CA2307321A1 - Use of substantially amorphous cellulose nanofibrils associated with a polyhydroxylated organic compound in cosmetic formulations - Google Patents

Abstract

The invention concerns the use of substantially amorphous cellulose nanofibrils having a crystalline index not more than 50 % in dispersible dry form associated with at least a polyhydroxylated (polyOH) organic compound, as texturizing and/or reinforcing agent in cosmetic formulations. The invention further concerns the resulting cosmetic formulations.

Description

USE OF ESSENTIALLY CELLULOSE NANOFIBRILLES
AMORPHS ASSOCIATED WITH AT LEAST ONE ORGANIC COMPOUND
POLYHYDROXYL IN COSMETIC FORMULATIONS
The present invention relates to the use of nanofibrils of cellulose essentially amorphous with a lower or equal rate of crystallinity at 50 in a form dispersible in cosmetic formulations and formulations thus obtained.
The present invention more specifically relates to a new texturing agent andlou reinforcement for cosmetic formulations.
For the purposes of the invention, the term “cosmetic formulation” means all of the products or cosmetic preparations of the type described in annex I
("Illustrative list by category of cosmetic products"} of the directive European n °
76I7681CEE of July 25, 1976, known as the Cosmetic Directive.
In general, the cosmetic compositions are formulated in the form of a large number of type of products intended to be applied either on the hair, such as mousses, gels (especially styling), conditioners, formulations for styling or to facilitate combing and / or detangling of hair, the rinsing formulas, either on the skin like hand lotions and body the products regulating the hydration of the skin, toilet milks, compositions make-up removers, depilatory products, protective creams or lotions against the sun and ultraviolet radiation, care creams, preparations anti-acne, local analgesics, make-up formulations like mascaras, funds complexion, nail polish products intended to be applied to the lips or other mucous membranes, sticks, solid compositions such as toilet soap as well as other formulations of the same type.
Conventionally, these different formulations incorporate, in addition to one or more active ingredients specific to the intended application, a number of so-called compounds more conventional which have the particular function of giving them either a stability prolonged in time (preservative for example) and / or a form galenic particular (such as gel, cream, milk, lotion for example). So general, this is surfactants and / or dispersants, stabilizers, emulsifiers, humectants, gelling or thickening.
As a representative of conventional stabilizers and / or thickeners we can in particular mention the crosslinked polyacrylates, the hydrocolloids obtained by fermentation like Xanthane-Rhodicare gum ~ and a succinoglycan such as Rheozan ~, the cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose, the guars and their derivatives which are used alone or in combination.

WU 99! 20241 PCT / FR98102031

2 The object of the present invention is to propose a new texturing agent and of reinforcement with an advantageous behavior in rheological terms for formulate cosmetic compositions. More specifically, he is an agent base of cellulose nanofibrils, essentially amorphous with a rate of crystallinity less than or equal to 50%, in a dry form dispersible in middle aqueous.
In general, native cellulose always occurs in a form fibrillar. These fibrils are well known materials which are in particular already proposed to modify the texture of the environments in which they are introduced. In in the case of fluid media, they modify their viscosities or even their rheological profits.
The nanofibrils can be of various origins, for example of origin vegetable, bacterial, fungal, amoebic ...
In general, in the fibers or plant walls there is a strong association between nanofibrils. Among the walls we can distinguish the secondary walls, issues mainly wood, primary walls of which a typical example is the parenchyma. Examples of parenchyma are constituted by the pulp of beet sugar, citrus (lemons, oranges, grapefruits} and most fruit and vegetables. In the secondary walls, these shells are organized in the form of very oriented sheets thus forming an inseparable fiber. They present conventionally in the form of aggregates of a few tens of manometers to a few micrometers. These aggregates are made up of elementary fibrils who does not cannot be entangled, during their homogenization, without causing their break.
In the context of the present invention, the cellulose fibrils considered are cellulose nanofibrils (NFC} which are essentially amorphous from preference of cells with primary walls.
Advantageously, the cellulose nanofibrils of the invention come from cells made up of at least about 80% primary walls, and preference of at minus 85% by weight.
Thus, essentially amorphous cellulose nanoparticles used according to the invention, preferably have at least 80% of cells with walls primary.
In contrast to the secondary wall cellulose fibrifles discussed above above, the cellulose nanoparticles have a diameter of at most a few pressure gauges and have the appearance of filaments which are detangled during the stages homogenization.
Elies preferably have a section of between approximately 2 and approximately nm. More preferably, this is between approximately 2 and approximately 4 nm.
In the context of the invention, the nano ~ shines considered are nanofibrils say essentially amorphous as opposed to fibrils say crystalline.

3 By essentially amorphous, we mean to define nanofibrils whose rate of crystallinity is less than or equal to 50%. According to a particular variant of the current invention, this crystallinity rate is between 15% and 50% and more preferably less than 50%.
These essentially amorphous cellulose nanofibrils are particularly advantageous with regard to crystalline microfibrils in the sense that they are dispensable in aqueous media, confer good rheological properties specific rheofluidifying type and are stable whether thermally or in backgrounds to significant ionic charges. This demonstrated good efficacy, at dose reduced, by cellulose nanofibrils is actually a consequence of their excellent behaviour rheological in terms of flow threshold and shear thinning power.
According to a preferred embodiment of the invention, the cellulose nanofibrils used according to the invention are loaded at the surface with carboxylic acids and polysaccharides acids, alone or as a mixture.
By carboxylic acids is meant simple carboxylic acids, as well than their salts. These acids are preferably chosen from uronic acids and are more particularly galacturonic acid and / or glucuronic acid.
As acidic polysaccharides, mention may be made of pectins, of which more particularly polygalacturonic acids. These acidic polysaccharides can be present in mixture with hemicelluloses.
In fact, these surface-charged nanofibrils are not the result of a simple mixture between said nanofibrils and acids and polysaccharides. II
rather it is a close combination between these two types of compounds derived directly from process used to prepare nanofibrils. Indeed, this preparation process may be such that acids and polysaccharides are not completely separated from fibers But remain on the surface of the latter, giving them properties well specific. It is important to emphasize that these same properties will not not reproduced if one proceeds successively to a complete separation of nanofibrils of these acids and / or polysaccharides then to an addition of these, to nanofibrils thus obtained.
More specifically, the present invention aims to implement these nanofibrils cellulose together with at least one organic polyhydroxy compound (polyOH), in a redispersible solid form.
Consequently, the subject of the present invention is the use of nanofibrils of essentially amorphous cellulose with a crystallinity rate less than or equal to 50% in a dispensable dry form associated with at least one compound organic polyhydroxylated (polyOH), as a texturing agent and / or reinforcement in formulations cosmetics.

4 For the purposes of the present invention, a texturing agent is an agent having a role stabilizer and thickener in the cosmetic composition incorporating it.
In the context of the present invention, a reinforcing agent is an agent able to improve the mechanical properties of the composition in which it is incorporated both wet and dry.
It has also been observed that the associations according to the invention can to be possibly used as an emulsifying and stabilizing agent even in medium aqueous containing surfactants.
The use of cellulose nanofibrils associated with at least one (polyOH) under dry form not only has an economic advantage, both in terms of storage as transport for example, but also from a technical point of view because with the redispersible dry form of aqueous suspensions with a content of materials Important dry active ingredients can be prepared.
Unexpectedly, the use of cellulose nanofibrils under this form dry redispersible as a texturing agent and / or reinforcement in compositions cosmetics has proven beneficial in several ways.
For example, in the particular case of cosmetic formulations intended for a cream type skin use for example, there is a significant improvement at level of skin penetration of said formulations. No phenomenon of "soaping" is not observed on the surface of the skin at the time of application of these formulations. Finally, the cellulose nanofibrils according to the invention, give a touch very soft skin as well as a tightening and protective effect on the surface skin, similarly that a moisturizing effect.
Regarding the particular case of hair formulations, incorporation cellulose nanofibrflles associated with at least one cnmnn ~~., r. "n ~ n ~ ~ o polyhydroxylé enhances the styling effect.
The use of said combination with a water-soluble film-forming polymer in solution or a film-forming polymer insoluble in water in dispersion, leads at obtaining a film-forming material having good adhesion on a support keratin with a cosmetic touch that is neither greasy nor sticky.
Water-soluble film-forming polymers used in accordance with this invention can be - or a water-soluble synthetic film-forming polymer with a temperature of transition glassy low Tg, preferably less than or equal to 20 ° C;
- or a water-soluble film-forming polymer of natural origin (polysaccharide derived from cellulose) with a high Tg generally greater than or equal to 40 ° C.

Mention may be made, for example, of polyvinyl alcohol, hydroxyethylcellulose, ethers cellulose generally used in cosmetics, guar gums, gums carob.
Similarly, unlike conventional thickeners,

5 cellulose nanofibrils according to the invention do not affect the properties cosmetics formulations incorporating them. Advantageously, there is no effect braking, neither loss of gloss and no decrease in the water persistence of the compositions.
In addition, a fragrance-enhancing effect has been highlighted.
As mentioned above, the association with cellulose nanofibrils of at least minus one (polyOH), operated during the process for preparing nanofibrils of cellulose, has the advantage of allowing their formulation in a dry form dispersible. This is, of course, of potential interest for the preparation of corresponding cosmetic formulations, in particular that of offering more big flexible formulation due to the high content of active ingredient.
The polyhydroxy organic compound (polyOH) is preferably chosen from carbohydrates and their derivatives and polyalcohols.
As a representative of these carbohydrates, it is particularly possible quote them linear or cyclic monosaccharides in C-3 to C-6, and preferably in C-5 or C-6, for example fructose, mannose, galactose, sucrose, talose, guiose, fallose, altrose, fidose, arabinose, xylose, lyxose and ribose, the oligosaccharides, for example maltose and lactose, polysaccharides, through example starch, cellulose, xanthan gum and guar, and their derivatives bold such as fatty acid sucroesters, alcohol carbohydrates, for example the sorbitol and mannitol, acid carbohydrates, e.g. acids gluconic, uronic, galacturonic as well as their salts and the ethereal carbohydrates by example methyl-, ethyl-, carboxymethyl-, hydroxyethyl- and hydroxypropyl- ethers of cellulose.
With regard to polyalcohols, it may especially be glycerol, pentaerythrol, propylene glycol, ethylene glycol and / or alcohols polyvinyl.
In the particular case of carbohydrates and their derivatives, used jointly with essentially amorphous cellulose nanofibrils, we can more particularly to mention carboxylated celluloses and preferably the cellulose carboxymethylated, also designated by CMC.
Cellulose is a polymer made up of monomeric glucose units:
degree of polymerization can vary within wide limits. The group carboxylated y is introduced in a manner known per se, by reacting the acid chloroacetic with cellulose. Its degree of substitution then corresponds to the number of groupings carboxymethylated per unit of glucose. The degree of theoretical substitution maximum is fi of 3. These carboxylated celluloses are said to have a high degree of substitution for a value greater than 0.95 and low degree for a value less than this this.
Thus, carboxymethylated celluloses of high masses are suitable, the content in retained carboxylated cellulose then being greater than or equal to 5% by weight and less than or equal to 30% by weight, or the carboxymethylated celluloses of weak masses, the content of carboxylated cellulose in this case being more particularly between 10 and 30% by weight.
At the same mass, it also appears possible to further reduce the proportion compared to nanofibrils, favoring the choice of a cellulose carboxymethylated to high degree of substitution.
Such mixtures of nanoparticles of cellulose and carboxylated cellulose are especially described in applications PCT / FR 97 01291 published under the number WO 98102487 and PCT / FR 97 01290 published under the number WO 98/02486.
Preferably, this polyhydroxylated organic compound (polyOH) is chosen from carboxymethylcellulose, xanthan range, guar, sorbitol, sucrose and their mixtures.
The cosmetic formulations obtained according to the invention include preferably the polyhydroxy compound (s) and the cellulose nanofibrils in one weight ratio (polyOH) x 100 lj {polyOH) + {NFC)] greater than or equal to 5%
and less than equal to 50% and preferably greater than or equal to 5% and less or equal to %.
According to a preferred embodiment of the invention, they comprise nanofibrils of cellulose in a form associated with carboxymethylcellulose (CMC) of high degree substitution in a weight ratio (CMC) x 100 / [(CMC) + (NFC)]
higher or 25 equal to 5% and less than or equal to 25%.
Another polyhydroxylated derivative, such as sucrose, propylene glycol or polyethylene glycol for example. In this case in particular, the weight ratio (CMC) x 100! ((polyOH) total + (NFC) j is then lowered significantly.
30 As regards the quantities of cellulose nanofibrils and (polyOH), able be used according to the invention, it is clear that they are a function of the type of shape targeted dosage and / or effect sought at the formulation level cosmetic by example reinforce a moisturizing effect or even provide a protective effect of the epidermis as in depilatory formulations.
This is how in cream-like dosage forms will be present higher amounts of texturing agent according to the invention compared to those implemented in fluid type formulations.

Preferably, the mixture amount of cellulose nanofibrils and polyOH (s}
East adjusted so that said nanofrbrids are present at a rate about 0.1 to 20% and, more preferably, about 0.15 and 5% by weight of the formulation cosmetic.
By way of illustration, it is possible to propose for the preparation of the formulations of type cream a concentration of cellulose nanofibrils and (polyOH) varying between 0.11 and 40%, and for fluid-type formulations, one concentration included between 0.11 and %. The values are proposed for a weight report (polyOH) x 100 / E (polyOH) + (NFC)] greater than or equal to 5% and less or equal to 50 10%.
The solid redispersible composition of cellulase nanofibrils, artwork according to the invention, may contain, in addition to the organic compound (s) polyhydroxylated defined) above, at least one co-additive chosen from ~ the compounds of formula (R ~ R2N) COA, in which R ~ or R2, identical or different, represent (hydrogen or a C-1 to C-10 alkyl radical, of preferably at C-1 to C-5, A represents hydrogen, an alkyl radical at C-1 to C
10, preferably in C-1 to C-5, or also the group R '~ R'2N with R' ~, R'Z, identical or different, representing hydrogen or a C-1 alkyl radical at C
10, preferably at C-1 to C-5; and ~ anionic, nonionic or amphoteric surfactants, these co-additives able be used alone or as a mixture.
Mention may in particular be made, as representative of these surfactants, of those identified below after in the text.
Note that the use of these co-additives allows, in combination with the (polyOH) such as for example carboxymethylcellulose, to reinforce the profile rheofluidifier of cellulose nanofibrils, after redispersion.
As regards the compounds of the (R ~ R2N) COA type, it is preferred to use the compounds comprising two amide functions. Preferably, urea is used as co-additive.
According to a particular embodiment of the invention, these compositions solid redispersible of essentially amorphous cellulose nanofibrils, include of carboxylated cellulose with a high degree of substitution and as a co-additive at least one compound chosen from surfactants.
When the cellulose nanofbrilles used according to the invention are associated with one or more polyhydroxy compounds and with one or more co-additive (s) above, the content of polyhydroxy compounds and co-additive is higher or equal to 5% by weight and less than or equal to 30% by weight relative to the weight in nanofibrils, compounds) polyhydroxylated (s) and co-additive (s).

WO 99/20241 PCTlFR98 / 02031 The nanofibrils used according to the invention can be obtained from of different processes, already described in the literature.
In particular, reference may be made to the process described in the application for patent European EP-A-726 356.
The treatment is carried out on the pulp of plants with primary walls to know wet pulp, dehydrated, preserved by silage or partially disrespectful, such as beet pulp, after it has suffered a step of prior extraction of sucrose, according to the known methods of the technical. More precisely, this treatment implements a first acid extraction or basic, after which a first solid residue is recovered, followed possibly a second extraction, carried out under conditions alkaline, first solid residue, recovery of a second solid residue, washing then the bleaching of the two residues of cellulosic material together, the dilution of the third solid residue obtained at the end of the bleaching step, then the dilution of suspension resulting, so as to obtain a dry matter content of between 2 and 10% in weight, and finally a homogenization step, comprising, at least one cycle of the diluted suspension.
This homogenization step corresponds to a mixing, grinding operation or any high mechanical shear operation, followed by one or many passage of the cell suspension through a small diameter orifice, submitting the suspension at a pressure drop of at least 20 mPa and an action of high speed shear followed by speed deceleration impact high.
The homogenization of the cellulosic suspension is obtained by a number of passages can vary between 1 and 20, preferably between 2 and 5, up to obtaining of a stable suspension.
Regarding the detailed protocol of each step of this treatment, reference will be made to the description of the request identified above.
The process which has just been described makes it possible to obtain nanofibrils which keep on their surface carboxylic acids and / or polysaccharides.
In the case of cellulose nanofibrils used according to the invention, a compound polyhydroxylated, for example carboxylated cellulose, is introduced into the protocol preparation described above, i.e. before the implementation of the step homogenization or after a homogenization cycle has been operated.
It should be noted that this variant of the process is described in the application for patent international number PCT / FR 97101291 published under number WO 98/02487, at which we can refer to if necessary.
The process for the preparation of cellulose nanofibrils, with additives compounds) polyhydroxylated (s) consists, in a first step, of adding to the suspension of nanofibrils, possibly having undergone at least one cycle homogenization, at least part of the polyhydroxylated compound considered and possibly co-additive (s). Then, in a second step, we put in artwork a step of drying the suspension thus added.
In fact, the addition of at least part of the polyhydroxy compound and optionally co-additive (s) can be carried out in three variants - either at the end of the homogenization step and according to a preferred mode, after the latter has undergone at least one concentration stage, - either to the suspension at the end of the homogenization step, before this the latter has undergone at least one concentration stage, or - before or during the homogenization step, the pulp having then undergone less a cycle of the homogenization step.
The concentration stage or stages can be carried out by any means conventional until a dry extract of approximately 35% by weight is obtained.
More in particular, the dry extract is between 5 and 25% by weight.
Prior to the actual drying step, it may be advantageous to carry out shaping, namely by extrusion or granulation, of the suspension which was concentrated. The temperature of the drying step is of course detention so as to limit any degradation of the carboxylic acids, polysaccharides acids, hemicelluloses, polyhydroxy compounds and, where appropriate, co-additives. It is more particularly between 30 and 80 ° C, preferably between 30 and 60 ° C.
The drying step, carried out by conventional means, is carried out so as to maintain at least 3% by weight of water relative to the weight of the solid made. More particularly, the weight of water maintained is between 10 and 30% in weight. Such an implementation makes it possible not to exceed the threshold beyond from which redispersion of nanofibrils can no longer be complete.
Advantageously, the suspension of cellulose nanofibrils obtained by redispersion in water of the mixture, obtained according to the protocol described previously, has a viscosity level corresponding to at least 50% for a rate of shear of at least 1 s-1, of the viscosity level of a suspension of nanofibrils cellulose that has not undergone a drying step and does not contain compound polyhydroxylated or co-additives.
Of course, the essentially amorphous cellulose nanofibrils charged in surface preferably in acid, and associated with a polyhydroxylated compound and optionally a co-additive are used in the formulations cosmetics obtained according to the invention, in mixture with at least one compatible vehicle with a hair, skin or sun application.

The term "compatible" with application to the hair and / or skin mean here that this vehicle does not damage or have a negative effect on the appearance of the hair and / or the skin or does not cause irritation of the skin and / or the eye and / or leather hairy.
5 The present invention also relates to cosmetic formulations using as a texturing agent and / or reinforcing nanofibrils cellulose essentially amorphous in a dispensable dry form and associated with less a polyhydroxy organic compound as defined above. These formulations may also contain an additive as defined above.
Preferably, the cosmetic formulations according to the invention make call to a vehicle, or a mixture of several vehicles, present in said formulations at concentrations between 0.5 and 99.5% approximately and more preferentially between 5 and 90% approximately.
Vehicles compatible with the formulations according to the invention include through example those used in sprays, foams, tonics, gels, shampoos, or rinsing lotions.
Of course the choice of the appropriate vehicle depends on the specific application targeted by the formulation. A vehicle suitable for a formulation intended at remain on the surface of which it was applied (for example spray, foam, lotion, tonic or gel), will not be the appropriate vehicle for formulation before be rinsed off after use (e.g. conditioner shampoo, body lotion rinsing).
The vehicles likely to be used can therefore be simple or complex and include a large number of products commonly used in formulations cosmetics intended for hair, skin or sun use.
It can thus be water optionally supplemented with a solubilizer for dissolve or disperse the active ingredients used, such as alcohols C-1 to C-6, and mixtures thereof, in particular ethanol, isopropanol or propylene glycol, and their mixtures.
Advantageously, there is good compatibility of the nanofibrils of cellulose associated with at least one polyhydroxylated organic compound with regard to solubilizers alcohol type. The texturing properties of these cellulose nanofibrils are not altered in hydroalcoholic environments.
Likewise, they consent to their properties in so-called more aggressive, either very acidic such as a-hydroxyacid creams or media alkaline like depilatory formulations or lotions for perms.
Examples 2 and 3 presented below illustrate this behavior advantageous cellulose nanofibrils associated with at least one polyOH in cosmetic application.

Advantageously, the NFCs formulated according to the invention prove to be excellent structuring agents for cosmetic media and retain their properties in the time. Their viscosity is higher than that of celluloses microcrystalline.
We can also associate, in a fatty phase distinct from the phase aqueous NFC according to the invention, one or more emollients chosen from:
oils mineral (like Marcol 82 ~), vegetable or marine oils, halogenated hydrocarbons, finalol, esters (such as myristate isopropyl), and silicones compatible with a cosmetic application (in particular cyclodimethicones and dimethicones and derivatives and hexamethyldisiloxane) and their derivatives or mixtures.
When cosmetic formulations are in the form of sprays, tonic lotions, gels, or foams, preferred solvents include the water, fethanol, volatile silicone derivatives, and mixtures thereof. Solvents used in these mixtures can be miscible or immiscible with each other.
The foams and aerosol sprays can also use any propellant able generate the products in the form of foam or fine, uniform sprays. AT
title examples that may be mentioned include dimethyl ether, propane, n-butane, or isobutane.
In the case where the cosmetic formulations are intended for an application topical local, vehicles must have good edonic properties, to be compatible with all other components, and present a perfect harmlessness.
These vehicles can take a large number of forms, of emulsion type, foams, sprays ... For example, vehicles in the form of emulsions include the water in silicone, water in oil, oil in water, and oil in water emulsions in silicone. These emulsions cover a wide range of viscosity, for example from 100 to 20,000 mPa.s at 25 ° C. These emulsions can also be delivered under form of sprays using either a mechanical pump type device or pressurized by the employment of a propellant gas.
These vehicles can also be delivered in the form of foam.
In addition to the vehicles identified above, the formulations cosmetics according to the invention may contain surfactants, artwork to disperse, emulsify, solubilize, stabilize various compounds used especially for their emollient or moisturizing properties. They can be of type anionic, non ionic, cationic, zwitterionic or amphoteric. As an illustration of these compounds on can more particularly cite - anionic surfactants such as alkyl esters sulfonates, alkyl sulfates, alkylamide sulfates and salts of saturated fatty acids or unsaturated;

- non-ionic surfactants such as alkylphenols polyoxyalkylenated, glucosamides, glucamides, glycerolamides derived from N-alkylamines, polyoxyalkylenated C-8 to C-22 aliphatic alcohols, the products resulting from the condensation of (ethylene oxide with a hydrophobic compound or resulting from the condensation of propylene oxide with propylene glycol, the oxides amines, alkylpolyglycosides and their polyoxyalkylenated derivatives, amides fatty C-8 to C-20 and fatty acids, amides, amines, amidoarnines ethoxylated;
- amphoteric and zwitterionic surfactants such as those of the betaine such as betaines, sulfo-betaines, amidoalkylbetaines and sulfo-betaines, alkylsultaines, fatty acid condensation products and protein hydroxylates, cocoamphoacetates and cocoamphodiacetates, alkylamphopropionates or -dipropionates, the amphoteric derivatives of alkylpolyamines.
Conditioners may also be present.
Among these, there may be mentioned those of synthetic origin better known as the polyquaternium name like polyquaterniums -2, -7, and -10, derivatives cationic polysaccharides, such as cocodimonium hydroxyethyl cellulose, guar hydroxypropyl trirnonium chloride, fhydroxypropyl guar hydroxypropyl trimonium chloride, non-volatile silicone derivatives such as famodimethicone, cyclomethicones, non-water-soluble and non-volatile organopolysiloxanes like the oils, resins or gums such as diphenyldimethicone gums.
Cosmetic formulations may also contain polymers having film-forming properties which can be used to provide function fixing. These polymers are generally present at concentrations included between 0.01 and 10%, preferably between 0.5 and 5%. They are preferably from polyvinylpyrrolidone type, polyvinylpyrrolidone and methyl copolymers methacrylate, copolymer of polyvinylpyrrolidone and vinyl acetate, copolymers polyerephthalene ethylene glycol / polyethylene glycol, polymer copolyesters sulfonated terephthalics.
Cosmetic formulations can also contain derivatives polymers exerting a protective function, in quantities of the order of 0.01 to 10%, preferably about 0.1 to 5% by weight, derivatives such as derivatives cellulosics, polyvinyl esters grafted on polyalkylene skeletons, alcohols polyvinyl, sulfonated terephthalic copolyester polymers, monoamines or polyamines ethoxylated and ethoxylated amine polymers.
Agents can also be incorporated into cosmetic formulations moisturizers. By way of illustration of the latter, mention may in particular be made of the glycerol, the propylene glycol, urea, collagen, gelatin, and emollients that are generally chosen from alkylmonoglycerides, alkyldiglycerides, triglycerides such as oils extracted from plants and plants or their derivatives hydrogenated, mineral oils or paraffinic oils, diols, fatty esters, silicones.
To these compounds, one or more perfumes, agents, are generally added.
dyes and / or opacifying agents such as pigments.
To protect the skin and / or hair from the aggressions of the sun and rays UV, we can add to these formulations sunscreens which either smells compounds organic strongly absorbing UV radiation or mineral particles to the state nanoparticulate, such as zinc oxide, titanium dioxide or oxides of cerium.
Active ingredients, such as vitamins, α-hydroxy acids, derivatives of plants, marine extracts, with purely cosmetic properties, can be incorporated into formulations containing NFCs for action treating.
Similarly, NFCs are preferred texturing agents for formulations depilatories such as calcium thioglycolate-based media by example.
Preservatives such as esters of p-hydroxybenzoic acid, sodium benzoate, or any chemical agent preventing proliferation bacterial or molds and traditionally used in cosmetic compositions are generally introduced into these compositions up to 0.01 to 3% by weight in accordance with Annex VII of the cosmetic regulations.
Finally, cosmetic formulations can also contain polymers viscosants or gelling agents such as crosslinked polyacrylates of the CARBOPOL type ~
marketed by GOODRICH, cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose, guars and their derivatives as fhydroxypropyl guar such as Jaguar HP ~, carob, tara gum or cassia, the xanthan gum such as Rhodicare ~, succinoglycans, alginates, carrageenans, chitin derivatives or any other polysaccharide to function texturing.
It is clear that the choice of these so-called conventional compounds and the appreciation of their respective quantities are directly linked to the type of formulation envisaged, to know gel, cream, milk, spray, lotion ... and with the desired edonic character.
These adjustments are actually routine operations for the formulator in cosmetic.
The cosmetic formulations according to the invention can advantageously be implemented in the hair, sun, body care and makeup.
The examples submitted below are presented for illustrative purposes only and no limiting of the present invention.

Preparation of a mixture of cellulose nanofibrils and carboxymethylcellulose.
A carboxymethylcellulose, with a degree of substitution equal to 1.2 (CMC BLANOSE
~ 12M8P of AQUALON) is dissolved in distilled water.
The solution is then added to the mother dispersion of 2.3% nanofrids.
in cellulose nanofibrils and prehomogenized with Ultra-Turrax at 14,000 rpm (1 min for 100 g of dispersion). The whole is agitated with pale deflocculation at 1000 rpm during 30 mins.
The amount of carboxymethylcellulose added is 15% by weight, per report by weight of cellulose nanofibrils and of carboxymethylcellulose.
The mixture is then poured into cups and then dried either in an oven ventilated at 40 ° C, up to a dry extract of 92%, controlled by dosage of water KARL-FISCHER method.
The dried mixture is then ground, then sieved through a 500 Wm sieve.
The powder obtained is redispersed at a rate of 0.43% by weight of nanofibrils of cellulose and carboxymethylcelluiose in distilled water. The agitation takes place at deflocculating blade at 1000 rpm for 5 min or 30 min. This dispersion is setting work in the examples below.

Behavior of NFCs associated with CMC in an alcoholic environment.
For this silence, we disperse in water, under shear, the mixture NFC / CMC
prepared in Example 1, then the alcohol in question is added or not.
Table I presented below gives an account of the composition of the two media.
hydroalcoholic thus prepared. The viscosities of these media and of a medium witness (water) are evaluated using a viscometer of the BROOKFIELD LVT type.
The results are shown in Table I.

TABLE I
NFC additive 0.43 Viscosit Pa.s Ethanol 10 Propylene glycol Distilled water %

'! 0 1 s 1 0.8 0.85 0.60 100 s 1 0.04 0.04 0.035 5 Behavior of NFCs associated with CMC in an acidic or alkaline medium.
The NFC mixture prepared according to Example 1 is introduced into buffered water at a pH of 4 or 9. The rheological behavior of this medium is assessed at look a control medium comprising 1% of microcrystalline cells with additives in CMC.
Table II reports the change in viscosity over time.
TABLE II
gent texturant Viscosit Pa.s _ 100 s-1 1 sec j pH = 4 pH = 9 pH = 4 pH = 9 0.43% in additive NFC 1 0.35 0.55 0.015 0.02 j 85115 CMC 5d 0.35 0.65 0.015 0.02 1% in Celluloses Micro- 1 0.02 0.03 j additive crystal 5d 0.02 0.03 CMC

It is noted that the NFCs formulated according to the invention prove to be excellent agents structuring of cosmetic media and retain their properties in the time. Their viscosity is higher than that of microcrystalline celluloses.

Cosmetic formulations according to the invention.
These formulations contain the NFC / CMC mixture prepared in Example 1.
1) A-hydroxy acid cream ingredients% by weight Phase A
Cetearyl alcohol 8 Diethylamine 2 cetyl phosphate IPVP 2 eicosene copolymer ~ Octyldodecyl neopentanoate 10 Mirasil ~ DM 300: Dimethicone 1 Phase 8 NFCICMC 0.2 Propylene glycol 5 Water qs 100 Phase C

Alpha hydroxy acids 5 Phase D

Trithanolamine 1.8 Phase E

~ Conservative qs 2) Gentle body scrub Ingredients% by weight Phase A

~ Water qs Phase 8 Phase C

Magnesium Lauryl Sulfate 8.5 ~ Sodium cocoyl sarcosinate 1.0 Sodium hydroxide 55 ~ 0.50 Dithylamine Lauramide 2.0 Staric acid 1.0 Gropon AC78 ~: cocoyl isthionate of 13 sodium Phase D

Polyethylene oxide 20 Phase E

Conservative qs Perfume and coloring qs 3) depilatory lotion Ingredients% by weight Phase A

NFC / CMC 0.5 Water qs 100 Phase 8 Propylene glycol 5 Phase C

WO 99I202a1 PCT / FR98 / 0203I

Lanolin mineral oil and alcohol 5 Polysorbate 80 and cetyl acetate and alcohol acetylated lanolin 2 PEG-100 stearate and glyceryl stearate 2 Phase D
Calcium thioglycolate 5 ° Calcium hydroxide 6 Phase E
Preservative, colorant, perfume qs 100 Behavior of NFCs associated with CMC as a reinforcing agent dispersion of ~~ film-forming polymer The purpose of this example is to show that the association of nanofibrils with at at least one (polyOH) can also be a reinforcing agent.
The tests were carried out with a film-forming latex Rhodopas DS 1003 marketed by Rhodia (aqueous dispersion of acrylic polymer), the glass transition temperature Tg is 12 ° C, the temperature of film formation TMF below 5 ° C, the dry extract of the dispersion is 50%, and the particle size of said latex is 0.1 Nm. The dispersion has a pH of approximately 8.
The dispersion of cellulose nanofibrils obtained in Example 1 from of the dry powder is used in this example.
Louvant formulation serving as a base for aau uncle varnish Two latex formulations DS 1003 as defined above are prepared F1 (comparison): 30% by weight of latex 1003 + 70% by weight of water, by compared to total weight of the formulation;
F2 (according to the invention): 30% by weight of latex 1003 + 1% by weight of NFC
obtained in Example 1 + 69% by weight of water, relative to the total weight of the formulation.
The pH of the medium is adjusted to 7.
F1 has a viscosity of less than 10 mPa.s while the viscosity of F2 East about 4500 mPa.s. Viscosities are assessed using a viscometer Of type BROOKFIELD LVT (needle 3, 10 turnslminute).
The results are summarized in Table III.

$ 1 Table III

film-like aspect not filmed translucent film born duret Persoz - 49 (in s) membership 0 0 (no removal) Persoz hardness is determined according to standard NFT 30-016: hardnesses are measured after more than 8 days of drying at (ambient in 3 different places of the plate. Each measurement corresponds to the average of 3 measurements. The results indicate the time (in seconds) that the pendulum takes to dampen its oscillation by one angle of 12 ° at an angle of 4 °.
The longer the time, the harder the film.
The adhesion on support is determined by a grid test according to the standard ISO 2409: the films were printed on a steel plate. The test consists of check out at cut the füm of 2 series of 6 perpendicular lines spaced 1 mm apart and snatch this grid with adhesive tape. The rating goes from 0 (no tearing) to 4 (tearing about 50% of the grid).
The formulation F2 which comprises the NFC additives of the invention, corresponds therefore to a material which could serve as a base for aqueous varnish. The formulation F2 obtained is stable. Of pseudo-plastic character, it spreads easily on the supports. The film has good adhesion, and good flexibility with a touch neither greasy nor sticky.

Claims (16)

1. Use of essentially amorphous cellulose nanofibrils having a rate of crystallinity less than or equal to 50% in a dispersible dry form associated with at least one polyhydroxy organic compound (polyOH), as agent texturizing and/or reinforcement in cosmetic formulations. 2. Use according to claim 1 characterized in that the compound organic polyhydroxylated (polyOH) is chosen from carbohydrates and their derivatives and the polyalcohols. 3. Use according to claim 2 characterized in that the carbohydrates are preferably chosen from linear or cyclic C-3 to C- monosaccharides 6, the oligosaccharides, polysaccharides and their fatty derivatives such as sucrose esters of fatty acids, carbohydrates alcohol, acids and ethers. 4. Use according to one of claims 1 to 3, characterized in that the compound polyhydroxylated organic (polyOH) is preferably chosen from the carboxymethylcellulose, xanthan gum, guar, sorbitol, sucrose and their mixtures. 5. Use according to one of claims 1 to 4, characterized in that the rate crystallinity is between 15 and 50% and preferably less than 50%. 6. Use according to one of claims 1 to 5 characterized in that the nanofibrils of cellulose have at least 80% cells with primary walls. 7. Use according to one of claims 1 to 6 characterized in that the nanofibrils of cellulose are derived from cells preferably consisting of at least about 80%
primary walls. 8. Use according to one of claims 1 to 7, characterized in that the cellulose nanofibrils are loaded with carboxylic acids and polysaccharides acids, alone or in combination. 9. Use according to one of claims 1 to 8 characterized in that the compound organic polyhydroxylated is associated with cellulose nanofibrils in a report by weight (polyOH) x 100 / [(polyOH) + (NFC)] greater than or equal to 5% and lower or equal to 50%. 10. Use according to claim 9 characterized in that the ratio weight (polyOH) x 100 / [(polyOH) + (NFC)] is greater than or equal to 5% and less or equal to 30 %. 11. Use according to one of claims 4 to 10 characterized in that the cellulose nanofibrils are associated with carboxymethylcellulose (CMC) of high degree of substitution in a weight ratio (CMC) x 100 / [(CMC) +(NFC)]
greater than or equal to 5% and less than or equal to 25%. 12. Use according to one of the preceding claims, characterized in that that the quantity of cellulose nanofibrils and (polyOH)(s) mixture is adjusted by way to that said nanofibrils are used in an amount of 0.1 to 20% by weight of the cosmetic formulation. 13. Use according to claim 12, characterized in that the nanofibrils are used at a rate of 0.15 to 5% by weight. 14. Use according to one of the preceding claims, characterized in that that cellulose nanofibrils and the (polyOH) are associated with at least one co-chosen additive among:
~ the compounds of formula (R1R2N)COA, in which R1 or R2, identical or different, represent hydrogen or a C-1 to C-10 alkyl radical, of preferably C-1 to C-5, A represents hydrogen, a C-1 to C-5 alkyl radical C-10, preferably C-1 to C-5, or else the R'1R'2N group with R'1, R'2, identical or different, representing hydrogen or a C-1 alkyl radical to C-10, preferably C-1 to C-5; and ~ anionic, nonionic or amphoteric surfactants, these co-additives can be used alone or in combination. 15. Use according to claim 14 characterized in that the content of compound(s) polyhydroxylated(s) and co-additive(s) is greater than or equal to 5% by weight and lower or equal to 30% by weight relative to the weight in nanofibrils, compound(s) polyhydroxylated(s) and co-additive(s). 16. Cosmetic formulation characterized in that it comprises as agent texturizing and/or reinforcement of essentially amorphous cellulose nanofibrils under a shape dispersible drier and combined with at least one polyhydroxy organic compound, such as defined according to one of Claims 1 to 13 and, where applicable, to at least an additive according to claim 14 or 15.