WO2022088051A1

WO2022088051A1 - Anhydrous composition for caring for and/or making up keratin materials

Info

Publication number: WO2022088051A1
Application number: PCT/CN2020/125290
Authority: WO
Inventors: Yujie HUANG
Original assignee: L'oreal
Priority date: 2020-10-30
Filing date: 2020-10-30
Publication date: 2022-05-05
Also published as: CN116507317A; FR3115693A1; FR3115693B1; JP2023547025A

Abstract

An anhydrous composition for caring for and/or making up keratin materials comprises, a) at least one non-volatile phenyl silicone oil optionally having a dimethicone fragment corresponding to formula (I) below: in which the groups R represent, independently of each other, methyl or a phenyl, with the proviso that at least one group R represents a phenyl; b) at least one non-volatile phenyl silicone oil optionally having at least one dimethicone fragment correspond to formula (II) below: in which Me is methyl and Ph is phenyl, OR' represents a group-OSiMe 3 and p is 0 or is between 1 and 1000, and m is between 1 and 1000; and c) at least one film-forming polymer selected from cellulose ethers; wherein the weight ratio of the non-volatile phenyl silicone oil corresponding to formula (I) to the non-volatile phenyl silicone oil corresponding to formula (II) is from 0.5 to 1. A process for caring for and/or making up keratin materials such as the skin and the lips, comprises applying the anhydrous composition according to the keratin materials.

Description

ANHYDROUS COMPOSITION FOR CARING FOR AND/OR MAKING UP KERATIN MATERIALS

TECHNICAL FIELD

The present invention relates to an anhydrous composition for caring for and/or making up keratin materials such as the skin and the lips, preferably the lips. The present invention also relates to a process for caring for and/or making up keratin materials such as the skin and the lips, preferably the lips.

BACKGROUND ART

Compositions for caring for and/or making up the skin and/or the lips are produced to satisfy the need of moisturization or hydration of the skin and the lips.

Many lipsticks will migrate, i.e., have featherings at small wrinkles of the lips after application.

To date, some prior art documents relating to cosmetic compositions for making up and/or caring for the skin and/or the lips have been published.

WO 2013/191300 discloses a solid cosmetic composition for making up and/or caring for the skin and/or the lips, comprising in a physiologically acceptable medium at least one fatty phase comprising:

- from 5 to 30%by weight of (a) non-volatile hydrocarbonated apolar oils, or a mixture thereof, relative to the total weight of the composition,

- from 43 to 90%by weight of the total content of (a) non-volatile silicone oil (s) relative to the total weight of the composition, wherein at least one of said non-volatile silicone oil (s) is a non-volatile phenylated silicon oil, and

- from 3 to 30%by weight of (a) wax (es) , or a mixture thereof, relative to the total weight of the composition.

WO 2012/165130 discloses a cosmetic for lips which is characterized by comprising: (a) 5 to 30 mass%of hydrogenerated polyisobutene; (b) 30 to 70 mass%of one or more kinds of methyl phenyl silicones separating when mixed with (a) at 25℃; (c) 0.5 to 15 mass%of an oil separating when: mixed with (a) at 25℃; and mixed with (b) at 25℃; and (d) 4 to 12 mass%of a wax.

In general, when women use makeup products, especially lip products such as lipstick or lip gloss, they hope that lip products are stable and have good application properties such as glideness and leave a deposit with a good shine level on the lips. It is desired that the products does not easily migrate after application.

Thus, there is still a need to obtain products for caring for and/or making up keratin materials such as the skin and the lips which are stable and have good glideness and will leave a shiny deposit having good migrate resistance on keratin materials such as the skin and the lips.

SUMMARY OF THE INVENTION

One object of the present invention is thus to provide products for caring for and/or making up keratin materials such as the skin and the lips which are stable and have good glideness and will leave a shiny deposit having good migrate resistance on keratin materials such as the skin and the lips.

Another object of the present invention is to provide a process for caring for and/or making up keratin materials such as the skin and the lips, preferably the lips.

Thus, according to one aspect, the present invention provides an anhydrous composition for caring for and/or making up keratin materials comprising:

a) at least one non-volatile phenyl silicone oil optionally having a dimethicone fragment corresponding to formula (I) below:

in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl;

b) at least one non-volatile phenyl silicone oil optionally having at least one dimethicone fragment correspond to formula (II) below:

in which Me is methyl and Ph is phenyl, OR' represents a group-OSiMe ₃ and p is 0 or is between 1 and 1000, and m is between 1 and 1000; and

c) at least one film-forming polymer selected from cellulose ethers;

wherein the weight ratio of the non-volatile phenyl silicone oil corresponding to formula (I) to the non-volatile phenyl silicone oil corresponding to formula (II) is from 0.5 to 1.

According to another aspect, the present invention provides a process for caring for and/or making up keratin materials such as the skin and the lips, comprising applying the anhydrous composition as described above to the keratin materials.

It has been surprisingly found that the anhydrous composition obtained has good glideness and leaves a shiny deposit having good migrate resistance on keratin materials such as the skin and the lips.

In addition, the anhydrous composition according to the present invention is stable, i.e. it would not lapse after being remained at 20℃, 37℃ and 45℃ for 2 months.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "between…and…" and "ranging from…to…” .

As used herein, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones.

As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of” ) .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the field the present invention belongs to. When the definition of a term in the present description conflicts with the meaning as commonly understood by those skilled in the field the present invention belongs to, the definition described herein shall apply.

Unless otherwise specified, all numerical values expressing amount of ingredients and the like used in the description and claims are to be understood as being modified by the term “about” . Accordingly, unless indicated to the contrary, the numerical values and parameters described herein are approximate values which are capable of being changed according to the desired performance obtained as required.

For the purposes of the present invention, the term "anhydrous" means that the composition according to the present invention contains less than 2 wt. %and preferably less than 0.5 wt. %of water relative to the total weight of the composition. Where appropriate, such small amounts of water may be provided by ingredients of the composition that contain it in residual amount, but are not deliberately provided.

As used herein, the term “keratin materials” refer to the skin and the lips. By “skin” , we intend to mean all the body skin, including the scalp. Preferably, the keratin material is the lips.

The anhydrous composition for caring for and/or making up keratin materials according to the present invention comprises:

c) at least one film-forming polymer selected from cellulose ethers;

In some embodiments, the anhydrous composition according to the present invention is solid.

The term "solid" used herein means the hardness of the composition at 20℃ and at atmospheric pressure (760 mmHg) is greater than or equal to 30 Nm ^-1 when it is measured according to the protocol described below.

The composition whose hardness is to be determined is stored at 20℃ for 24 hours before measuring the hardness.

The hardness may be measured at 20℃ via the “cheese wire” method, which consists in transversely cutting a wand of product, which is preferably a circular cylinder, by means of a rigid tungsten wire 250 μm in diameter, by moving the wire relative to the stick at a speed of 100 mm/minute.

The hardness of the samples of compositions of the present invention, expressed in Nm ^-1, is measured using a DFGS2 tensile testing machine from the company Indelco-Chatillon.

The measurement is repeated three times and then averaged. The average of the three shear values read using the tensile testing machine mentioned above, noted Y, is given in grams. This average is converted into Newtons and then divided by L which represents the longest distance through which the wire passes. In the case of a cylindrical wand, L is equal to the diameter (in metres) .

The hardness is converted into Nm ^-1 by the equation below:

(Y×10 ^-3×9.8) /L

For a measurement at a different temperature, the composition is stored for 24 hours at this new temperature before the measurement.

According to this measuring method, the composition according to the present invention preferably has hardness at 20℃ and at atmospheric pressure of greater than or equal to 40 Nm ^-1 and preferably greater than 55 Nm ^-1.

Preferably, the composition according to the present invention especially has a hardness at 20℃ of less than 200 Nm ^-1, especially less than 150 Nm ^-1 and preferably less than 100 Nm ^-1.

Advantageously, the composition has a shear value ranging from 50 to 90 gF and preferably from 65 to 80 gF. Thus, the composition may be formulated in standard packaging that does not require any composition support means.

Non-volatile phenyl silicone oil (s)

According to one aspect, the composition according to the present invention comprises at least one non-volatile phenyl silicone oil corresponding to formula (I) and at least one second non-volatile phenyl silicone oil corresponding to formula (II) .

The term "oil" means a water-immiscible non-aqueous compound that is liquid at room temperature (25℃) and atmospheric pressure (760 mmHg) .

The term "non-volatile" means an oil of which the vapor pressure at 25℃ and atmospheric pressure is non-zero and is less than 0.02 mmHg (2.66 Pa) and better still less than 10 ^-3 mmHg (0.13 Pa) .

The term "silicone oil" means an oil containing at least one silicon atom, and in particular containing Si-O groups.

The expression "phenyl silicone oil" denotes a silicone oil bearing at least one phenyl substituent.

These non-volatile phenyl silicone oils may be selected from those having at least one dimethicone fragment, or from those not having one.

According to the present invention, a dimethicone fragment corresponds to the following unit:

-Si (CH ₃) ₂-O-.

Non-volatile phenyl silicone oils optionally having a dimethicone fragment corresponding to formula (I) :

in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.

Preferably, the phenyl silicone oil of formula (I) comprises at least three, at least four or at least five, phenyl groups.

Mixtures of different phenylorganopolysiloxane compounds described above can be used.

Examples that may be mentioned include mixtures of triphenyl-, tetraphenyl-or pentaphenyl-organopolysiloxanes.

Among the compounds of formula (I) , mention may be made more particularly of phenyl silicone oils not having any dimethicone fragments, corresponding to formula (I) in which at least 4 or at least 5 radicals R represent a phenyl radical, the remaining radicals representing methyls.

Such non-volatile phenyl silicone oils are preferably trimethylpentaphenyltrisiloxane or tetramethyltetraphenyltrisiloxane. They are in particular sold by Dow Corning under the reference PH-1555 HRI or Dow

555 Cosmetic Fluid (chemical name: 1, 3, 5-trimethyl-1, 1, 3, 5, 5-pentaphenyltrisiloxane; INCI name: trimethylpentaphenyltrisiloxane) , or the tetramethyltetraphenyltrisiloxane sold under the reference Dow Corning 554 Cosmetic Fluid by Dow Corning can also be used.

They correspond in particular to formulae (Ia) and (Ib) below:

in which Me represents methyl and Ph represents phenyl.

According to some embodiments, the non-volatile phenyl silicone oil of formula (I) is selected from trimethylpentaphenyltrisiloxane and tetramethyltetraphenyltrisiloxane.

Preferably, the non-volatile phenyl silicone oil of formula (I) is present in amount ranging from 1 wt. %to 30 wt. %, preferably from 2 wt. %to 20 wt. %and more preferably from 5 wt. %to 12 wt. %, relative to the total weight of the composition.

Non-volatile phenyl silicone oils optionally having at least one dimethicone fragment correspond to formula (II) :

in which Me is methyl and Ph is phenyl, OR' represents a group-OSiMe ₃ and p is 0 or is between 1 and 1000, and m is between 1 and 1000. In particular, m and p are such that the phenyl silicone oil of formula (II) is a non-volatile oil.

According to an embodiment, the non-volatile phenyl silicone of formula (II) has at least one dimethicone fragment, p is between 1 and 1000 and m is more particularly such that the compound (II) is a non-volatile oil. Trimethylsiloxyphenyl dimethicone, sold in particular under the reference Belsil PDM 1000 by the company Wacker, may, for example, be used.

According to an embodiment, the non-volatile phenyl silicone of formula (II) does not has a dimethicone fragment, p is equal to 0 and m is between 1 and 1000, and in particular m is such that the compound (II) is a non-volatile oil.

Phenyltrimethylsiloxytrisiloxane, sold in particular under the reference Dow

556 Cosmetic Grade Fluid (DC556) , may, for example, be used.

According to some embodiments, the non-volatile phenyl silicone oil of formula (II) is selected from phenyltrimethylsiloxytrisiloxane and trimethylsiloxyphenyl dimethicone.

Preferably, the non-volatile phenyl silicone oil of formula (II) is present in amount ranging from 2 wt. %to 40 wt. %, preferably from 6 wt. %to 30 wt. %and more preferably from 10 wt. %to 24 wt. %, relative to the total weight of the composition.

Cellulose ethers

According to one aspect, the composition according to the present invention comprises at least one film-forming polymer selected from cellulose ethers.

Non-limiting examples of cellulose ethers include methyl cellulose, ethyl cellulose, propyl cellulose, methylethyl cellulose, carboxymethyl cellulose (cellulose gum) , ethyl carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, and a mixture thereof.

In some preferred embodiments, the at least one film-forming polymer is selected from methyl cellulose, ethyl cellulose, propyl cellulose and methylethyl cellulose.

As a commercial example of cellulose ether, mention can be made of AQUALON ^TM EC N7 PHARM (ethyl cellulose) available from the company ASHLAND.

Preferably, the film-forming polymer is present in amount ranging from 0.5 wt. %to 10 wt. %, preferably from 1 wt. %to 8 wt. %and more preferably from 2 wt. %to 6 wt. %, relative to the total weight of the composition.

Additional oils

The anhydrous composition according to the present invention may further comprises one or more additional oils besides the non-volatile phenyl silicone oils described above.

The additional oils can be non-volatile oils and/or volatile oils.

The term "volatile oil" means any non-aqueous medium that is capable of evaporating on contact with the skin or the lips in less than one hour, at room temperature and atmospheric pressure. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm ²/min, limits included.

The oils may be silicone oil, fluoro oil, hydrocarbon-based oil, or a mixture thereof.

The term “fluoro oil” means an oil comprising at least one fluorine atom.

The oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.

The silicone oil and fluoro oil may be selected from polar oils, apolar oils, or mixtures thereof.

The “hydrocarbon-based oil” used as the additional oil can be polar oils.

Forthe purposes of the present invention, the term “polar oil” means an oil solubility parameter thereof at 25℃, δa, is other than 0 (J/cm ³) ^1/2.

According to a preferred embodiment, the composition according to the present invention comprises at least one additional oil selected from octyldodecanol, stearyl heptanoate, stearyl caprylate, isohexadecane, C12-15 alkyl benzoate, dimethicone, and mixtures thereof.

When exists, the additional oil (s) is present in the composition according to the present invention in an amount ranging from 30 wt. %to 70 wt. %, preferably from 40 wt. %to 65 wt. %, relative to the total weight of the composition.

Advantageously, the total amount of all oils is present in the composition of the present invention ranges from 50 wt. %to 80 wt. %, preferably from 60 wt. %to 75 wt. %, relative to the total weight of the composition.

The anhydrous composition according to the present invention may further comprises additional oil at least one wax and/or at least one colorant.

Wax (s)

The wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25℃) , with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30℃, preferably greater than or equal to 40℃, which may be up to 200℃ and in particular up to 120℃.

Waxes used in the present invention includes waxes of animal origin, waxes of plant origin, waxes of mineral origin, synthetic waxes, and various fractions of waxes of natural origin.

Animal waxes include, but are not limited to, beeswax, spermaceti, lanolin wax, derivatives of lanoline and China insect waxes. Vegetable waxes includes, but are not limited to, rice wax, carnauba wax, candelilla wax, ouricurry wax, cork fiber wax, sugar cane wax, cocoa butter, Japan wax and sumac wax. Mineral waxes include, but are not limited to, montan wax, microcrystalline waxes, paraffins, ozokerite, petroleum jelly and ceresine. Synthetic waxes include, but are not limited to, polyethylene homopolymer and compolymer waxes, synthecit beewax, waxes obtained by the Fisher and Tropsch synthesis, and silicon waxes.

Waxes obtained by catalytic hydrogenation of animal or vegetable oils, having linear or branched C ₈-C ₃₂ fatty chains are also used, as well as fatty esters and glycerides.

Waxes also include silicone waxes, among which, mention may be made of polymethylsiloxane alkyls, alkoxys and/or esters. The waxes may be in the form of stable dispersions of colloidal wax particles, in according with known methods, such as "Microemulsions Theory and Practice" , L.M. Prince Ed., Academic Press (1977) , pages 21-32. Lignate wax may also be used.

Waxes useful in the composition according to the present invention may provide one or more of the following properties, including, but not limited to, bulking, texture, and a degree of water resistance. The waxes should not substantially reduce the gloss properties of a glossy film former, if presents.

According to a particularly preferred embodiment, the wax used in the present invention is selected from synthetic wax, paraffin, microcrystalline wax, polyethylene, VP/eicosene copolymer, and mixtures thereof.

If presents, the wax can be present in an amount ranging from 5 wt. %to 30 wt. %, preferably from 7 wt. %to 20 wt. %, more preferably from 8 wt. %to 15 wt. %, relative to the total weight of the composition.

Colorant (s)

For the purposes of the present invention, the term "colorant" means a compound that is capable of producing a colored optical effect when it is formulated in sufficient amount in a suitable cosmetic medium.

The colorant under consideration in the context of the present invention may be selected from water-soluble or water-insoluble, liposoluble or non-liposoluble, organic or inorganic colorants, and materials with an optical effect, and mixtures thereof.

Water-soluble dyes

The water-soluble colorants used according to the present invention are more particularly water-soluble dyes.

For the purposes of the present invention, the term "water-soluble dye" means any natural or synthetic, generally organic compound which is soluble in an aqueous phase or water-miscible solvents and which is capable of imparting colour. In particular, the term "water-soluble" is intended to characterize the capacity of a compound to dissolve in water, measured at 25℃, to a concentration at least equal to 0.1 g/l (production of a macroscopically isotropic, transparent, coloured or colourless solution) . This solubility is in particular greater than or equal to 1 g/l.

As water-soluble dyes that are suitable for use in the present invention, mention may be made in particular of synthetic or natural water-soluble dyes, for instance FD&C Red 4 (CI: 14700) , DC Red 6 (Lithol Rubine Na; CI: 15850) , DC Red 22 (CI: 45380) , DC Red 28 (CI: 45410 Na salt) , DC Red 30 (CI: 73360) , DC Red 33 (CI: 17200) , DC Orange 4 (CI: 15510) , FDC Yellow 5 (CI: 19140) , FDC Yellow 6 (CI: 15985) , DC Yellow 8 (CI: 45350 Na salt) , FDC Green 3 (CI: 42053) , DC Green 5 (CI: 61570) , FDC Blue 1 (CI: 42090) .

As non-limiting illustrations of sources of water-soluble colorant (s) that may be used in the context of the present invention, mention may be made in particular of those of natural origin, such as extracts of cochineal carmine, of beetroot, of grape, of carrot, of tomato, of annatto, of paprika, of henna, of caramel and of curcumin.

Thus, the water-soluble colorants that are suitable for use in the present invention are in particular carminic acid, betanin, anthocyans, enocyanins, lycopene, β-carotene, bixin, norbixin, capsanthin, capsorubin, flavoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, riboflavin, rhodoxanthin, cantaxanthin and chlorophyll, and mixtures thereof.

They may also be copper sulfate, iron sulfate, water-soluble sulfopolyesters, rhodamine, betaine, methylene blue, the disodium salt of tartrazine and the disodium salt of fuchsin.

Some of these water-soluble colorants are in particular approved for food use. Representatives of these dyes that may be mentioned more particularly include dyes of the carotenoid family, referenced under the food codes E120, E162, E163, E160a-g, E150a, E101, E100, E140 and E141.

Pigments

The term “pigments” should be understood as meaning white or coloured, inorganic (mineral) or organic particles, which are insoluble in a liquid organic phase, and which are intended to color and/or opacify the composition and/or the deposit produced with the composition.

The pigments may be selected from mineral pigments, organic pigments and composite pigments (i.e. pigments based on mineral and/or organic materials) .

The pigments may be selected from monochromatic pigments, lakes and pigments with an optical effect, for instance goniochromatic pigments and nacres.

The mineral pigments may be selected from metal oxide pigments such as chromium oxides, iron oxides (black, yellow, red) , titanium dioxide, zinc oxides, cerium oxides and, zirconium oxides, chromium hydrate, manganese violet, Prussian blue, ultramarine blue, ferric blue, SYNTHETIC FLUORPHLOGOPITE, metal powders such as aluminium powders and copper powder, and mixtures thereof.

Organic lakes are organic pigments formed from a dye attached to a substrate.

The lakes, which are also known as organic pigments, may be selected from the materials below, and mixtures thereof:

- cochineal carmine;

- organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes or fluorane dyes.

Among the organic pigments that may in particular be mentioned are those known under the following names: D&C Blue No. 4, D&C Brown No. 1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6;

- the organic lakes may be insoluble sodium, potassium, calcium, barium, aluminium, zirconium, strontium or titanium salts of acidic dyes such as azo, anthraquinone, indigoid, xanthene, pyrene, quinoline, triphenylmethane or fluorane dyes, these dyes possibly comprising at least one carboxylic or sulfonic acid group.

The organic lakes may also be supported on an organic support such as rosin or aluminium benzoate, for example.

Among the organic lakes, mention may be made in particular of those known under the following names: D&C Red No. 2 Aluminium lake, D&C Red No. 3 Aluminium lake, D&C Red No. 4 Aluminium lake, D&C Red No. 6 Aluminium lake, D&C Red No. 6 Barium lake, D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6 Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7 Aluminium lake, D&C Red No. 7 Barium lake, D&C Red No. 7 Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red No. 9 Aluminium lake, D&C Red No. 9 Barium lake, D&C Red No. 9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C Red No. 10 Sodium lake, D&C Red No. 19 Aluminium lake, D&C Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C Red No. 21 Aluminium lake, D&C Red No. 21 Zirconium lake, D&C Red No. 22 Aluminium lake, D&C Red No. 27 Aluminium lake, D&C Red No. 27 Aluminium/Titanium/Zirconium lake, D&C Red No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red No. 27 Zirconium lake, D&C Red No. 28 Aluminium lake, D&C Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No. 33 Aluminium lake, D&C Red No. 34 Calcium lake, D&C Red No. 36 lake, D&C Red No. 40 Aluminium lake, D&C Blue No. 1 Aluminium lake, D&C Green No. 3 Aluminium lake, D&C Orange No. 4 Aluminium lake, D&C Orange No. 5 Aluminium lake, D&C Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminium lake, D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminium lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6 Aluminium lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow No. 10 Aluminium lake, FD&C Blue No. 1 Aluminium lake, FD&C Red No. 4 Aluminium lake, FD&C Red No. 40 Aluminium lake, FD&C Yellow No. 5 Aluminium lake and FD&C Yellow No. 6 Aluminium lake.

Mention may also be made of liposoluble dyes, such as, for example, Sudan Red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow.

The chemical substances corresponding to each of the organic colorants cited above are mentioned in the publication "International Cosmetic Ingredient Dictionary and Handbook" , 1997 edition, pages 371 to 386 and 524 to 528, published by "The Cosmetic, Toiletries and Fragrance Association" , the content of which is incorporated into the present patent application by way of reference.

The pigments may also have been subjected to a hydrophobic treatment.

The hydrophobic treatment agent may be selected from silicones such as methicones, dimethicones, alkoxysilanes and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminium dimyristate, the aluminium salt of hydrogenated tallow glutamate, perfluoroalkyl phosphates, perfluoroalkylsilanes, perfluoroalkylsilazanes, polyhexafluoropropylene oxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, and amino acids; N-acylamino acids or salts thereof; lecithin, isopropyl triisostearyl titanate, and mixtures thereof.

The N-acylamino acids can comprise an acyl group containing from 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid may be, for example, lysine, glutamic acid or alanine.

The term “alkyl” mentioned in the compounds cited above in particular denotes an alkyl group containing from 1 to 30 carbon atoms and preferably containing from 5 to 16 carbon atoms.

Hydrophobically treated pigments are described in particular in patent application EP-A-1 086 683.

Nacres

For the purposes of the present patent application, the term "nacre" means coloured particles of any shape, which may or may not be iridescent, in particular produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.

Examples of nacres that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye in particular of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.

They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic colorants.

The nacres may more particularly have a yellow, pink, red, bronze, orangey, brown, gold and/or coppery colour or tint.

As illustrations of nacres that may be introduced as interference pigments into the first composition, mention may be made of the gold-coloured nacres sold in particular by the company BASF under the name Brilliant gold 212G (Timica) , Gold 222C (Cloisonne) , Sparkle gold (Timica) and Monarch gold 233X (Cloisonne) ; the bronze nacres sold in particular by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne) ; the orange nacres sold in particular by the company BASF under the name Orange 363C (Cloisonne) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna) ; the brown tinted nacres sold in particular by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chroma-lite) ; the copper-tinted nacres sold in particular by the company BASF under the name Copper 340A (Timica) ; the red-tinted nacres sold in particular by the company Merck under the name Sienna fine (17386) (Colorona) ; the yellow-tinted nacres sold in particular by the company BASF under the name Yellow (4502) (Chromalite) ; the gold-tinted red nacres sold in particular by the company BASF under the name Sunstone G012 (Gemtone) ; the pink nacres sold in particular by the company BASF under the name Tan opal G005 (Gemtone) ; the gold-tinted black nacres sold in particular by the company BASF under the name Nu antique bronze 240 AB (Timica) , the blue nacres sold in particular by the company Merck under the name Matte blue (17433) (Microna) , the silvery-tinted white nacres sold in particular by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold in particular by the company Merck under the name Indian summer (Xirona) , and mixtures thereof.

Goniochromatic pigments

For the purposes of the present invention, the term "goniochromatic pigment" denotes a pigment which makes it possible to obtain, when the composition is spread onto a support, a colour trajectory in the a*b* plane of the CIE 1976 colorimetric space that corresponds to a variation Dh° in the hue angle h° of at least 20° when the angle of observation relative to the normal is varied between 0° and 80°, for an incident light angle of 45°.

The color trajectory may be measured, for example, using an Instrument Systems brand spectrogonioreflectometer of reference GON 360 Goniometer, after the composition has been spread in fluid form to a thickness of 300 μm using an automatic spreader onto an Erichsen brand contrast card of reference Typ 24/5, the measurement being taken on the black background of the card.

The goniochromatic pigment may be chosen, for example, from multilayer interference structures and liquid-crystal colouring agents.

In the case of a multilayer structure, it may comprise, for example, at least two layers, each layer being made, for example, from at least one material selected from the group consisting of the following materials: MgF ₂, CeF ₃, ZnS, ZnSe, Si, SiO ₂, Ge, Te, Fe ₂O ₃, Pt, Va, Al ₂O ₃, MgO, Y ₂O ₃, S ₂O ₃, SiO, HfO ₂, ZrO ₂, CeO ₂, Nb ₂O ₅, Ta ₂O ₅, TiO ₂, Ag, Al, Au, Cu, Rb, Ti, Ta, W, Zn, MoS ₂, cryolite, alloys, polymers and combinations thereof.

The multilayer structure may or may not have, relative to a central layer, symmetry in the chemical nature of the stacked layers.

Different effects are obtained depending on the thickness and the nature of the various layers.

Examples of symmetrical multilayer interference structures are, for example, the following structures: Fe ₂O ₃/SiO ₂/Fe ₂O ₃/SiO ₂/Fe ₂O ₃, a pigment having this structure being sold under the name Sicopearl by the company BASF; MoS ₂/SiO ₂/mica-oxide/SiO ₂/MoS ₂; Fe ₂O ₃/SiO ₂/mica-oxide/SiO ₂/Fe ₂O ₃; TiO ₂/SiO ₂/TiO ₂ and TiO ₂/Al ₂O ₃/TiO ₂, pigments having these structures being sold under the name Xirona by the company Merck.

The liquid-crystal coloring agents comprise, for example, silicones or cellulose ethers onto which are grafted mesomorphic groups. Examples of liquid-crystal goniochromatic particles that may be used include, for example, those sold by the company Chenix and also those sold under the name

HC by the company Wacker.

Goniochromatic pigments that may also be used include certain nacres, pigments with effects on a synthetic substrate, in particular a substrate such as alumina, silica, borosilicate, iron oxide or aluminium, or interference flakes obtained from a polyterephthalate film.

By way of nonlimiting examples of goniochromatic pigments, mention may in particular be made, alone or in mixtures, of

goniochromatic pigments sold by SunChemicals, Cosmicolor

from Toyo Aluminium K.K.,

from Merck and Reflecks

from BASF.

Optionally, these particles may comprise or be covered with optical brightener (s) (or organic white fluorescent substances) .

Optical brighteners are compounds well known to a person skilled in the art. Such compounds are described in "Fluorescent Whitening Agent, Encyclopedia of Chemical Technology, Kirk-Othmer" , vol. 11, pp. 227-241, 4 ^th Edition, 1994, Wiley.

Their use in cosmetics in particular exploits the fact that they consist of chemical compounds having fluorescence properties, which absorb in the ultraviolet region (maximum absorption at a wavelength of less than 400 nm) and re-emit energy by fluorescence for a wavelength of between 380 nm and 830 nm. They may be defined more particularly as compounds that absorb essentially in the UVA region between 300 and 390 nm and re-emit essentially between 400 and 525 nm. Their lightening effect is based more particularly on an emission of energy between 400 and 480 nm, which corresponds to an emission in the blue part of the visible region, which contributes to lightening the skin visually when this emission takes place on the skin.

Optical brighteners that are in particular known include stilbene derivatives, in particular polystyrylstilbenes and triazinylstilbenes, coumarin derivatives, in particular hydroxycoumarins and aminocoumarins, oxazole, benzoxazole, imidazole, triazole and pyrazoline derivatives, pyrene derivatives, porphyrin derivatives and mixtures thereof.

The optical brighteners that can be used may also be in the form of copolymers, for example of acrylates and/or methacrylates, grafted with optical brightener groups as described in application FR 99 10942.

According to a preferred embodiment, the colorant used in the present invention is selected from metal oxide pigments, organic lakes, synthetic or natural water-soluble dyes and mixtures thereof.

According to a particularly preferred embodiment, the colorant used in the present invention is selected from YELLOW 5 LAKE, Blue 1 lake, RED 22 LAKE, RED 21, RED 7, titanium dioxide, iron oxides, synthetic fluorphlogopite, and mixtures thereof.

If presents, the colorant can be present in an amount ranging from 3 wt. %to 20 wt. %, preferably from 3 wt. %to 15 wt. %, more preferably from 5 wt. %to 12 wt. %, relative to the total weight of the composition.

Additives

The anhydrous composition according to the present invention may further comprise at least one additive usually used in the field under consideration. In particular the additive is selected from anionic, cationic, amphoteric or nonionic surfactants, thickening agents, fillers (such as methyl methacrylate crosspolymer) , antioxidants, preserving agents, fragrances, neutralizers, antiseptics, additional cosmetic active agents, such as vitamins, moisturizers, emollients or collagen-protecting agents, and mixtures thereof.

It is a matter of routine operations for a person skilled in the art to adjust the nature and amount of the additives present in the compositions in accordance with the present invention such that the advantageous properties of the composition used according to the present invention are not, or are not substantially, adversely affected by the envisaged addition.

According to a preferred embodiment, the present invention provides an anhydrous composition for caring for and/or making up keratin materials comprising, relative to the total weight of the composition:

a) from 5 wt. %to 12 wt. %of trimethyl pentaphenyl trisiloxane;

b) from 10 wt. %to 24 wt. %of trimethylsiloxyphenyl dimethicone;

c) from 2 wt. %to 6 wt. %of ethyl cellulose; and

d) from 8 wt. %to 15 wt. %of at least one wax selected from synthetic wax, paraffin, microcrystalline wax, polyethylene, VP/eicosene copolymer, and mixtures thereof;

e) from 5 wt. %to 12 wt. %of at least one colorant selected from YELLOW 5 LAKE, BLUE 1 lake, RED 22 LAKE, RED 21, RED 7, titanium dioxide, iron oxides, synthetic fluorphlogopite, and mixtures thereof; and

f) from 60 wt. %to 75 wt. %of at least one additional oil selected from octyldodecanol, stearyl heptanoate, stearyl caprylate, isohexadecane, C12-15 alkyl benzoate, dimethicone, and mixtures thereof.

Galenic form

The composition of the present invention is suitable to be used as a skincare or makeup product. More particularly, the composition of the present invention is in the form of lipstick and so on.

The composition according to the present invention may be prepared in a conventional manner.

The present invention also provides a process for caring for/making up keratin materials such as the skin and the lips, comprising applying the anhydrous composition as described above to the keratin materials.

The examples that follow are given as non-limiting illustrations of the present invention. The percentages are weight percentages.

Examples

Example 1

Lipsticks according to invention formula (IE. ) 1 and comparative formulas (CE. ) 1-3 were prepared with the ingredients listed in Table 1 (the contents are expressed as weight percentages of active material with regard to the total weight of each lipstick, unless otherwise indicated) :

Table 1

Preparation procedure:

The lipsticks were prepared by following the steps of:

i) Grinding all colorants (lakes, dyes, titanium dioxide and iron oxides) with a three roller mill into a pigment paste;

ii) Mixing the pigment paste and all other ingredients except ethyl cellulose, dimethicone, trimethylsiloxyphenyl dimethicone, and trimethyl pentaphenyl trisiloxane under 105℃ until homogeneous, stirring the mixture at 300rpm with a VMI type homogenizer;

iii) Then introducing ethyl cellulose little by little into the mixture and stirring at 500rpm with the VMI type homogenizer until ethyl cellulose dissolve completely;

iv) Introducing the rest ingredients and mixing;

v) Pouring the homogenized mixture into a lip stick mold preheated to 42±2℃, leaving the mixture in the mold under 25℃ until solidation; and

vi) Demolding the solid mixture from the lip stick mold cooled to about 4℃.

Evaluation:

Evaluation on the shear value, hardness and stability of the lipsticks, and usage effect such as glideness, and shininess of the deposit after application were performed.

Shear value and hardness were evaluated according to the protocol described previously.

Stability was evaluated by 5 experts by the following steps:

i) putting the lipsticks in ovens at 20℃, 37℃ and 45℃; and

ii) checking the appearance of lipsticks after 2 months.

Glideness is used to evaluate whether the lipstick can slide easily and smoothly during application on the lips.

Glideness was evaluated by 5 experts as follows: slowly applying a lipstick on the upper lip to both sides twice and lower lip two times using the same force, while feeling carefully the force between the lipstick and skin of lips during the second application. The weaker friction force, the higher glideness is.

Shininess and migration resistance were evaluated by 5 experts by applying a lipstick on the upper lip to both sides for twice and lower lip two times using the same force. Migration means that the product has featherings at the small wrinkles of the lips. The less migration, the better.

Finally, comments or scores were given by the experts on stability, glideness, shininess, and migration resistance.

5: very good;

4: basically good;

3: acceptable;

2: slightly poor and not acceptable;

1: poor, not acceptable.

The evaluation results of each lipstick were summarized in the following Table 2.

Table 2

Properties	Inv. 1	Comp. 1	Comp. 2	Comp. 3
Shearing value (gF)	75	80	62	48
Hardness (Nm ^-1) *	64	68	53	41
Stability	5	5	5	3
Shininess	4.5	5	2	4
Migration resistance	4.5	2	5	1
Glideness	5	5	2	5

It was observed that lipstick of Inv. 1 is stable and has desired shear value and hardness, and usage effect such as glideness, and leaves a shiny deposit having good migration resistance on keratin materials.

Claims

An anhydrous composition for caring for and/or making up keratin materials comprising:

a) at least one non-volatile phenyl silicone oil optionally having a dimethicone fragment corresponding to formula (I) below:

in which the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl;

b) at least one non-volatile phenyl silicone oil optionally having at least one dimethicone fragment correspond to formula (II) below:

in which Me is methyl and Ph is phenyl, OR' represents a group-OSiMe ₃ and p is 0 or is between 1 and 1000, and m is between 1 and 1000; and

c) at least one film-forming polymer selected from cellulose ethers;

wherein the weight ratio of the non-volatile phenyl silicone oil corresponding to formula (I) to the non-volatile phenyl silicone oil corresponding to formula (II) is from 0.5 to 1.
The composition according to claim 1, wherein the non-volatile phenyl silicone oil of formula (I) comprises at least three, at least four or at least five phenyl groups.
The composition according to claim 1, wherein the non-volatile phenyl silicone oil of formula (I) is selected from trimethylpentaphenyltrisiloxane and tetramethyltetraphenyltrisiloxane.
The composition according to any of claims 1-3, wherein the non-volatile phenyl silicone oil of formula (I) is present in amount ranging from 1 wt. %to 30 wt. %, preferably from 2 wt. %to 20 wt. %and more preferably from 5 wt. %to 12 wt. %, relative to the total weight of the composition.
The composition according to any of claims 1-4, wherein the non-volatile phenyl silicone of formula (II) has at least one dimethicone fragment, p is between 1 and 1000 and m is more particularly such that the compound (II) is a non-volatile oil.
The composition according to any of claims 1-4, wherein the non-volatile phenyl silicone oil of formula (II) is selected from phenyltrimethylsiloxytrisiloxane and trimethylsiloxyphenyl dimethicone.
The composition according to any of claims 1-6, wherein the non-volatile phenyl silicone oil of formula (II) is present in amount ranging from 2 wt. %to 40 wt. %, preferably from 6 wt. %to 30 wt. %and more preferably from 10 wt. %to 24 wt. %, relative to the total weight of the composition.
The composition according to any of claims 1-7, wherein the at least one film-forming polymer is selected from methyl cellulose, ethyl cellulose, propyl cellulose and methylethyl cellulose.
The composition according to any of claims 1-8, wherein the film-forming polymer is present in amount ranging from 0.5 wt. %to 10 wt. %, preferably from 1 wt. %to 8 wt. %and more preferably from 2 wt. %to 6 wt. %, relative to the total weight of the composition.
The composition according to any of claims 1-9 further comprising at least one additional oil selected from octyldodecanol, stearyl heptanoate, stearyl caprylate, isohexadecane, C12-15 alkyl benzoate, dimethicone, and mixtures thereof, in an amount ranging from 30 wt. %to 70 wt. %, preferably from 40 wt. %to 65 wt. %, relative to the total weight of the composition.
The composition according to any of claims 1-10, further comprising at least one wax selected from synthetic wax, paraffin, microcrystalline wax, polyethylene, VP/eicosene copolymer, and mixtures thereof, in an amount ranging from 5 wt. %to 30 wt. %, preferably from 7 wt. %to 20 wt. %, more preferably from 8 wt. %to 15 wt. %, relative to the total weight of the composition.
The composition according to any of claims 1-11, further comprising at least one colorant selected from YELLOW 5 LAKE, Blue 1 lake, RED 22 LAKE, RED 21, RED 7, titanium dioxide, iron oxides, synthetic fluorphlogopite, and mixtures thereof, in an amount ranging from 3 wt. %to 20 wt. %, preferably from 3 wt. %to 15 wt. %, more preferably from 5 wt. %to 12 wt. %, relative to the total weight of the composition.
The composition according to claim 1, comprising, relative to the total weight of the composition:

a) from 5 wt. %to 12 wt. %of trimethyl pentaphenyl trisiloxane;

b) from 10 wt. %to 24 wt. %oftrimethylsiloxyphenyl dimethicone;

c) from 2 wt. %to 6 wt. %of ethyl cellulose; and

d) from 8 wt. %to 15 wt. %of at least one wax selected from synthetic wax, paraffin, microcrystalline wax, POLYETHYLENE, VP/EICOSENE COPOLYMER, and mixtures thereof;

e) from 5 wt. %to 12 wt. %of at least one colorant selected from YELLOW 5 LAKE, Blue 1 lake, RED 22 LAKE, RED 21, RED 7, titanium dioxide, iron oxides, synthetic fluorphlogopite, and mixtures thereof; and

f) from 60 wt. %to 75 wt. %of at least one additional oil selected from octyldodecanol, stearyl heptanoate, stearyl caprylate, isohexadecane, c12-15 alkyl benzoate, dimethicone, and mixtures thereof.
A process for caring for and/or making up keratin materials such as the skin and the lips, comprising applying the composition as defined in any of claims 1-13 to the keratin materials.