 5% Monoisopropanolamide of coconut acids 2% Aculyn 44 sold by the company Rohm & Haas 1.4% MA * Poly (acrylic acid) crosslinked 0.6% Compound of Example 1 3% MA * Merqua t 100 sold by Calgon 0, 4% MA * Reducers 0.7% Sequestering agents 0.2% 1,3-dihydroxybenzene (resorcinol) 0.6% 1,4-diaminobenzene 0.5% 1-hydroxy-3- aminobenzene 0.1% 1-hydroxy-2-aminobenzene 0.05% 1-hydroxy-4-aminobenzene 0.09% 6-hydroxy-benzomorpholine 0.017% 1- (3-hydroxyethyloxy-2,4-diaminobenzene, 0.039% dihydrochloride Propylene glycol monobutyl ether 2.5% Pure monoethanolamine 1.06% Ammonia (20.5% ammonia) 11.1% Water qs 100% MA * = Active material The coloring composition was mixed at the time of use in a plastic bowl and for 2 minutes, to the oxidizing composition given above, at a rate of 1 part of dye composition for 1.5 parts of oxidizing composition.

  The resulting mixture was applied to locks of natural hair at 90% white and left for 30 minutes.

  The locks were then rinsed with water, washed with shampoo, rinsed again with water and then dried and disentangled.

  The hair was then dyed in a powerful light brown shade.

Example 9

  Another dyeing composition was prepared from the following ingredients, the amounts of which are indicated in percent by weight of active ingredient relative to the total weight of the oleocetyl alcohol composition oxyethylenated with 30 moles of oxide 7% ethylene (nCA = 17 HLB = 16.5) Lauryl alcohol (C12-C14 / 55-45%) oxyethylenated with 12 8% moles of ethylene oxide (nCA = 12.5 - HLB = 14) Cetylstearyl alcohol (C16 / C1850 / 50) (nCB = 17-5% HLB = 1) Decyl alcohol (C10-C12-C14 / 85-8.5-6.5) oxyethylenated at 22% 3.5 moles of ethylene oxide, sold under the denomination MERGITAL BL 309 by the company HENKEL (nCB = 10.4 - HLB = 8.5) Copolymer of diallyldimethylammonium chloride and 3% MA of acrylic acid, sold under the name MERQUAT 280 by the company CALGON at 35% of MA Compound of Example 1 1% Poly (acrylic acid) crosslinked sold under the name 0.4% CARBOPOL 934 (MW 3,000,000) by the Company

GOODRICH

  Propylene Glycol 8% Monoethanolamine 8.3% Hydroquinone 0.1% 1-phenyl-3-methyl-5-pyrazolone 0.1% Aqueous solution of sodium bisulfite at 35% MA 1.3% Para-phenylenediamine 0.5% m-dihydroxybenzene 0, 4% Perfume, sequestering qs Water qs 100% pH = 11.0 MA: Active matter

Claims (24)

  1. Amphoteric polysaccharide compound with sulfonate function (s) corresponding to formula (I): (M-x-o) n P (O (Y-) CAT) m IO Z   Sulfo / p (I) in which: the oxygen atoms belong to one or more saccharide units of P, P represents a polysaccharide chain, X, Y and Z each represent independently of each other: a hydrocarbon group divalent C1-C12, linear or branched, saturated or unsaturated, optionally hydroxylated and optionally comprising at least one ether and / or amine function in the hydrocarbon chain, or a group R R 1 1    If 0 Si A 1 1 R 1 R q the silicon atom being attached to the oxygen atom in the group An-XO-, CAT- (Y) rO- or Sulfo ZO, where each R, identical or different , represents R1 or OR1, R1 represents a linear or branched, saturated or unsaturated, optionally hydroxylated, C1-C8 monovalent hydrocarbon group and optionally comprising at least one ether and / or amine function in the hydrocarbon chain, q represents an integer ranging from 0 to 10, and A represents a divalent C1-C12 hydrocarbon group, linear or branched, saturated or unsaturated, optionally hydroxylated and optionally comprising at least one ether and / or amine function in the hydrocarbon chain, r is equal to 0 or 1, r being 0 when CAT represents a cationic polymer chain obtained by grafting and polymerization of ethylenic monomers carrying an ammonium group, An represents an anionic group chosen from O O Il II  C O V, P 0 V, O V   with V representing a hydrogen atom or an alkali or alkaline earth metal atom, CAT represents: - an ammonium group R2 N + R3 Q-R4 where R2, R3 and R4 each represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated, optionally hydroxylated, C1-C22 monovalent hydrocarbon group optionally comprising at least one ether and / or amine functional group in the hydrocarbon chain, and Q represents an inorganic or organic anion or a cationic polymer chain obtained by grafting and polymerizing ethylenic monomers carrying an ammonium function, Sulfo represents a sulphonate or sulphonate group, n is such as the degree of substitution of the polysaccharide compound by an anionic group CO2V and / or PO 3 V 2, is in the range from 0.01 to 1.5 m is such that the degree of substitution of the polysaccharide compound by a cationic group is included in the range from 0.01 to 1.5, is such that the degree of polysaccharide substitution by a sulfonic or sulfonate group is in the range of 0.01 to 1.5, the degree of total substitution polysaccharide compound not exceeding 3.   2. amphoteric polysaccharide compound according to claim 1, characterized in that P represents a cellulose, a starch, an inulin, a guar gum, a xanthan gum, a pullulan, an agar-agar, a sodium alginate, of potassium or ammonium, carrageenan, dextran, furcellaran, gellan gum, acacia, tragacanth, hyaluronic acid, konjac mannan, lignin sulfonate, locust bean gum, partially N chitin - actylated, pectin, polydextrose, rhamsane gum or welan gum.   3. amphoteric polysaccharide compound according to claim 2, characterized in that P represents a cellulose, a carboxymethylcellulose, a hydroxyethylcellulose, a hydroxypropylcellulose, a hydroxypropylmethylcellulose, a methylcellulose, a starch, a starch acetate, a hydroxyethylstarch, a hydroxypropyl starch, a inulin, guar gum, carboxymethylguar gum, carboxymethylhydroxypropyl guar gum, P   hydroxyethyl guar gum, hydroxypropyl guar gum or xanthan gum.   4. Amphoteric polysaccharide compound according to any one of the preceding claims, characterized in that the divalent hydrocarbon group X, Y, Z or A, C 1 -C 12 is chosen from linear or branched C 1 -C 8 alkylene groups, and linear or branched C2-C8 alkenylene groups optionally bearing at least one hydroxyl group and / or possibly comprising at least one ether and / or amine function in the alkylene or alkenylene chain.   Amphoteric polysaccharide compound according to Claim 4, characterized in that the divalent C 1 -C 12 hydrocarbon group is chosen from methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, hexylene, octylene and vinylene groups. allylene, crotonylene, butenylene, isobutenylene, tert-butenylene, hexenylene and octenylene.   Amphoteric polysaccharide compound according to any one of the preceding claims, characterized in that R1 represents a linear or branched C1-C4 alkyl group, or a linear or branched C2-C4 alkenyl group.   7. amphoteric polysaccharide compound according to claim 6, characterized in that R1 is chosen from methyl, ethyl, npropyl, isopropyl, n-butyl, tert-butyl, vinyl, allyl, crotonyl, butenyl, isobutenyl or tert-butenyl groups.   An amphoteric polysaccharide compound according to any one of the preceding claims, characterized in that Q represents a halogen atom, an acetate, a citrate, a lactate, an oleate or a behenate.   Amphoteric polysaccharide compound according to any one of the preceding claims, characterized in that R2, R3 and R4 each represent, independently of one another, a hydrogen atom, a linear C 1 -C 4 alkyl group or branched, linear or branched C12 -C18 alkyl, or linear or branched C2-C6 alkenyl group.   Amphoteric polysaccharide compound according to Claim 9, characterized in that R2, R3 and R4 each represent, independently of one another, a hydrogen atom, a methyl, ethyl, n-propyl, isopropyl or n-butyl group. , tert-butyl, lauryl, myristyl, cetyl, stearyl, vinyl, allyl, crotonyl or butenyl.   Amphoteric polysaccharide compound according to any one of the preceding claims, characterized in that the ethylenic monomers bearing an ammonium group have the formula: R5 N R6 R7 in which R5, R6 and R, each independently represent one of the other, a hydrogen atom, a linear or branched C1-C22 alkyl group, or a linear or branched C2-C22 alkenyl group.   Amphoteric polysaccharide compound according to Claim 11, characterized in that R5, R6 and R3 each represent, independently of one another, a hydrogen atom, a linear or branched C1-C4 alkyl group, an linear or branched C12-C18 alkyl group, or a linear or branched C2-C6 alkenyl group.   Amphoteric polysaccharide compound according to claim 12, characterized in that R5, R6 and R5 are each, independently of one another, a hydrogen atom, a methyl, ethyl, n-propyl or isopropyl group. butyl, tert-butyl, lauryl, myristyl, cetyl, stearyl, vinyl, allyl, crotonyl or butenyl.   14. Use of at least one amphoteric polysaccharide compound with sulfonate function (s) according to any one of the preceding claims, in cosmetics, as a conditioning agent.   15. Use according to claim 14, for the cosmetic treatment of keratin materials.   16. Use according to claim 15, for care and hair protection.   17. Use according to claim 15, for cleaning and care of the skin.   18. Use according to claim 15, for the makeup of the skin, lips and nails.   19. Cosmetic composition comprising in a cosmetically acceptable medium at least one amphoteric polysaccharide compound with sulfonate function (s) according to any one of claims 1 to 13.   20. Cosmetic composition according to claim 19, characterized in that it comprises said amphoteric polysaccharide compound with sulfonate function (s) in an amount ranging from 0.01 to 50% by weight relative to the total weight of the composition.   21. Cosmetic composition according to claim 20, characterized in that it comprises said amphoteric polysaccharide compound with sulfonate function (s) in an amount ranging from 0.03 to% by weight relative to the total weight of the composition.   22. Cosmetic composition according to any one of claims 19 to 21, characterized in that the cosmetically acceptable medium comprises water or a mixture of water and at least one organic solvent.   23. Cosmetic composition according to claim 22, characterized in that the organic solvent is selected from C1-C4 lower alcohols, alkylene polyols, polyol ethers, and mixtures thereof.   24. Cosmetic composition according to any one of claims 19 to 23, characterized in that it comprises at least one additive selected from anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, anionic, cationic, non-ionic polymers. ionic, amphoteric or zwitterionic, thickening agents, nacrants, opacifiers, UV filters, perfumes, mineral, vegetable and / or synthetic oils, fatty acid esters, dyes, volatile or non-volatile silicones, organomodified or not, cyclic or acyclic, branched or unbranched, mineral or organic particles, natural or synthetic, preservatives and pH stabilizers.