JP2001520180A - Use of essentially amorphous cellulose nanofibrils in combination with at least one polyhydroxylated organic compound in a cosmetic formulation - Google Patents

Abstract

  (57) [Summary] The subject of the present invention is to provide, as a texturizing agent and / or reinforcing agent in cosmetic preparations, essentially amorphous cellulose nanofibrils having a crystallinity of less than 50% in dry dispersible form with at least one type of cellulose nanofibrils. Polyhydroxylated (polyOH) is to be used in combination with an organic compound. The invention furthermore relates to the cosmetic preparations obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the use of essentially amorphous cellulose nanofibrils in a dispersible form having a degree of crystallinity of not more than 50% in cosmetic preparations and to the preparations thus obtained. It is.

[0002] A more particular subject of the invention is a novel texturizing and / or reinforcing agent for cosmetic formulations.

[0003] Within the meaning of the present invention, the term "cosmetic formulation"
) "Is called the Directive Cosmetique, July 25, 1976
European directive no. 76/768 / EEC Appendix I II "Illustrative list by category of cosmetic prod"
ucts) means any cosmetic product or formulation of the type described in｝.

[0004] Cosmetic compositions are generally formulated in the form of a number of product types intended for application to either hair or skin. Examples of applications to hair are foams, gels (especially styling gels), conditioners, styling preparations, preparations or rinse preparations for facilitating combing and / or unraveling of the hair. Examples of skin applications include hand and body lotions, skin moisturizing products, cleansing emulsions, makeup remover compositions, hair remover products, creams or lotions for protection against the sun and ultraviolet light,
Care creams, anti-acne preparations, topical anesthetics, mascara, foundation or nail polish type makeup preparations, products intended to be applied to the lips or other mucous membranes, sticks, solid soap type solid compositions and other of the same type There are formulations.

[0005] Conventionally, these various formulations contain, in addition to one or more active ingredients which are specific for the intended use, a certain number of so-called even more conventional compounds, especially Compounds which have the function of imparting stability over time (for example preservatives) and / or which have the role of imparting a particular pharmaceutical preparation form (for example gel, cream, emulsion, lotion type) are incorporated. These are generally surfactants and / or dispersants, stabilizers, emulsifiers, wetting agents, gelling agents or thickeners.

Representative examples of conventional stabilizers and / or thickeners include cross-linked polyacrylates, fermentable hydrocolloids such as Xanthane-Rhodicare® gum and succinoglycans {for example. Rheozan®, cellulose derivatives (eg, hydroxylpropylcellulose or carboxymethylcellulose) or guars and their derivatives (which may be used alone or in combination).

[0007] It is an object of the present invention to provide novel texturizing and / or reinforcing agents which have a rheologically advantageous behavior in formulating cosmetic compositions. More specifically, it is based on essentially amorphous cellulose nanofibrils having a crystallinity of 50% or more, provided in a dry form dispersible in an aqueous medium.

[0008] Natural cellulose generally generally exhibits a fibril morphology. These fibrils are well-known substances that have already been particularly proposed for modifying the texture of the medium into which they have been introduced. In the case of fluid media, they modify their viscosity, and even their rheological properties.

[0009] Nanofibrils can be of various origins, for example, from plants, bacteria, fungi or amoeba and the like.

In plant fibers or walls, there is generally a strong bond between nanofibrils. A secondary wall, which is primarily of wood origin, and a primary wall, a typical example of which is parenchyma, can be distinguished in plant walls. An example of a soft tissue is
Consists of sugar beet (sugar beet, sugar beet) pulp, citrus fruits (lemon, orange, grapefruit) and most fruits and vegetables. In the secondary wall these fibrils are arranged in the form of highly oriented sheets,
For this reason, fibers that cannot be separated are formed. These are usually several tens nm to several μm
Exist in the form of an aggregate. These assemblages consist of individual fibrils that cannot be unwound during their homogenization without cutting.

In the present invention, the cellulosic fibrils in question are essentially amorphous cellulose nanofibrils (CNF) and are preferably obtained from cells having primary walls.

[0012] The cellulose nanofibrils of the present invention are conveniently obtained from cells comprising at least about 80% by weight of the primary wall (cells having at least about 80% by weight of the cell wall being the primary wall), wherein the primary wall comprises Preferably it is at least 85% by weight.

[0013] The essentially amorphous cellulose nanofibrils used according to the present invention preferably exhibit at least 80% of cells with primary walls.

[0014] In contrast to the cellulose fibrils from the secondary walls described above, cellulose nanofibrils exhibit a diameter of up to several nanometers and have the appearance of filaments, which filaments during the homogenization stage It turns out that it can be unraveled.

Preferably, they exhibit a cross section in the range of about 2 to about 10 nm. Even more preferably, the cross section ranges from about 2 to about 4 nm.

In the present invention, the pending nanofibrils are so-called essentially amorphous nanofibrils, as opposed to so-called crystalline nanofibrils.

The term “essentially amorphous” is intended to define nanofibrils having a crystallinity of 50% or less. According to another particular aspect of the invention, this crystallinity is 15
% To 50%, and even more preferably less than 50%.

These essentially amorphous cellulose nanofibrils are dispersible in aqueous media, impart very specific rheological properties of the shear-thinning type, and are thermally ionic Is particularly advantageous in light of crystalline microfibrils in the sense that they are stable even in high media. This high effect of cellulose nanofibrils in reduced amounts is in fact the result of their excellent rheological behavior in terms of yield point and possible shear thinning.

According to a preferred embodiment of the present invention, the cellulose nanofibrils used according to the present invention carry carboxylic acids or acidic polysaccharides alone or as a mixture on a surface (
Loading).

The term “carboxylic acid” shall mean only carboxylic acids and their salts. These acids are preferably selected from uronic acids, even more preferably from galacturonic acid and / or glucuronic acid.

[0021] Acidic polysaccharides include pectin, and even more particularly include polygalacturonic acid. These acidic polysaccharides can be present as a mixture with hemicellulose.

In practice, the nanofibrils on which they are carried are not the result of a simple mixing between said nanofibrils, acids and polysaccharides. Rather, it is important that the close combination between these two types of compounds be derived directly from the process employed to prepare the nanofibrils. In fact, this preparation process allows the acids and polysaccharides to remain on the surface of these fibers without completely separating them from the fibers, thus giving them very specific properties. If the nanofibrils are completely separated from these acids and / or polysaccharides and then the acid and / or polysaccharides are added again to the nanofibrils thus obtained, these same treatments will be performed. It is important to emphasize that the properties will not be reproduced.

More particularly, the present invention is directed to the use of these cellulose nanofibrils with at least one polyhydroxylated (polyOH) organic compound in a solid, redispersible form. .

Accordingly, the subject of the present invention is an essentially amorphous cellulose nanofibril having a crystallinity of not more than 50% in dry dispersible form as a texturizing and / or reinforcing agent in cosmetic preparations Is used in combination with at least one polyhydroxylated (polyOH) organic compound.

In the meaning of the present invention, a texture agent is an additive having a role of stabilization and thickening in a cosmetic composition containing it.

In the context of the present invention, a reinforcing agent is an additive that can improve the mechanical properties of the composition to which it has been added, both in the wet state and in the dry state.

It has furthermore been observed that the combinations according to the invention can optionally be used as emulsifying and stabilizing agents even in aqueous media containing surfactants.

The use of cellulose nanofibrils in combination with at least one (polyOH) in dry form is not only economically advantageous, for example both with respect to storage and transport, but also because of the dry redispersible form An aqueous suspension with a high active material content can be produced, which is also advantageous from a technical point of view.

The use of this dry, redispersible form of cellulose nanofibrils as a texture agent and / or a reinforcing agent in cosmetic formulations has been unexpectedly discovered,
It has proven advantageous in several respects.

For example, in the particular case where the cosmetic formulation is of the cream type for use on the skin, a significant improvement in the degree of penetration of such formulation into the skin is observed. No "soaping" phenomenon is observed on the surface of the skin when these formulations are applied. Finally, the cellulose nanofibrils according to the invention provide a very soft skin feel and a firming and protecting effect on the skin surface as well as a moisturizing (moisturizing or moisturizing) effect.

For the specific case of hair preparations, the styling effect is reinforced by combining cellulose nanofibrils combined with at least one polyhydroxylated organic compound.

By using the above combination with a dissolved water-soluble film-forming polymer or a dispersed water-insoluble film-forming polymer, it exhibits good adhesion to keratin substrates with a greasy and non-greasy feel. A film forming material is produced.

The water-soluble film-forming polymers used according to the invention include: a synthetic water-soluble film-forming polymer having a low glass transition temperature Tg, preferably less than 20 ° C .; A natural water-soluble film-forming polymer (polysaccharide derived from cellulose) with a high Tg.

For example, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose ethers commonly used in cosmetics, guar gum or locust bean (
Carob, locust bean) gum.

Also, in contrast to conventional thickeners, the nanofibrils according to the invention do not affect the cosmetic properties of the blended formulations. Advantageously, no effect of reducing or losing luster is observed, and no reduction in the water resistance of the composition is observed. Furthermore, the aroma enhancement effect was also shown.

As mentioned above, the operation of combining at least one (polyOH) with the cellulose nanofibrils during the manufacturing process of the cellulose nanofibrils allows them to be formulated in a dry dispersible form. Is provided. Of course, this is a potential advantage for the production of the corresponding cosmetic preparations, especially in that the higher the active ingredient content, the greater the flexibility (versatility) of the preparations. is there.

The polyhydroxylated (polyOH) organic compound is preferably selected from carbohydrates and their derivatives and polyalcohols.

Representative examples of these carbohydrates include, very particularly, C ₃ -C ₆ , preferably C ₅ or C ₆ cyclic or linear monosaccharides (eg fructose, mannose,
Galactose, sucrose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose, oligosaccharides (eg maltose and lactose), polysaccharides (eg starch, cellulose, xanthan gum and guar) and their fats Derivatives (eg fatty acid sucrose esters)
, Alcohol carbohydrates (eg sorbitol and mannitol), acid carbohydrates (
For example, gluconic acid, uronic acid and galacturonic acid and salts thereof, and ether carbohydrates (eg, methyl-, ethyl-, carboxymethyl- of cellulose).
, Hydroxyethyl- and hydroxypropyl ether).

As regards polyalcohols, this can be in particular glycerol, pentaerythritol, propylene glycol, ethylene glycol and / or poly (vinyl alcohol).

In the particular case of using carbohydrates and their derivatives together with essentially amorphous cellulose nanofibrils, more particularly carboxylated cellulose, preferably carboxymethylated cellulose (also denoted CMC) Can be mentioned.

Cellulose is a polymer composed of glucose monomer units. The degree of polymerization can vary within wide limits. Carboxyl groups are introduced therein by reacting chloroacetic acid with cellulose in a manner known per se. In that case, the degree of substitution corresponds to the number of carboxymethyl groups per glucose unit. The theoretical maximum degree of substitution is 3. These carboxylated celluloses are said to have a high degree of substitution for values greater than 0.95 and are said to have a low degree of substitution for values less than 0.95.

Thus, a carboxymethylated cellulose having a high mass (in this case, the content of the carboxylated cellulose is 5% by weight or more and 30% by weight or less) or a carboxymethylated cellulose having a low mass (in this case, The content of carboxylated cellulose is more specifically in the range of 10 to 30% by weight).

Furthermore, it can be seen that, given the same mass, the proportion of nanofibrils can be further reduced by choosing a carboxymethylated cellulose with a high degree of substitution.

The mixture of such cellulose nanofibrils and carboxylated cellulose is
In particular, the pamphlet of International Publication WO98 / 02487 (international application PCT / FR97)
/ 01291) and WO 98/02486 (International Application No. PCT / FR97 / 01290).

The polyhydroxylated (polyOH) organic compound is preferably selected from carboxymethylcellulose, xanthan gum, guar, sorbitol, sucrose and mixtures thereof.

The cosmetic preparation obtained according to the invention comprises a polyhydroxylated compound (polyO
H) and cellulose nanofibrils (CNF) in a weight ratio of (polyOH) × 100 / [(polyOH) + (CNF)] of 5% to 50%, preferably 5% to 30%. preferable.

According to a preferred form of the present invention, they comprise cellulose nanofibrils with a high degree of substitution of carboxymethylated cellulose (CMC) and 5% to 25% (CMC).
× 100 / [(CMC) + (CNF)] in combination in weight ratio.

Also, for example, sucrose, propylene glycol or poly (ethylene glycol)
Other polyhydroxylated derivatives such as can be combined with CMC.
In this particular case, (CMC) × 100 / [(polyOH) _total + (CNF)
)] Significantly lower weight ratio.

[0049] Cellulose nanofibrils and (polyOH
With regard to the amounts of these, they contribute to the type of pharmaceutical formulation form sought and / or to the effect desired in the cosmetic formulation (for example to enhance the moisturizing effect or to protect the epidermis as in depilatory formulations). It is evident that it depends on

Thus, a higher amount of the textured agent according to the invention is present in the cream-type pharmaceutical formulation compared to that used in the fluid-type pharmaceutical formulation.

The amount of the mixture of cellulose nanofibrils and polyOH is preferably adjusted so that the cellulose nanofibrils are present in a proportion of about 0.1 to 20% by weight of the cosmetic formulation, preferably about 0.15 to Even more preferably, it is adjusted to be present in a proportion of 5% by weight.

By way of example, it is recommended that the concentration of cellulose nanofibrils and polyOH be in the range of 0.11-40% for the preparation of cream type formulations, and 0.1% for the preparation of fluid type formulations. A range of 11 to 10% can be recommended. These values are 5% or more and 50% or less of (polyOH) × 100 / [(polyOH) +
(CNF)] recommended for weight ratio.

The solid redispersible composition of cellulose nanofibrils used according to the present invention may comprise, in addition to the above-mentioned polyhydroxylated organic compound, at least one auxiliary additive selected from the following: Can be: Formula (R ¹ R ² N) COA where R ¹ and R ² may be the same or different and are hydrogen or a C ₁ -C ₁₀ , preferably C ₁ -C ₅ alkyl group A represents hydrogen, a C ₁ -C ₁₀ , preferably a C ₁ -C ₅ alkyl group or a group R ′ ¹ R ′ ² N (where R ′ ¹ and R ′ ² are the same or different. Or a hydrogen or a C ₁ -C ₁₀ , preferably a C ₁ -C ₅ alkyl group), and an anionic, nonionic or amphoteric surfactant. These auxiliary additives can be used alone or as a mixture.

Representative examples of these surfactants include those particularly shown later in this specification.

These auxiliary additives can be used, for example, such as carboxymethylcellulose (polyOH
It is noteworthy that the use in combination with (1) can reinforce the shear thinning properties of the cellulose nanofibrils after redispersion.

For compounds of the type (R ¹ R ² N) COA, it is preferred to use compounds containing two amide functional groups. Preferably, urea is used as an auxiliary additive.

According to a particular embodiment of the present invention, these solid redispersible compositions of essentially amorphous cellulose nanofibrils comprise a highly substituted carboxylated cellulose and, as an auxiliary additive, And at least one compound selected from the group consisting of surfactants.

When the cellulose nanofibrils used according to the invention are combined with one or more polyhydroxylated compounds as described above and one or more auxiliary additives. The content of the polyhydroxylated compound and the auxiliary additive is not less than 5% by weight and not more than 30% by weight based on the weight of the nanofibril, the polyhydroxylated compound and the auxiliary additive.

The nanofibrils used according to the invention can be obtained from various methods already disclosed in the literature. In particular, reference may be made to the method disclosed in EP-A-726356.

The treatment was a pulp from a plant with primary walls—ie wet pulp, dehydrated and stored by ensilage (silo storage) or partially depectinized, for example subjected to a preliminary sucrose extraction step. The later beet pulp is performed according to methods well known in the art. More specifically, the treatment comprises performing a first acid or base extraction, recovering the resulting first solid residue, and then optionally removing a first solid residue of the first solid residue. A second extraction is carried out under alkaline conditions, a second solid residue is recovered, washed and then the two residues consisting of cellulosic material are bleached together and the third obtained from the bleaching step is obtained. Diluting the solid residue and then diluting the resulting suspension to a proportion of dry matter in the range from 2 to 10% by weight, and finally homogenizing the diluted suspension in at least one cycle .

The homogenization step involves mixing, milling or high mechanical shearing operations, then passing the cell suspension through the small orifice one or more times and passing the suspension at least 20 m.
Subject to a pressure drop of Pa and a high speed shearing action followed by a high speed deceleration impact. Homogenization of the cellulosic suspension is achieved with 1-20, preferably 2-5 passes, until a stable suspension is obtained.

For the detailed protocol of each step of this process, refer to the description of the above-mentioned patent specification.

The method just described makes it possible to obtain nanofibrils carrying carboxylic acids and / or polysaccharides on their surface.

In the case of the cellulose nanofibrils used according to the invention, for example, polyhydroxylated compounds of the carboxylated cellulose type are subjected to the above-mentioned preparation protocol either before performing the homogenization step or after performing the homogenization cycle. be introduced.

This alternative form is described in WO 98/02487 pamphlet (International Application P
CT / FR97 / 01291), which should be referred to if necessary.

The process for the preparation of cellulose nanofibrils to which a polyhydroxylated compound has been added comprises a process in which the suspension of nanofibrils, which has optionally been subjected to at least one homogenization cycle in the first stage, is added to the suspension of the polyhydroxylated compound. And optionally adding at least a portion of the auxiliary additives, and then performing a drying step of the suspension thus added in a second stage.

In practice, the addition of the polyhydroxylated compound and at least a part of the optional auxiliary additives can be carried out according to three different forms: • Addition to the suspension obtained from the homogenization step (Preferably after at least one concentration step);-added to the suspension obtained from the homogenization step, and then subjected to at least one concentration step; or-before or during the homogenization step (In this case, the pulp has been subjected to at least one cycle of the homogenization step).

The concentration step can be carried out by conventional means until a dry extract of about 35% by weight is obtained. More specifically, the dry extract ranges from 5 to 25% by weight.

Prior to the actual drying step, it may be advantageous to shape the concentrated suspension by shaping, ie by extrusion or granulation. The temperature of the drying process is, of course, carboxylic acid,
It is selected to suppress the degradation of acidic polysaccharides, hemicellulose, polyhydroxylated compounds and optional auxiliary additives. This temperature is more particularly between 30 and
It is in the range of 80C, preferably in the range of 30-60C.

The drying step is carried out by conventional means and is carried out so as to keep the water at a minimum of 3% by weight, based on the weight of solids produced. More specifically, the weight of water is 10
Keep in the range of ３０30% by weight. Such an implementation does not exceed the threshold above which the redispersion of the nanofibrils is no longer complete.

By redispersing the mixture obtained according to the above protocol in water
The resulting suspension of cellulose nanofibrils is advantageously at least 1 s ^-1 At shear rates of no polyhydroxylated compounds and no auxiliary additives and
Low viscosity levels of the suspension of cellulose nanofibrils that have not been subjected to the drying step
It shows a viscosity level corresponding to at least 50%.

Of course, the combination of essentially amorphous surface-loaded cellulose nanofibrils (preferably acid-loaded) with a polyhydroxylated compound and optional auxiliary additives is described by the present invention. At least one vehicle (excipient) adapted for hair, skin or sun protection applications in the cosmetic formulation obtained according to
Used as a mixture with

The term “adapted for use on hair and / or skin” means that the vehicle damages or exerts a negative effect on the appearance of hair and / or skin And no irritation to the skin and / or eyes and / or scalp.

Another subject matter of the present invention is to provide essentially amorphous cellulose nanofibrils in dry dispersible form in combination with at least one polyhydroxylated organic compound as described above, as a texturizing agent and / or reinforcing agent. In cosmetic formulations used as agents.
These formulations may also contain the aforementioned additives.

In the cosmetic preparation according to the invention, the vehicle or a mixture of several vehicles is preferably present at a concentration in the range of approximately 0.5 to 99.5%, preferably in the range of approximately 5 to 90%. It is even more preferred to be present.

Vehicles suitable for the formulation according to the invention include, for example, those used in sprays, foams, tonics, gels, shampoos or rinse lotions.

Of course, the choice of the appropriate vehicle will depend on the type of application for which the formulation is intended.
Vehicles suitable for formulations intended to remain on the surface to which they are applied (eg sprays, foams, lotions, tonics or gels) are suitable for formulations which must be rinsed after use (eg conditioners, rinse lotions). Would not be a vehicle.

Thus, the vehicles which can be used can be simple or complex, and such vehicles are used in cosmetic formulations for hair, skin and sun protection applications Numerous commonly used products are included.

Thus, it may optionally be provided with a solubilizing agent (eg, C ₁ -C ₆ alcohol and mixtures thereof, especially ethanol, isopropanol or propylene glycol and mixtures thereof) to dissolve or disperse the active ingredients used. Can be refilled water.

Advantageously, with respect to solubilizers of the alcohol type, a good compatibility of the cellulose nanofibrils in combination with at least one polyhydroxylated organic compound is observed. The texture properties of these cellulose nanofibrils are not adversely affected in aqueous or alcoholic media.

Also, they maintain their properties in so-called more aggressive media, ie acidic media such as creams containing α-hydroxy acids or alkaline media such as depilatory formulations or permanent lotions.

Examples 2 and 3 given below describe this advantageous behavior of cellulose nanofibrils combined with at least one polyOH in cosmetic applications.

CNFs formulated according to the present invention have been found to be excellent structurants for cosmetic media and to maintain their properties over time. Their thickening power is greater than that of microcrystalline cellulose.

Also, in the fatty phase separated from the aqueous phase of CNF according to the invention, mineral oil {eg Ma
rcol 82®, vegetable oils or oils of marine origin, halogenated hydrocarbons, linalool, esters (eg isopropyl myristate) and silicones (suitable for cosmetic use) (especially cyclodimethicone and One or more emollients selected from dimethicones and derivatives and hexamethyldisiloxane) and their derivatives or mixtures can also be combined.

When the cosmetic preparation is provided in the form of a spray, tonic lotion, gel or foam, preferred solvents include water, ethanol, volatile silicone derivatives and mixtures thereof. The solvents used in these mixtures may be miscible or immiscible with each other. Aerosol sprays and foams also
Any propellant that can produce a uniform fine spray or a foam form of the substance can also be used. By way of example, mention may be made of dimethyl ether, propane, n-butane or isobutane.

If the cosmetic formulation is intended for topical topical application, the vehicle must have good comfort properties, be compatible with all other ingredients and be completely harmless .

[0087] These vehicles can take many forms, such as emulsion, foam or spray types. For example, vehicles in the form of emulsions include water-in-silicone, water-in-oil, oil-in-water, and oil-in-water-in-silicone emulsions. These emulsions have a wide viscosity range, e.g.
It covers a viscosity range of 0000 mPa · s. These emulsions can also be ejected in the form of a spray by using a mechanical pump type device or a device pressurized with propellant gas. These vehicles can also be spouted in the form of a foam.

At the same time as the above-mentioned vehicles, the cosmetic preparations according to the invention are for dispersing, emulsifying, dissolving or stabilizing the various compounds used, in particular those used for their softening and moisture properties. May be used. These are anionic, nonionic, cationic, zwitterionic (
zwitterionic) can also be of the amphoteric type. Illustrative of these compounds are the following:-as anionic surfactants, alkyl ester sulfonates, alkyl sulfates, alkyl amide sulfates and salts of saturated or unsaturated fatty acids;
- Examples of the nonionic surfactant, polyoxyalkylene alkylphenols, N- alkylamines derived from the glucosamide, glucamide or glycerol amide, polyoxyalkylenated C ₈ -C ₂₂ aliphatic alcohols, ethylene oxide Sid hydrophobic compound and the product obtained from the condensation or propylene oxide with the product resulting from the condensation of propylene glycol, amine oxides, alkyl polyglycosides and their polyoxyalkylenated derivatives, C ₈ -C ₂₀ fatty amine de, and ethoxylated Fatty acids, ethoxylated amides, ethoxylated amines or ethoxylated amidoamines.-As amphoteric and zwitterionic surfactants, those of the betaine type, such as betaine, sulfobetaine, amidoalkylbetaine and amide alkyl Sulfobetaine, alkyl sultaine, condensation product of fatty acid and protein hydrolyzate, amphoteric cocoamphoacetate and cocoamphodiacetate, alkylamphopropionate or alkylamphodipropionate, or alkylpolyamine Derivatives.

Further, a conditioner can be present. Among these are those synthesized by well known polyquaternium names such as polyquaternium-2, polyquaternium-7 and polyquaternium-10, cocodimonium hydroxyethylcellulose, Guar hydroxypropyltrimonium (trimon
ium) chloride or a cationic derivative of a polysaccharide such as hydroxypropyl guar hydroxypropyltrimonium chloride, or amodimethicone (amod
Non-volatile silicone derivatives such as imethicone), cyclomethicone or water-insoluble and non-volatile organopolysiloxanes such as oils, resins or gums, for example diphenyl dimethicone gum.

The cosmetic formulation can also include a polymer that exhibits film-forming properties that can be used to provide a fixing action. These polymers have a
It is generally present at a concentration in the range of 1 to 10%, preferably at a concentration in the range of 0.5 to 5%. These are preferably of the following types: polyvinylpyrrolidone, copolymers of polyvinylpyrrolidone and methyl methacrylate, copolymers of polyvinylpyrrolidone and vinyl acetate, poly (ethylene glycol terephthalate) / poly (ethylene glycol) copolymers or Sulfonated terephthalic acid copolyester polymer.

[0091] The cosmetic formulation also comprises a polymer-based derivative that exerts a protective effect by about 0.01.
10 to 10% by weight, preferably about 0.1 to 5% by weight, and the derivative may be, for example, a cellulose derivative, a poly (graft) grafted onto a polyalkylene backbone.
Vinyl esters), poly (vinyl alcohol), sulfonated terephthalic acid copolyester polymers, ethoxylated monoamines or polyamines, and ethoxylated amine polymers.

[0092] Moisturizing agents can also be incorporated into cosmetic formulations. Examples of these additives include, in particular, glycerol, propylene glycol, urea, collagen, gelatin and softeners (generally alkyl monoglycerides, alkyl diglycerides or alkyl triglycerides, such as oils extracted from plants and vegetables or their hydrogenation). Derivatives, mineral or paraffin oils, diols, fatty acid esters or silicones).

In general, one or more fragrances, colorants and / or opacifiers (eg pigments) are added to these compounds.

In order to protect the skin and / or hair from attack by sunlight and ultraviolet light,
Sunscreens (sunscreens, sunscreens, filtres solaires) in these formulations
Can be added. This light-shielding agent is either an organic compound that strongly absorbs ultraviolet light or inorganic particles in a nanoparticle state such as zinc oxide, titanium dioxide or cerium oxide.

Active ingredients with purely cosmetic properties, such as vitamins, α-hydroxy acids, plant derivatives or marine extracts, can be combined with the CNF-containing formulation for the purpose of a therapeutic effect.

Also, CNF is a preferred texturizing agent in depilatory formulations, for example, a medium based on calcium thioglycolate.

In accordance with supplementation VII of the cosmetic cosmetique, p-hydroxybenzoic acid esters, sodium benzoate or any chemical agent that prevents the growth of bacteria or fungi conventionally used in cosmetic compositions Such preservatives are generally incorporated into these compositions at a rate of 0.01 to 3% by weight.

Finally, cosmetic formulations are also available from Carbopol (marketed by Goodrich)
(Registered trademark) type crosslinked polyacrylates, cellulose derivatives such as hydroxypropylcellulose or carboxymethylcellulose, guars and their derivatives {eg hydroxypropyl guar, eg Jaguar HP (registered trademark)}, locust bean gum, cod (Tara) or cassia
Gumifying or gelling polymers such as gums, xanthan gums such as Rhodicare®, succinoglycans, alginate, carrageenan, chitin derivatives or any other polysaccharide having a texturing effect can also be included. .

The selection of these so-called conventional compounds and the evaluation of their respective amounts is directly related to the type of formulation in question (ie gels, creams, emulsions, sprays, lotions, etc.) and the desired comfort properties. It is clear. These adjustments are, in fact, a matter of routine operation for cosmetics formulators.

The cosmetic preparations according to the invention can be used advantageously in the fields of hair, sun protection, body care and makeup.

The following examples are given by way of illustration only and are not intended to limit the invention.

Example 1 Preparation of a Mixture of Cellulose Nanofibrils and Carboxymethyl Cellulose Carboxymethyl cellulose with a substitution degree of 1.2 (CMC Blanose® 12M8P from Aqualon) is dissolved in distilled water. This solution was then dispersed in a nanofibril-dispersed mother liquor (1) using Ultra-Turrax in advance.
2.3 homogenized at 4000 rpm (1 minute per 100 g of dispersion)
% Cellulose nanofibrils. The combined mixture is stirred for 30 minutes at 1000 rpm using a deagglomeration paddle. The amount of carboxymethylcellulose added is 15% by weight based on the weight of cellulose nanofibrils and carboxymethylcellulose.

The mixture is then poured into dishes and then dried (ie dried at 40 ° C. in a vented oven) to a solids content of 92% as monitored by quantitative water measurement by the Karl-Fischer method. The dried mixture is then milled and then sieved through a 500 μm sieve. The obtained powder is redispersed in distilled water at a ratio of 0.43% by weight of cellulose nanofibrils and carboxymethyl cellulose. 100 using a paddle for deagglomeration
Stirring is performed at 0 rpm for 5 or 30 minutes. This dispersion is used in the following examples.

Example 2 Behavior of CNF in Combination with CMC in an Alcoholic Medium To do this, the CNF / CMC mixture prepared in Example 1 is dispersed in water with shear and then the alcohol to be investigated is added. The one without this alcohol is also prepared. The compositions of the two aqueous / alcoholic media thus prepared are described in Table I below. The viscosities of these media and the control media (water) are evaluated using a Brookfield LVT type viscometer. The results are shown in Table I.

[0105]

[Table 1]

Example 3 Behavior of CNF in Combination with CMC in Acidic or Alkaline Medium The CNF mixture prepared according to Example 1 is introduced into water treated with a buffer to a pH of 4 or 9. The rheological behavior of this medium is evaluated against a control medium containing 1% of microcrystalline cellulose with the addition of CMC. The change over time in viscosity is shown in Table II.

[0107]

[Table 2]

CNFs formulated according to the present invention have been found to be excellent structurants for cosmetic media and to maintain their properties over time. Their viscosity-imparting power was greater than that of microcrystalline cellulose.

Example 4 Cosmetic formulations according to the invention These formulations include the CNF / CMC mixture prepared in Example 1.

(1) Cream having α-hydroxy acid

[Table 3] qs 100 = amount sufficient to make the whole 100% by weight qs = appropriate amount

(2) Soft skin friction agent for body (exfoliant, exfolliant)

[Table 4]

(3) Hair removal lotion

[Table 5]

Example 5 Behavior of CNF in Combination with CMC as Reinforcing Agent for Dispersions of Film Forming Polymers The purpose of this example is to provide a combination of nanofibrils and at least one (polyOH) To show that it can also be an agent. The test used Rhodopas DS 1003 film-forming latex (aqueous dispersion of acrylic polymer) sold by Rhodia. Its glass transition temperature Tg is 1
The film formation temperature TMF is below 5 ° C., the solids content of the dispersion is 50% and the particle size of this latex is 0.1 μm. This dispersion exhibits a pH of about 8. In this example, a dispersion of cellulose nanofibrils obtained in Example 1 from a dry powder is used.

Formulations That Can Serve as a Base for Aqueous Nail Polish Two formulations are prepared based on the DS 1003 latex described above. F1 (comparative example): 30% by weight of 1003 latex + 70% by weight of water, based on the total weight of the formulation; F2 (according to the invention): 30 parts by weight of 1003 latex, based on the total weight of the formulation + obtained in Example 1 1% by weight of obtained CNF + 69% by weight of water. The pH of the medium is adjusted to 7.

F1 exhibited a viscosity of less than 10 mPa · s, whereas F2 exhibited a viscosity of about 4
It was 500 mPa · s. These viscosities were evaluated using a Brookfield LVT type viscometer (rotor 3, 10 rpm).

The results are summarized in Table III.

[Table 6]

The Persoz hardness was measured according to NF standard T30-016. The hardness was measured at three different points on the plate after drying for at least 8 days at room temperature. Each measurement corresponds to the average of three measurements. The results show the time (seconds) required for the pendulum amplitude angle to decay from 12 ° to 4 °. This time increases as the "hardness" of the film increases.

The adhesion to the substrate was measured by a cross hatching test according to ISO standard 2409. A film was prepared on a steel plate. This test consists of making a cut in the film by a cross hatch (oblique parallel line pattern) method using a cutter with six parallel lines at 1 mm intervals, and peeling off the cross hatch portion with an adhesive tape. The grading ranged from 0 (no peeling) to 4 (about 50% of the crosshatch was peeled).

The formulation F2 comprising the added CNF of the invention thus represents a material which can be used as an aqueous varnish (manicure) base. The resulting formulation F2,
It was stable. Due to the pseudoplastic nature, it spreads easily on the substrate. The film exhibited good adhesion and good flexibility and had a non-greasy and non-greasy feel.

[Procedure amendment]

[Submission date] June 12, 2000 (2000.6.12)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

Thus, carboxymethylated cellulose having a high molecular weight (in this case, the content of carboxylated cellulose is 5% by weight or more and 30% by weight or less) or carboxymethylated cellulose having a low molecular weight (in this case, The content of carboxylated cellulose is more specifically in the range of 10 to 30% by weight).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) A61K 7/48 A61K 7/48 7/50 7/50 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD) , RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, G , GE, GH, GM, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW F-term (reference) 4C083 AB032 AC022 AC072 AC122 AC131 AC242 AC302 AC392 AC402 AC422 AC442 AC542 AC642 AC762 AC772 AC782 AC902 AD042 AD072 AD092 AD152 AD221 AD261 AD262 AD271 AD351 AD512 BB04 BB05 BB07 CC02 CC03 CC05 CC18 CC28 CC31 DD27 DD31

Claims (16)

[Claims] 1. An essentially amorphous cellulose nanofibril having a degree of crystallinity of less than 50% in dry dispersible form, which is used as a texture agent and / or a reinforcing agent in a cosmetic formulation and at least one of the same. In combination with a polyhydroxylated (polyOH) organic compound. 2. The combination according to claim 1, wherein the polyhydroxylated (polyOH) organic compound is selected from carbohydrates and their derivatives and polyalcohols. 3. The method according to claim 2, wherein the carbohydrate is selected from C _{3 to} C ₆ cyclic or linear monosaccharides, oligosaccharides, polysaccharides and their fatty derivatives, and alcohol, acid and ether carbohydrates. A combination according to claim 2. 4. The method as claimed in claim 1, wherein the polyhydroxylated (polyOH) organic compound is selected from carboxymethylcellulose, xanthan gum, guar, sorbitol, sucrose and mixtures thereof. The combination as described. 5. The combination according to claim 1, wherein said crystallinity is in the range of 15 to 50%. 6. The combination according to claim 1, wherein the cellulose nanofibrils exhibit at least 80% of cells having primary walls. 7. The combination according to claim 1, wherein the cellulose nanofibrils are obtained from cells consisting of at least about 80% of the primary wall. 8. The combination according to claim 1, wherein the cellulose nanofibrils are loaded with carboxylic acids and acidic polysaccharides alone or as a mixture. 9. The polyhydroxylated organic compound is combined with the cellulose nanofibrils in a weight ratio of (poly OH) × 100 / [(poly OH) + (C NF)] of 5% or more and 50% or less. A combination according to any of the preceding claims, characterized in that: 10. The combination according to claim 9, wherein the weight ratio of (polyOH) × 100 / [(polyOH) + (CNF)] is 5% or more and 30% or less. 11. The cellulose nanofibril is combined with carboxymethyl cellulose (CMC) having a high degree of substitution at a weight ratio of (CMC) × 100 / [(CMC) + (CNF)] of 5% or more and 25% or less. The combination according to any one of claims 4 to 10, characterized in that: 12. The method of claim 11, wherein the cellulose nanofibrils are present in the cosmetic preparation in an amount of from 0.1 to 20.
The combination according to any of the preceding claims, characterized in that the amount of the mixture of cellulose nanofibrils and (polyOH) has been adjusted to be used in proportions by weight. 13. The combination according to claim 12, wherein the nanofibrils are used in a proportion of 0.15 to 5% by weight. 14. The cellulose nanofibril and (polyOH) are represented by the following formula (R ¹ R ² N) COA, wherein R ¹ and R ² may be the same or different and include hydrogen or C ₁ to A represents a C ₁₀ alkyl group, A represents hydrogen, a C ₁ -C ₁₀ alkyl group or a group R ′ ¹ R ′ ² N (where R ′ ¹ and R ′ ² may be the same or different, the compounds of hydrogen or represent C ₁ -C ₁₀ alkyl group)}; and anionic, at least one co-additive chosen from nonionic or amphoteric surface active agent (these auxiliary additives used alone Can also be used as a mixture).
A combination according to any of claims 1 to 13. 15. The content of the polyhydroxylated compound and the auxiliary additive is 5% by weight based on the weight of the nanofibrils, the polyhydroxylated compound and the auxiliary additive.
The combination according to claim 14, wherein the content is at least 30% by weight. 16. The composition as claimed in claim 1, wherein the composition is a texture agent and / or a reinforcing agent.
A cosmetic preparation comprising the combination according to any one of the above.