Patent Application
20080124294
The present invention relates to novel amphoteric polysaccharide compounds containing sulfonate function(s), to their use in cosmetics and to compositions comprising them.
In the cosmetics field, it is especially sought to improve the cosmetic properties of keratin materials, such as the hair and the skin, and more particularly sensitized hair, i.e. hair that has become damaged or embrittled, especially due to the chemical action of atmospheric agents and/or of hair treatments such as permanent-waving, dyeing or bleaching.
With this aim, it is common practice to use complementary cosmetic agents known as conditioning agents, for example cationic polymers or silicones, which are intended mainly to repair or limit the harmful or undesirable effects induced by the various treatments or attacking factors to which hair fibres are more or less repeatedly subjected. These conditioning agents also improve the cosmetic behaviour of natural hair.
Other conditioning agents, such as the amphoteric polysaccharides described in documents U.S. Pat. No. 4,803,071, U.S. Pat. No. 4,464,523, WO 90/03779 and FR 2 883 599 may be used in cosmetic hair compositions. However, these polysaccharides are not very efficient as regards conditioning and remanence.
The Applicant has found that, after several uses, the hair becomes laden and lacks lightness.
The Applicant has thus found, surprisingly and unexpectedly, novel amphoteric polysaccharide compounds containing sulfate function(s), which, when used in cosmetics, make it possible to overcome the drawbacks described above and to obtain excellent cosmetic properties such as an excellent conditioning and protecting effect on the hair, good disentangling of the hair, good hold and good discipline of the hairstyle. In addition, the use of these amphoteric polysaccharide compounds containing sulfonate function(s) leads to good remanence of these properties, even after washing the hair several times, without observing an excessive deposit that would lead to laden, non-maleable and non-supple hair.
These conditioning agents also give the skin cosmetic properties such as good moisturization.
One subject of the present invention is thus novel amphoteric polysaccharide compounds containing sulfonate function(s) as described below.
A second subject of the invention consists of a use of such a polysaccharide compound in cosmetics and especially for the cosmetic treatment of keratin materials, such as caring for and protecting the hair, hairstyling, permanent-waving, relaxing, dyeing or bleaching the hair, or alternatively cleansing and care of the skin, or makeup of the skin, the lips or the nails.
A subject of the invention is also a cosmetic composition comprising at least one polysaccharide compound according to the invention, in a cosmetically acceptable medium.
Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the various examples that follow.
The amphoteric polysaccharide compounds containing sulfonate function(s) according to the invention bear, as substituents other than the sulfonate functions, at least one anionic group and at least one cationic group, the said groups being linked to the polysaccharide chain via the oxygen atoms of the saccharide units.
The amphoteric polysaccharide compounds containing sulfonate function(s) according to the invention may be represented by formula (I) below:
in which:
The term “degree of substitution DS(−)1 of the amphoteric polysaccharide compounds” according to the invention means the ratio of the number of hydroxyl groups substituted with an anionic group —CO2V and/or —PO3V2 in the repeating unit to the number of elementary monosaccharides constituting the unit.
The term “degree of substitution DS(−)2 of the amphoteric polysaccharide compounds” according to the invention means the ratio of the number of hydroxyl groups substituted with a sulfonic or sulfonate group in the repeating unit to the number of elementary monosaccharides constituting the unit.
The term “degree of substitution DS(+) of the amphoteric polysaccharide compounds” according to the invention means the ratio of the number of hydroxyl groups substituted with a cationic group in the repeating unit to the number of elementary 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, a dextran, a furcellaran, a gellan gum, a gum arabic, a gum tragacanth, a hyaluronic acid, a konjac mannan, a lignin sulfonate, a carob gum, a partially N-acetylated chitin, a pectin, a polydextrose, a rhamsan 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 hydroxyethyl starch, a hydroxypropyl starch, an inulin, a guar gum, a carboxymethylguar gum, a carboxymethylhydroxypropylguar gum, a hydroxyethylguar gum, a hydroxypropylguar gum or a xanthan gum.
The polysaccharide chain containing sulfonate function(s) preferably has a weight-average molecular mass within the range from 500 to 15 000 000 and better still from 1 000 to 10 000 000.
Examples of linear or branched, saturated or unsaturated C1-C12 and preferably C1-C8 divalent hydrocarbon-based groups X, Y, Z or A that may especially be mentioned include linear or branched C1-C8 alkylene groups, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, hexylene or octylene; linear or branched C2-C8 alkylene groups, such as vinylene, allylene, crotonylene, butenylene, isobutenylene, tert-butenylene, hexenylene or octenylene. These groups may also bear at least one hydroxyl substituent and/or may comprise at least one ether and/or amine function in the alkylene or alkenylene chain.
Examples of linear or branched, saturated or unsaturated C1-C8 and preferably C1-C4 monovalent hydrocarbon-based groups R1 that may especially be mentioned include linear or branched C1-C4 alkyl groups, such as methyl, 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; the said groups possibly bearing at least one hydroxyl substituent and possibly comprising at least one ether and/or amine function in the alkyl or alkenyl chain.
Examples of R2 to R7 that may especially be mentioned include linear or branched C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl groups, and linear or branched C12-C18 alkyl groups, such as lauryl, myristyl, cetyl or stearyl groups. Examples of linear or branched C2-C18 and preferably C2-C6 alkenyl groups that may especially be mentioned include vinyl, allyl, crotonyl and butenyl groups.
The amphoteric polysaccharide compounds that are most particularly preferred in the invention are those corresponding to formula (I) in which:
The amphoteric polysaccharide compounds containing sulfonate function(s) as described above may be used in cosmetics, as conditioning agents, and especially for the cosmetic treatment of keratin materials, such as caring for and protecting the hair, hold and discipline of the hairstyle, but also for cleansing and caring for the skin and for making up the skin, the lips and the nails.
A subject of the present invention is also a cosmetic composition comprising, in a cosmetically acceptable medium, at least one amphoteric polysaccharide compound containing sulfonate function(s) according to the invention, preferably in an amount ranging from 0.01% to 50% by weight and better still from 0.03% to 25% by weight relative to the total weight of the composition.
The term “cosmetically acceptable medium” means a medium that is compatible with any keratin material, such as the skin, the hair, the nails, the eyelashes, the eyebrows and the lips and any other area of body or facial skin.
The cosmetically acceptable medium may consist solely of water or of a mixture of water and of a cosmetically acceptable solvent such as a C1-C4 lower alcohol, such as ethanol, isopropanol, tert-butanol or n-butanol; alkylene polyols, for instance propylene glycol; polyol ethers; and mixtures thereof.
The composition according to the invention may also comprise one or more standard additives that are well known in the art, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, anionic, cationic, nonionic, amphoteric or zwitterionic polymers, thickeners, nacreous agents, opacifiers, UV-screening agents, fragrances, mineral, plant and/or synthetic oils, fatty acid esters, dyes, volatile or non-volatile, organomodified or non-organomodified, cyclic or acyclic, branched or unbranched silicones, mineral or organic, natural or synthetic particles, preserving agents and pH stabilizers.
A person skilled in the art will take care to select the optional additives and the amount thereof such that they do not harm 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 rinse-out or leave-in application.
The compositions in accordance with the invention may be used as hair products, especially rinse-out or leave-in products, and in particular for washing, caring for and/or conditioning the hair, holding the hairstyle, and shaping, dyeing, bleaching, permanently reshaping or relaxing the hair.
The compositions of the invention may also be used as care or hygiene products such as protective, treating or care creams for the face, the hands or the body, protective or care body milks, gels or mousses for caring for or cleansing the skin, or alternatively as products for making up or for removing makeup from the skin, the lips, the nails and the eyelashes.
The examples presented below are given as illustrations of the present patent application.
The sulfonation and then quaternization of a sodium salt of carboxymethylcellulose is performed.
57 g of sodium salt of carboxymethylcellulose with a DS of 0.6-0.95, sold by the company Fluka, are dispersed with vigorous stirring in 200 ml of anhydrous 1,4-dioxane.
1.2 g (50 mmol) of sodium hydride are added portionwise. The mixture is refluxed (99-100° C.) for 2 hours.
The mixture is allowed to cool until the temperature is 80° C., and 6.1 g (50 mmol) of 1,3-propanesultone predissolved in 50 ml of anhydrous dioxane are then rapidly introduced. The mixture is refluxed for a further 5 hours.
After cooling to room temperature, a beige-coloured powder is collected by filtration, and reslurried 3 times in dioxane and dried under vacuum at 50° C. 59.3 g of product are obtained.
All of the sulfonated product is dispersed in 500 ml of acetonitrile and 0.5 ml of 50% sodium hydroxide solution.
9.7 g of aqueous 78% 2,3-epoxypropyltrimethylammonium chloride solution (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 reslurried twice in 200 ml of acetonitrile: the acetonitrile penetrates the gum and allows certain impurities to be extracted, which are then removed by suction-filtering the gum, this operation being repeated twice. The product is dried under vacuum at 50° C.
A shampoo was prepared using the following ingredients, the amounts of which are given as weight percentages of active material relative to the total weight of the composition:
A conditioner was prepared using the following ingredients, the amounts of which are given as weight percentages of active material relative to the total weight of the composition:
Dye compositions were prepared using the following ingredients, the amounts of which are given as weight percentages of active material relative to the total weight of the composition:
At the time of use, each dye composition described above was mixed weight-for-weight with a 20-volumes hydrogen peroxide solution (6% by weight).
The mixtures thus prepared were applied for 30 minutes to locks of natural or permanent-waved grey hair containing 90% white hairs. 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 the Examples 4 to 6.
Another dye composition was prepared using the following ingredients, the amounts of which are given as weight percentages of active material relative to the total weight of the composition:
This composition is mixed at the time of use with an oxidizing composition in emulsion form containing as oxidizing agent 7.5% hydrogen peroxide, in a proportion of 1 part by weight of dye composition per 1.5 parts by weight of oxidizing composition. The mixture obtained is applied to locks of natural hair containing 90% white hairs, and is left to act for 30 minutes. After rinsing, washing with shampoo and drying, hair dyed in a strong coppery-red light-chestnut shade is obtained.
The following compositions were prepared, the percentages indicated being weight percentages relative to the total weight of the composition:
The hair was then dye in a strong light-chestnut shade.
Another dye composition was prepared using the following ingredients, the amounts of which are given as weight percentages of active material relative to the total weight of the composition:
| Number | Date | Country | Kind |
|---|---|---|---|
| 04/08996 | Aug 2004 | FR | national |
| 60612178 | Sep 2004 | US | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/09991 | 8/19/2005 | WO | 00 | 9/18/2007 |
