Cosmetic compositions containing block copolymers, tackifiers and a selective solvent for hard blocks

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DESCRIPTION

Cosmetic compositions containing block copolymers and corresponding long-lasting cosmetic product system.

Many developments have been made in relation to improving the comfort, durability, shine and / or longevity of cosmetic compositions for the face, eyes, lips, nails or hair. Commercially available lip treatment compositions such as lip glosses and lipsticks possess a certain level of luster or shine depending on their composition. Efforts have been made through the use of high refractive index fluids to further improve the gloss or luster of such products, but the duration of the luster or gloss is limited. In addition, these lip treatment compositions are sticky and uncomfortable to apply, often due to the presence of high molecular weight polymers exhibiting high viscosity which are used to maintain gloss / gloss life.

Although other efforts to improve gloss / luster involve the use of silicone fluids, the duration of the gloss leaves much to be desired.

Therefore, one of the aspects of the present invention is to provide a lip treatment composition that is comfortable to apply and wear, and that exhibits a long-lasting gloss / luster.

Consequently, a first aspect of the present invention refers to a cosmetic composition comprising:

(a) at least one block copolymer having at least one hard segment and at least one soft segment;

(b) at least one tackifying component;

(c) at least one solvent that can solubilize said at least one hard segment; and (d) optionally, at least one colorant, and wherein said at least one hard segment has a Tg value of 50 ° C or more, and said at least one soft segment has a Tg value of 20 ° C or minus, where (a) is a mixture of: (i) at least one di-block thermoplastic elastomer of an AB type copolymer and (ii) at least one tri-block thermoplastic elastomer of an ABA type copolymer, in which A corresponds to styrene and B corresponds to rubber, in wherein said at least one tackifier is a hydrogenated styrene / methylstyrene / indene copolymer, and wherein said at least one solvent that can solubilize said at least one hard segment has a viscosity equal to or less than 200 cps at room temperature and has a weight average molecular weight equal to or less than 500, said solvent (c) being a non-volatile solvent, selected from among monoesters, diesters, triesters; polar aromatic and / or mixed aliphatic oils; natural or synthetic esters of formula R1COOR2, wherein Ri is a higher fatty residue comprising 7 to 19 carbon atoms, and R2 is a branched hydrocarbon-based chain comprising 3 to 20 carbon atoms; synthetic esters of formula R³COR⁴, in which R³ is a C3 to C19 alkyl radical, and R⁴ is a C3 to C alkyl radical₂₀; fatty alcohols comprising at least 12 carbon atoms; cyclic hydrocarbons; aromatic hydrocarbons; primary, secondary or tertiary amines and mixtures thereof.

Therefore, it has surprisingly been found that a lip treatment composition containing:

(a) a block copolymer having at least one hard segment and at least one soft segment, (b) a tackifier, and (c) at least one solvent that can solubilize said at least one hard segment, in admixture or Not with at least one solvent that can solubilize the soft segment of the block copolymer, it can provide a long-lasting, comfortable shine or luster when applied to the lips.

The physical and rheological properties of block copolymers can be controlled using specific types of solvents that can solubilize the soft and / or hard block segments. A solvent that can solubilize the soft segment causes the block copolymer to have a different rheology and morphology from those obtained using a solvent that can solubilize the hard segment. Similarly, the physical properties of a mixed solvent block copolymer solution that can solubilize both soft and hard segments are different from those obtained when using solvents that can solubilize only soft segments or solvents that they can solubilize only the hard segments.

Furthermore, the present invention relates according to another of its aspects to a long-lasting cosmetic product system and to the method of making up a keratinous substrate using said cosmetic product system. Compositions used to enhance cosmetic products are known in the art. Such compositions, sometimes referred to as topcoats, include those that are applied over basecoat compositions, such as a lipstick, in order to impart attributes such as luster, shine, and lubricity not normally provided by compositions. of the base coat. These enhancement products use a variety

ES 2 365 754 T3 of polymeric fluids in order to impart luster, shine and lubricity.

Although such topcoat compositions can provide these types of enhancements, they have been found not to be particularly resistant to transfer. As a result, these topcoats must be reapplied over the course of one day in order to maintain luster, shine, and lubricity in the cosmetic basecoat composition.

Therefore, the present invention relates to a cosmetic procedure for making up a keratinous substrate that involves:

(a) provide a keratinous substrate;

(b) applying a basecoat composition over the keratinous substrate, the basecoat composition containing:

(i) at least one polyorganosiloxane-containing polymer selected from (1) the (co) polymers comprising at least one organosiloxane unit and at least two other groups that can form hydrogen interactions selected from an ester group, a group sulfonamide, a carbamate group, a thiocarbamate group, a urea group, a thiourea group, an oxamido group, a guanidino group, a biguanidino group, an amide group, and mixtures thereof;

(2) silicone polyamide copolymers and mixtures thereof (ii) at least one silicone film-forming compound;

(iii) at least one volatile oil; and (iv) at least one colorant; and (c) applying a topcoat composition on top of the basecoat composition, the topcoat composition being the composition as defined above.

Apart from the working examples, or where otherwise indicated, it is to be understood that all numbers expressing amounts of components or reaction conditions are in all cases modified by the term "about".

COSMETIC COMPOSITION

BLOCK COPOLYMER

The block copolymers of the present invention are characterized by the presence of at least one hard segment, and at least one soft segment. Aside from their compositional nature, the soft and hard segments of the block copolymers of the present invention are defined in terms of their respective glass transition temperatures, Tg. More particularly, the hard segment has a Tg of 50 ° C or more, while the soft segment has a Tg of 20 ° C or less. The glass transition temperature Tg for the hard block can be between 50 ° C and 150 ° C; 60 ° C and 125 ° C; 70 ° C and 120 ° C; 80 ° C and 110 ° C. The glass transition temperature Tg for the soft segment of the block copolymer can be between 20 ° C and 150 ° C; 0 ° C and -135 ° C; -10 ° C and -125 ° C; -25 ° C and -100 ° C. A broader explanation can be found in US Patent Nos. 5,294,438 and 6,403,070, the full contents of which are incorporated herein by reference.

The block copolymer used by the present invention is a thermoplastic elastomer. The hard segments of the thermoplastic elastomer comprise styrene.

The soft segments of the thermoplastic elastomer comprise ethylene / butylene copolymers.

The block copolymer for use in the present invention is a combination of di-block and tri-block copolymers of styrene-ethylene / butylene-styrene, commercially available from Shell Chemical Company under the tradename Kraton G1657M.

The block copolymer is generally present in the cosmetic composition in an amount comprised between more than 0% and 50% by weight; more than 0% and 40% by weight; more than 0% and 30% by weight; more than 0% and 20% by weight; more than 0% and 10% by weight, based on the weight of the composition.

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STICKING AGENTS

A substance is described as a tackifier if, when added to a block copolymer, the resulting composition exhibits the properties of a pressure sensitive adhesive. In general, tackifiers can be divided into four different families in terms of their chemical composition: hydrocarbon resins, terpenes, amorphous (i.e. non-crystalline) rosins, rosin esters and their derivatives, and pure monomeric resins. These tackifiers are characterized by their compatibility with at least one segment of the block copolymer. By the term "compatible", it is meant that when the block copolymer and the tackifier are mixed, the combination of at least one segment of the block copolymer with the tackifier forms a polymer combination exhibiting a glass transition temperature. T_gunique that can be measured by DMA, DSC or neutron light scattering.

The compatibility of the block copolymer and the tackifier can also be defined in terms of solubility parameters. The bone solubility parameter according to the Hansen solubility space is defined in the article Solubility parameter Values ​​by Eric A. Grulke in the publication Polymer Handbook 3^to edition, chapter VII, pages 519-559, the complete content of which is incorporated herein by reference, by means of the following:

δ = (d_D² + dp² + dj |²)^1/2 , in which:

- do characterize the London scattering forces resulting from the formation of induced dipoles during molecular impacts,

- dp characterizes the forces of Debye interactions between permanent dipoles,

- dH characterizes the specific interaction forces (hydrogen bond, acid / base or donor / acceptor type and the like). The definition of solvents in Hansen's three-dimensional solubility space is provided in CM Hansen's article: The three-dimensional solubility parameters J. Paint Technol., 39, 105 (1967), the full content of which is incorporated herein as reference.

Said at least one tackifier used in the present invention will have a solubility parameter corresponding to a number o and the block copolymer will have at least one segment whose solubility parameter corresponds to or ± 2, preferably δ ± 1.7, more preferably δ ± 1.5, more preferably δ ± 1.3, more preferably δ ± 1.0, more preferably δ ± 0.7, more preferably δ ± 0.5, and most preferably δ ± 0.3.

In some embodiments, the tackifier may have a softening point (Ring and Ball, as measured according to ASTM E-28) of 80 ° C to 150 ° C, preferably 100 ° C to 130 ° C. In other embodiments, the tackifier may be liquid and have a softening point R and B of between about -70 ° C and 70 ° C.

Tackifiers according to the present invention are hydrogenated hydrocarbon resins such as a hydrogenated styrene / methylstyrene / indene copolymer e.g. styrene / methylstyrene / indene copolymers including R1090, R1100, R7100, S1100 and S5100, all of which are available. commercially from Eastman Chemical under the trade name Regalite®. In other embodiments, tackifying resins based on aliphatic or aromatic hydrocarbons can also be used, for example the resins sold under the name Piccotac and Hercotac from Hercules or Escorez from Exxon. It is also understood that mixtures of tackifiers may also be employed without departing from the spirit of the invention.

A particularly preferred tackifier for use in the present invention is a hydrogenated hydrocarbon resin such as, for example, a hydrogenated styrene / methylstyrene / indene copolymer, commercially available from Eastman under the trade name Regalite® R1100.

The tackifier is present in the present composition in an amount ranging from more than 0% to 90% by weight; more than 0% and 70% by weight; more than 0% and 60% by weight; more than 0% and 50% by weight; more than 0% and 40%; more than 0% and 30% by weight; more than 0% and 20% by weight, based on the weight of the composition.

SOLVENTS

Solvents that can solubilize the hard segment of the block copolymer that can be used herein are typically characterized in terms of room temperature viscosity, average molecular weight, and solubility parameter relative to at least one hard segment of the block copolymer. .

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The solvent that can solubilize the hard segment of the block copolymer will have a viscosity, at room temperature, of between 0.001 and 0.2 Pa ^ s; preferably between 0.001 and 0.15 Pa ^s, more preferably between 0.001 and 0.1 Pa ^s, more preferably between 0.002 and 0.6 Pa ^s and more preferably between 0.002 and 0.4 Pa ^s.

The solvent that can solubilize the hard segment of the block copolymer used in the present invention will present a solubility parameter corresponding to a number δ 'and the block copolymer will present at least one hard segment whose solubility parameter corresponds to δ' ± 2, preferably δ '± 1.7, more preferably δ' ± 1.5, more preferably δ '± 1.3, more preferably δ' ± 1.0, more preferably δ '± 0.7, more preferably δ '± 0.5 and more preferably δ' ± 0.3.

Non-volatile solvents that can solubilize the hard segment of the block copolymer used in the invention are monoesters, diesters, triesters, mixed polar aromatic and / or aliphatic oils such as: hydrocarbon-based oils of animal origin, such as perhydrosqualene ; hydrocarbon-based vegetable oils such as liquid triglycerides of fatty acids and glycerol, in which the fatty acids can have varied chain lengths, these chains being straight or branched, and saturated or unsaturated; These oils can be selected, for example, from wheat germ oil, sunflower oil, corn oil, soybean oil, pumpkin oil, grape seed oil, blackcurrant seed oil, sesame oil, oil hazelnut, apricot oil, macadamia oil, castor oil, avocado oil, shea butter, sweet almond oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, evening primrose oil, Son, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candela nut oil, passion fruit oil, rosehip oil and caprylic / capric acid triglycerides such as those marketed by the Stéarineries Dubois company or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; natural or synthetic esters of formula R1COOR2, wherein R1 is a higher fatty acid residue comprising 7 to 19 carbon atoms, and R2 is a branched hydrocarbon-based chain comprising 3 to 20 carbon atoms, such such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate and alkyl or polyalkyl octanoates, decanoates or ricinoleates, synthetic ethers of formula R³COR⁴, in which R³ is a C3 to C19 alkyl radical, and R⁴ is a C3 to C20 alkyl radical; fatty alcohols comprising at least 12 carbon atoms, such as octyldodecanol or oleyl alcohol; cyclic hydrocarbons such as (alkyl) cycloalkanes, in which the alkyl chain is straight or branched, saturated or unsaturated and comprises from 1 to 30 carbon atoms, such as cyclohexane or dioctylcyclohexane; aromatic hydrocarbons, for example alkenes such as benzene, toluene, 2,4-dimethyl-3-cyclohexene, dipentene, p-cymene, naphthalene or anthracene, and esters such as isostearyl benzoate; primary, secondary, or tertiary amines such as triethanolamine; and mixtures thereof. In one embodiment, synthetic esters such as isopropyl myristate are used.

Preferred esters are those having a weight average molecular weight (Mw) in the range of 100 to 600, preferably 100 to 500. Examples thereof include, but are not limited to, C12-15 alkyl benzoate, myristate isopropyl (Mw = 270), isopropyl palmitate (Mw = 300), isononyl isononanoate, cetyl ethylhexanoate (Mw = 368), neopentyl glycol diethylhexanoate (Mw = 356), diisopropyl sebacate (Mw = 286).

The solvent that can solubilize the hard segment of the block copolymer can normally be present in the composition of the invention in an amount of up to 85% by weight; more than 0% to 75% by weight; more than 0% to 55% by weight; more than 0% to 45% by weight; more than 0% to 40% by weight; more than 0% to 30% by weight; more than 0% to 20% by weight; more than 0% to 10% by weight; more than 0% to 5% by weight, based on the weight of the composition.

According to a preferred embodiment of the present invention, this solvent can be mixed with at least one solvent that can solubilize the soft segment of the block copolymer.

Solvents that can solubilize the soft segment of the block copolymer that can be used herein are typically characterized in terms of their room temperature viscosity, average molecular weight, and solubility parameter relative to the at least one soft segment of the block copolymer.

The solvent that can solubilize the soft segment of the block copolymer will have a viscosity, at room temperature, between 0.001 and 0.5 Pa.s, preferably between 0.001 and 0.4 Pa.s, more preferably between 0.001 and 0.3 Pa.s, more preferably between 0.002 and 0.2 Pa.s, and more preferably between 0.002 and 0.1 Pa.s.

The solvent that can solubilize the soft segment of the block copolymer used in the present invention will present a solubility parameter corresponding to a number δ 'and the block copolymer will present at least one soft segment whose solubility parameter corresponds to δ' ± 2, preferably δ '± 1.7, more preferably δ' ± 1.5, more preferably δ '± 1.3, more preferably δ' ± 1.0, more preferably δ '± 0.7, more preferably δ '± 0.5 and more preferably δ' ± 0.3.

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The solvent that can solubilize the soft segment of the block copolymer can be selected from volatile solvents and non-volatile solvents. The term "volatile solvent" means a solvent that can evaporate at room temperature from a support on which has been applied, in other words, a solvent exhibiting a measurable vapor pressure at room temperature. See US Patent No. 6,656,458, the entire contents of which are incorporated herein by reference.

Representative examples of suitable volatile organic solvents include, but are not limited to, volatile hydrocarbon based oils. The term "hydrocarbon-based oil" means oil containing only hydrogen and carbon atoms. Examples of oils based on volatile hydrocarbons include isoparaffins, that is, branched alkanes containing from 8 to 16 carbon atoms, and in particular isododecane (also known as 2,2,4,4,6-pentamethylheptane). It is also possible to use mixtures of such isoparaffins. Other volatile hydrocarbon based oils, such as petroleum distillates, can also be used.

Suitable non-volatile solvents that can be used are those having an average molecular weight in the range of 150 to 450, preferably 200 to 350. Examples thereof include, but are not limited to, hydrogenated polydecene, hydrogenated polyisobutene, isoeicosan, polydecene and polybutene.

The solvent that can solubilize the soft segment of the block copolymer can normally be present in the composition of the invention in an amount of up to 85% by weight; greater than 0% to 75% by weight; greater than 0% to 55% by weight; greater than 0% to 45% by weight; greater than 0% to 40% by weight; greater than 0% to 30% by weight; greater than 0% to 20% by weight; greater than 0% to 10% by weight; greater than 0% to 5% by weight, based on the weight of the composition.

According to a preferred embodiment of the present invention, at least one cosolvent having a high molecular weight and high viscosity can also be used in order to impart flow and leveling of the lip treatment composition during application to the lips. , as well as their feeling and comfort on them.

Examples of suitable high viscosity cosolvents that are compatible with the hard segment of the block copolymer include, but are not limited to, capric / caprylic triglyceride (Mw = 500), diisopropyl dilinoleate dimer (Mw = 644), diisostearyl (Mw = 620), diisostearyl malate (Mw = 640), pentaerythrityl tetraoleate, neopentylglycol diethylhexanoate, diethylhexyl sebacate, and tricaprylate / tricaprate. The average molecular weight of these cosolvents is preferably from 500 to 1,000, and more preferably from 500 to 800.

Examples of suitable high viscosity cosolvents that are compatible with the soft segment of the block copolymer include, but are not limited to, polyisobutene, hydrogenated polyisobutene, polybutene, hydrogenated polybutene, polydecene, and hydrogenated polydecene. The average molecular weight of these cosolvents is preferably from 2,500 to 100,000 and more preferably from 3,000 to 10,000.

These cosolvents can be used in the composition of the invention in an amount of up to 50% by weight; greater than 0% to 40% by weight; greater than 0% to 30% by weight; greater than 0% to 25% by weight; all weights being based on the weight of the composition.

According to yet another embodiment of the present invention, it has been found that the use of at least one homopolymer of the same type as said at least one solvent that can solubilize the soft segment, but that has an average molecular weight greater than 2,000 , improves adhesion, thereby limiting migration, of the lip treatment composition on the skin.

Examples of suitable homopolymers include, but are not limited to, polyisobutene, hydrogenated polyisobutene, polybutene, hydrogenated polybutene, polydecene, and hydrogenated polydecene. The average molecular weight of these homopolymers is preferably between 2,500 and 100,000 and more preferably between 3,000 and 10,000.

The homopolymer can be present in the composition of the invention in an amount of from more than 0% to 30% by weight; greater than 0% to 25% by weight; greater than 0% to 20% by weight; greater than 0% to 18% by weight; greater than 0% to 15% by weight, all weights being based on the weight of the composition.

In the case that at least one solvent that can solubilize the hard segment is used, and at least one solvent that can solubilize the soft segment in combination with one or more of said at least one cosolvent compatible with the hard segment, at least one A cosolvent compatible with the soft segment and at least one homopolymer, the mixture will have a viscosity between 0.02 and 5 Pa.s, preferably between 0.02 and 2 Pa.s, and more preferably between 0.02 and 1,500 Pa. s. The viscosity of the mixture is determined using the formula:

ES 2 365 754 T3 in which qmez represents the viscosity of the mixture, q¡ represents the viscosity of the individual components and φ represents the weight fraction of the individual components.

COLORANT

The composition of the present invention may also contain at least one cosmetically acceptable colorant such as a pigment or dye. Examples of suitable pigments include, but are not limited to, inorganic pigments, organic pigments, lacquers, pearlescent pigments, iridescent, or optically variable pigments and mixtures thereof. A pigment is to be understood to mean white or colored, inorganic or organic particles. Such pigments may optionally be surface treated within the scope of the present invention but are not limited to treatments such as silicones, perfluorinated compounds, lecithin, and amino acids.

Representative examples of inorganic pigments useful in the present invention include those selected from the group consisting of rutile titanium dioxide or anatase, color-indexed as CI 77,891; black, yellow, red and brown iron oxides, coded with CI references 77,499, 77,492 and 77,491; manganese violet (CI 77,742); ultramarine blue (CI 77.007); chromium oxide (CI 77,288); chromium hydrate (CI 77,289); and ferric blue (CI 77,510) and mixtures thereof.

Examples of representative organic pigments and lacquers useful in the present invention include, but are not limited to, D&C Red No. 19 (CI 45,170), D&C Red No. 9 (CI 15,585), D&C Red No. 21 (CI 45,380) , D&C Orange # 4 (CI 15,510), D&C Orange # 5 (CI 45,370), D&C Red # 27 (CI 45,410), D&C Red # 13 (CI 15,630), D&C Red # 7 (CI 15,850) , D&C Red # 6 (CI 15.850), D&C Yellow # 5 (CI 19.140), D&C Red # 36 (CI 12.085), D&C Orange # 10 (CI 45.425), D&C Yellow # 6 (CI 15.985) , D&C red n ° 30 (CI 73,360), D&C red n ° 3 (CI 45,430) and dyes or lacquers based on cochineal carmine (CI 75,570) and mixtures thereof.

Representative examples of pearlescent pigments useful in the present invention include those selected from the group consisting of white pearlescent pigments such as titanium oxide coated mica, titanium dioxide coated mica, bismuth oxychloride, titanium oxychloride, pearlescent pigments. colored such as titanium mica with iron oxides, titanium mica with ferric blue, chromium oxide and the like, titanium mica with an organic pigment of the type mentioned above as well as those based on bismuth oxychloride and mixtures thereof.

The precise type and amount of colorant employed in the compositions of the present invention will depend on the color, intensity and use of the cosmetic composition and, as a result, will be determined by the person skilled in the art of cosmetic formulation.

BRIGHTNESS ENHANCEMENT AGENTS

Sometimes it may be desirable to provide cosmetic compositions that exhibit enhanced gloss / luster properties. In those cases, at least one gloss enhancing agent would be employed in the composition.

Suitable gloss enhancing agents include compounds having a refractive index ranging from 1.45 to 1.60, and an average molecular weight of less than 15,000, preferably less than 10,000, preferably less than 2,000. Examples thereof include, but are not limited to, phenylated silicones such as those sold under the trade name Abil AV 8853 by Goldschmidt, those sold under the trade names DC 554, DC 555, DC 556, SF 558 by Dow Corning and sold under the trade name Silbione 70633 V 30 by Rhóne-Poulenc.

Additional examples of suitable phenylated silicones include, but are not limited to, those available from Wacker Silicones such as Belsil PDM 20, a phenylated silicone with a viscosity at 25 ° C of about 20 cSt; Belsil PDM 200, a phenylated silicone with a viscosity at 25 ° C of approximately 200 cSt; Belsil PDM 1000, a phenylated silicone with a viscosity at 25 ° C of approximately 1,000 cSt.

Additional examples of suitable gloss enhancing agents include, but are not limited to, polycyclopentadiene, poly (propylene glycol) dibenzoate (nD = 1.5345), aminopropylphenyltrimethicone (nD = 1.49-1.51), pentaerythrityl tetraoleate commercially available as Puresyn 4E68 (nD = 1.473) from ExxonMobil and benzyl ether myristate PPG-3 commercially available as Crodamol STS (nD = 1.4696) from Croda Inc.

Particularly preferred shine enhancing agents are phenylated silicones such as phenyltrimethicone and trimethylpentaphenyltrisiloxane and esters such as pentaerythrityl tetraoleate and benzyl ether myristate PPG-3.

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The gloss enhancing agent can be present in the composition of the invention in an amount of up to 40% by weight; up to 30% by weight; up to 20% by weight; from 1 to 20% by weight; from 2 to 20% by weight, based on the weight of the composition.

MODIFIED SILICONES

The cosmetic compositions of the present invention may contain at least one modified silicone to improve texture and comfort. Examples of suitable modified silicone include, but are not limited to, polyethyleneoxy and / or polypropylenexy modified silicone, alkoxy modified silicone, hydroxyalkyl modified silicone, acyloxyalkyl modified silicone, alkyl modified silicone, amino modified silicone, modified silicone with epoxy resin, carboxyl modified silicone, chloroalkyl modified silicone, higher alkyl alcohol ester modified silicone, alcohol-modified silicone, polyether-modified silicone, phenyl-modified silicone, alkylpolyglyceryl-modified silicone, perfluoroalkyl-polyether-modified silicone, and fluorine-modified silicone.

The modified silicone can be present in the composition of the invention in an amount of up to 30% by weight; up to 25% by weight; up to 20% by weight; up to 10% by weight; up to 8% by weight, based on the weight of the composition.

WAXES

In some embodiments, it may be desirable to formulate cosmetic compositions according to the present invention that are free of wax. However, where a wax is used, it will be present in an amount of from about 0.1% to about 30% by weight, based on the total weight of the composition. Suitable waxes are those generally used in cosmetics and dermatology. Examples thereof include, but are not limited to, those of natural origin such as beeswax, carnauba wax, candelilla wax, uricuri wax, Japan wax, cork fiber wax, sugar cane wax, paraffin wax, lignite wax, microcrystalline waxes, lanolin wax, montana wax, ozokerites, and hydrogenated oils such as hydrogenated jojoba oil. Examples of suitable synthetic waxes include, but are not limited to, polyethylene waxes derived from the polymerization of ethylene, waxes obtained by Fischer-Tropsch synthesis, fatty acid esters and glycerides that are solid at 40 ° C, for example, above 55 ° C, silicone waxes such as alkyl alkoxy-poly (di) methylsiloxanes and / or poly (di) methylsiloxane esters which are solid at 40 ° C, for example above 55 ° C.

GELLING AGENTS

The compositions of the invention may also optionally be gelled with an oil phase gelling agent. The gelling agent increases the viscosity of the liquid fatty phase and leads to a solid or fluid composition when introduced into said fatty phase. The gelling agent does not encompass waxes, in the sense that it is not waxy. Said at least one gelling agent can be chosen from gelling agents in polymeric form and gelling agents in mineral form. The gelling agent can be chosen from agents that gelling through chemical crosslinking and agents that gelling through physical crosslinking.

Modified clays can be used as gelling agents, examples of which include, but are not limited to, hectorites modified with an ammonium chloride of a C10 to C22 fatty acid, such as distearyldimethylammonium chloride modified hectorite, also known as quaternium- 18 bentonite, such as the products marketed or manufactured under the names Bentona 34 by the company Rheox, Claytone XL, Claytone 34 and Claytone 40 marketed or manufactured by Southern Clay, modified clays known by the name quaternium-18 benzalkonium bentonites and marketed or manufactured under the names Claytone HT, Claytone GR and Claytone PS by Southern Clay, modified clays with stearyldimethylbenzoylammonium chloride, known as stearalkonium bentonites, such as products marketed or manufactured under the names Claytone APA and Claytone AF by the Southern Clay Company and Baragel 24 marketed or manufactured by the Rheox Company.

Other mineral gelling agents, which can be used in the invention, include silica, such as fumed silica. The fumed silica can have a particle size that can be nanometric to micrometer, ranging for example between 5 nm and 200 nm.

Fumed silicas can be obtained by high temperature hydrolysis of a volatile silicon compound in a hydrogen-oxygen flame, producing a finely divided silica. This procedure makes it possible to obtain hydrophilic silicas that have a large number of silanol groups on their surface. Such hydrophilic silicas are marketed or manufactured, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by Degussa, and CABO-SIL HS-5®, CAB- O-SIL EH-5®, CAB-O-SIL LM-130®, CAB-O-SIL MS-55® and CAB-O-SIL M-5® by the Cabot company.

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Therefore, it is possible to chemically modify the surface of the hydrophilic silica by chemical reaction, producing a reduction in the number of silanol groups. Silanol groups can be substituted, for example, by hydrophobic groups: this then provides a hydrophobic silica. Hydrophobic groups can be: trimethylsiloxy groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as silica silylate according to the CTFA dictionary. They are marketed or manufactured, for example, under the references Aerosil R812® by the company Degussa and CAB-O-SIL TS-530® by the company Cabot; dimethylsilyloxy or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as silica dimethylsilylate according to the CTFA dictionary. They are marketed or manufactured, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa, and CAB-O-SIL TS-610® and CaB-O-SIL TS-720® by the company Cabot; groups derived from the reaction of fumed silica with siloxanes or silane alkoxides. These treated silicas are, for example, the products marketed or manufactured with the reference Aerosil R805^® by the company Degussa.

According to the invention, hydrophobic silica, such as fumed silica, can be used as a lipophilic gelling agent. The use of fumed silica makes it possible to obtain a translucent or even transparent composition, in particular in the form of a stick, which does not exude, in the absence of opacifying particles such as waxes, fillers and pigments (including pearlescent).

Said at least one lipophilic gelling agent can allow the exudation of the composition to be limited and can allow its stability to be increased, while preserving the glossy appearance of the composition, which is not possible with waxes such as those conventionally used in cosmetics and dermatology.

Said at least one gelling agent, if used, will normally be present in an amount between 0.1% and 20% by weight, preferably between 0.1% and 15% by weight, and more preferably between 0.1% and 20% by weight. 0.1 and 10% by weight, based on the weight of the composition.

AUXILIARY AGENTS / ADDITIVES

The compositions of the present invention may further comprise at least one cosmetically or dermatologically acceptable additive such as a thickener, a film former, a plasticizer, an antioxidant, an essential oil, a preservative agent, a fragrance, a filler, a fatty substance. pasty, a waxy fatty substance, a neutralizing agent and a polymer, and cosmetically active agents and / or dermatologically active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids, and medications.

Although the use of a plasticizer is not necessary in the lip treatment compositions of the present invention, its use may nevertheless be desirable. Plasticizers are organic compounds added to a high molecular weight polymer both to facilitate its processing and to increase the flexibility and toughness of the final product through internal modification of the polymer molecule. Examples of suitable plasticizers include, but are not limited to, oils, cellulose esters, phthalate esters, adipate esters, sebacate esters, tricresyl phosphate, castor oil, glycol ethers, benzyl alcohol, triethyl citrate and carbonate. propylene.

Particularly preferred plasticizers include isopropyl palmitate and alkyl benzoate. A plasticizer, if used, will normally be present in an amount of from 1 to 70% by weight, preferably from 2 to 50% by weight, and more preferably from 5 to 20% by weight, based on the weight of the composition.

Representative examples of preservatives include alkyl para-hydroxybenzoates, in which the alkyl radical has from 1, 2, 3, 4, 5 or 6 carbon atoms and preferably from 1 to 4 carbon atoms, for example para-hydroxybenzoate methyl (methyl paraben), ethyl para-hydroxybenzoate (ethyl paraben), propyl parahydroxybenzoate (propyl paraben), butyl para-hydroxybenzoate (butyl paraben) and isobutyl para-hydroxybenzoate (isobutyl paraben). Mixtures of preservatives can of course be used, for example, the mixture of methyl paraben, ethyl paraben, propyl paraben and butyl paraben sold under the name Nipastat by Nipa, and the mixture of phenoxyethanol, methyl paraben, ethyl paraben, propyl paraben and butyl paraben sold under the name Phenonip, also by Nipa. These preservatives may be present in amounts of between about 0.01 and about 10% by weight, preferably between 0.5% and 5% by weight, and more preferably between about 0.8 and about 3%. by weight, based on the weight of the composition.

Fillers that can be used in the compositions of the invention include, for example, silica powder; talcum powder; polyamide particles and especially those marketed under the name Orgasol by the company Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those based on ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by Dow Corning under the name Polytrap; expanded powders such as hollow microspheres and especially microspheres marketed with

ES 2 365 754 T3 the name Expancel by the company Kemanord Plast or with the name Micropearl F 80 ED by the company Matsumoto; powders of natural organic materials such as cross-linked or non-cross-linked cornstarch, wheat starch or rice starch, such as octenylsuccinate anhydride cross-linked starch powders, marketed under the name Dry-Flo from National Starch; silicone resin microbeads such as those sold under the name Tospearl by Toshiba Silicone; clays (benthone, laponite, saponite, etc.) and mixtures thereof. These fillers may be present in amounts ranging from about 0.1 to about 50% by weight, preferably from 0.5 to about 30% by weight, and more preferably from about 1 to about 20% by weight. weight, based on the weight of the composition.

The compositions of the present invention may further comprise a safe and effective amount of at least one active component or pharmaceutically acceptable salt thereof. The term "safe and effective amount" as used herein, means an amount sufficient to modify the condition to be treated or to provide the desired benefit to the skin, while at the same time avoiding serious side effects, at a Reasonable risk-benefit ratio within the scope of sound medical judgment. What is a safe and effective amount of the active component will vary with the specific active agent, the ability of the active agent to penetrate through the skin, the age, health and condition of the skin of the user, and other similar factors. Typically, the active component may be present in amounts ranging from about 0.01 to about 20% by weight, preferably from 0.1 to about 10% by weight, and more preferably from about 0.5 to about 5% by weight, based on the weight of the composition.

Active ingredients useful herein can be classified by their therapeutic benefit or postulated mode of action. However, it should be understood that the active components useful herein may in some cases provide more than one therapeutic benefit or function through more than one mode of action. Therefore, the classifications herein are made for the sake of convenience and are not intended to limit the active component to the particular application or applications listed. Furthermore, pharmaceutically acceptable salts of these active components are useful herein. The following active components are useful in the compositions of the present invention.

Anti-acne actives: Examples of useful anti-acne actives include keratolytics such as salicylic acid (o-hydroxybenzoic acid), salicylic acid derivatives such as 5-octanoylsalicylic acid, and resorcinol; retinoids such as retinoic acid and its derivatives (eg, cis and trans); sulfur-containing amino acids D and L and their derivatives and salts, particularly their N-acetyl derivatives, a preferred example of which is N-acetyl-L-cysteine; lipoic acid; antibiotics and antimicrobials such as benzoyl peroxide, octopirox, tetracycline, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorobanilide, azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, acetate ethyl, clindamycin, and meclocycline; sebostatics such as flavonoids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate and cholate.

Antimicrobial and antifungal active ingredients: Examples of antimicrobial and antifungal active ingredients include beta-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'- trichlorobanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, hexamidine isethionate, metronidazole, pentamidine, gentamicin, line kanamycin, methacycline, methenamine, minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, miconazole, tetracycline hydrochloride, erythromycin, erythromycin-zinc, erythromycin stolate, erythromycin stearate, amikacin sulfate, doxycycline sulfate, kaconomycin sulfate, gluconomycin sulfate, doxycycline hydrochloride chlorhexidine, chlorhexidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride, Metronidazole Hydrochloride, Pentamidine Hydrochloride, Gentamicin Sulfate, Kanamycin Sulfate, Lineomycin Hydrochloride, Methacycline Hydrochloride, Methenamine Hippurate, Methenamine Mandelate, Minocycline Hydrochloride, Neomycin Sulfate, Nethyl Deomycin Sulfate, Paromycin Sulfate streptomycin, tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride, amanfadine sulfate, octopirox, parachloromethaxylenol, nystatin, tolnaphtate and clotrimazole.

The cosmetic compositions of this invention may also contain sunscreens, which are chemical absorbents that actually absorb harmful ultraviolet radiation. It is well known that chemical absorbers are classified, depending on the type of radiation against which they protect, as either UV-A or UV-B absorbers. UV-A absorbers generally absorb radiation in the 320-400 nm region of the ultraviolet spectrum. UV-A absorbers include anthranlates, benzophenones, and dibenzoylmethanes. UV-B absorbers generally absorb radiation in the 280-320 nm region of the ultraviolet spectrum. UVB absorbers include derivatives of p-aminobenzoic acid, derivatives of camphor, cinnamates, and salicylates.

Sunscreens useful in the present invention typically comprise chemical absorbents, but may also comprise physical blockers. Exemplary sunscreens that may be formulated into the compositions of the present invention are chemical absorbents such as p-aminobenzoic acid derivatives, anthranlates, benzophenones, camphor derivatives, cinnamic derivatives, dibenzoylmethanes (such as avobenzone

ES 2 365 754 T3 also known as Parsol® 1789), diphenylacrylate derivatives, salicylic derivatives, triazine derivatives, benzimidazole compounds, bis-benzoazolyl derivatives, methylene-bis- (hydroxyphenylbenzotriazole) compounds, filter polymers and silicones solar or mixtures thereof. Also exemplary of sunscreens that can be formulated in the compositions of this invention are physical blockers such as cerium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone-treated titanium dioxide, carbon dioxide. titanium, zinc oxide and / or zirconium oxide or mixtures thereof.

Examples of suitable sunscreens include, but are not limited to: Aminobenzoic acid, amyldimethyl PABA, cinoxate, diethanolamine p-methoxycinnamate, digalloyl trioleate, dioxybenzone, 2-ethoxyethyl p-methoxycinnamate, ethyl 4-bis (hydroxypropyl) aminobenzoate, 2-ethylhexyl-2-cyano diphenylacrylate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate, homomenthyl salicylate, homosalate, 3-imidazole-4ylacrylic acid and ethyl ester, methyl anthranilate, octyldimethyl PABA, 2-Phenylbenzimidazole-5-sulfonic acid and salts, red vaseline, sulisobenzone, titanium dioxide, triethanolamine salicylate, N, N, N-trimethyl-4- (2oxoborn-3-ylidenemethyl) anillinium methylsulfate, and mixtures thereof.

The lip treatment composition of the invention may be in the form of a lipstick, a lip gloss or a lipstick, optionally exhibiting care or treatment properties.

Rheology

The rheological properties of the compositions according to the present invention are determined using a controlled stress rheometer, commercially available from TA Instruments under the name AR-G2. Samples are measured using a parallel plate featuring a 40 mm diameter cross-hatched stainless steel plate. The space adjusts to 1,000 microns. The desired temperature is precisely controlled by a Peltier system.

The lip gloss sample is transferred to the rheometer, and heated to 35 ° C for approximately 10 minutes. The sample is then cooled and held at 25 ° C for about 10 minutes or more.

The linear viscoelastic regime is determined by a sweep mode of oscillating forces with a range from 1 mN.m to 100 mN.m, at a constant frequency of 1 rad / s. Said linear viscoelastic regime corresponds to the elastic / storage modulus G ', within the above range, when the elastic / storage modulus G' is constant, or nearly constant, at the applied oscillation force.

The frequency sweep experiment is then performed from 100 rad / s to 0.01 rad / s at a low oscillation force in the linear viscoelastic regime. The elastic / storage modulus G 'at a frequency ω of 0.01 rad / s is determined from the frequency sweep mode.

The lower the elastic / storage modulus G 'value, at a frequency ω of 0.01 rad / s, the better the wetting property and the lower the slip resistance for the lip gloss composition.

In the linear viscoelastic regime, the elastic / storage modulus G 'at a frequency ω of 0.01 rad / s, of compositions according to the present invention, is in the range of from 0.01 Pa to 500 Pa at 25 ° C .

After the end of the dynamic oscillation experiment, the same sample is equilibrated for 10 minutes, at a constant temperature of 25 ° C. Slip and recovery measurements are then made at a constant force of 0.8 Pa.

The shear viscosity (qdesisation) of the lip gloss composition, measured at a constant force (σ) of 0.8 Pa, is determined from the shear stress (and shear) and the recoverable stress ( and recovery), in which the duration of the slip stress (tdesisation) is 10 minutes and the duration of the recoverable stress is 30 minutes. The slip viscosity is calculated using the following expression:

& t slip slip i

Vslip

<img file="ES2365754T3_D0001.tif" />

^ recovery

<img file="ES2365754T3_D0002.tif" />

A high value of slip viscosity (qdesisation) at low force, with a slip time of 10 minutes (shear rate close to zero), provides a longer life of the composition. Therefore, a lip composition with a high slip viscosity value (qdesisation) at low force will maintain its structure, therefore its stability, at rest, will show less migration and will provide a long-lasting shine.

ES 2 365 754 T3

The sliding viscosity (qdischarge) of compositions according to the present invention, at a constant force (σ) of 0.8 Pa, is in the range from 2 Pa.s to 150,000 Pa.s at 25 ° C .

MAKEUP PROCEDURE

FINISH COAT COMPOSITION

As indicated above, the composition according to the present invention can advantageously be used as a top coat in the claimed make-up process according to the invention.

This composition is as defined above.

In addition, it may be desirable to improve the comfort of the topcoat composition on the keratinous substrate to which it is applied such as, for example, the lips. This can be achieved by using a short chain ester.

According to the invention, the esters can be either monoesters, diesters or polyesters. These esters can be linear, branched or cyclic, saturated or unsaturated. These esters should preferably be branched and saturated. They can also be aliphatic or aromatic.

These esters can have from 6 to 25 carbon atoms and particularly from 14 to 22 carbon atoms. They can be chosen from acid esters having from 2 to 18 carbon atoms, and particularly from alcohol esters having from 2 to 20 carbon atoms or from polyols having from 2 to 8 carbon atoms or their mixtures, provided that the number of carbon atoms is greater than 10, so that the ester is not volatile and penetrates the skin.

In particular, these esters are hydrocarbon-based esters corresponding to the following formula RCOOR 'in which R represents a fatty acid residue having from 1 to 29 carbon atoms, and R' represents a hydrocarbon-based chain containing from 2 to 30 carbon atoms, provided that the number of carbon atoms in R 'is greater than 10, so that the ester is not volatile and penetrates the skin.

The ester can be chosen from a non-limiting list that includes the following:

Neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldocecyl neopentanoate, isononanoic acid esters such as isononyl isononanoate, isotridecyl isononanoate isononanoate, isodecyl isononane isononanoate, isoidecyl isononane isononanoate ethylhexyl, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, Isopropyl isostearate or stearate, isopropyl laurate, diisopropyl adipate, alkyl or polyalkyl octanoates, decanoates or ricinoleates, such as cetyl octanoate, tridecyl octanoate, polyalkylene glycol esters, such as polyethylene glycol diheptanoate, diethylene glycol 2-hexanoate their mixtures, alkyl benzoates, particularly alkyl benzoates having 12 to 15 carbon atoms, hydroxylated esters such as isotearyl lactate and diisostearyl malate, and pentaexitritol esters.

Examples of short chain esters also include Purcellin oil (cetostearyl octanoate), ethylhexyl ethylhexanoate, dicapryl ester, 2-ethylhexyl palmitate, 2-ethyl palmitate, and isostearyl isostearate.

Isononyl isononanoate and diisostearyl malate are particularly suitable for carrying out this invention.

The short chain ester (s) may be used in the topcoat composition in an amount of up to about 15% by weight, preferably up to about 10% by weight, based on the weight of the composition. finish coat. It should be noted that the use of too short chain ester (s) in the top coat will have a detrimental effect on the non-transfer properties of the cosmetic product system as it will cause the top coat to become too compatible with the top coat. of

ES 2 365 754 T3 base.

BASE COAT COMPOSITION

The terms "film-forming compound" or "film-forming agent" as used herein mean a polymer which, upon dissolution in at least one solvent (such as, for example, water and organic solvents), leaves a film on the substrate to which it is applied, for example, once at least one solvent evaporates, is absorbed and / or dissipates on the substrate.

The expression resistance to transfer. As used herein, it refers to the quality exhibited by compositions that are not easily removed by contact with another material, such as, for example, glass, a garment or the skin, for example, when you eat or drink. The transfer resistance can be evaluated by any method known in the art for its evaluation. For example, the transfer resistance of a composition can be assessed by a kiss test. The kiss test may involve application of the composition to human lips followed by kissing a material, for example a sheet of paper, after a certain amount of time has elapsed after application, such as 2 minutes after application. Similarly, the resistance to transfer of a composition can be evaluated by the amount of product transferred from the wearer to any other substrate, such as transfer from the neck of an individual to the neck of a garment after the course of a certain period of time. amount of time after application. The amount of composition transferred to the substrate (eg, to the collar of a garment, or paper) can then be evaluated and compared. For example, a composition may be resistant to transfer if most of the product remains on the user, eg, on the lips, neck, etc. In addition, the amount transferred can be compared to that transferred by other compositions, such as commercially available compositions. In a preferred embodiment of the present invention, little or no composition is transferred to the substrate.

Long-lasting compositions, as used herein, refers to compositions in which at least one property selected from consistency, texture, and color remains the same as the time of application, as seen with the naked eye, after an extended period of time, such as, for example, 1 hour, 2 hours, and additionally such as 8 hours. Long-lasting properties can be evaluated by any method known in the art to evaluate such properties. For example, long life can be evaluated by a test involving the application of a composition to human skin (including the lips) and the evaluation of the consistency, texture and color of the composition after a prolonged period of time. For example, the consistency, texture and color of a lip composition can be evaluated immediately upon application and these characteristics can then be re-evaluated and compared after an individual has worn the lip composition for a certain amount of time. weather. In addition, these characteristics can be evaluated relative to other compositions, such as commercially available compositions.

The term "water resistant" as used herein refers to the ability to repel water and to permanence with respect to water. Water resistance properties can be evaluated by any method known in the art to evaluate such properties. For example, a mascara composition can be applied to false eyelashes, which can then be placed in water for a certain amount of time, such as, for example, 20 minutes. After the preset amount of time has elapsed, the false eyelashes can be removed from the water and passed over a material, such as, for example, a sheet of paper. The degree of residue remaining on the material can be evaluated and then compared to other compositions, such as, for example, commercially available compositions. Similarly, for example, a composition can be applied to the skin, and the skin can be immersed in water for a certain amount of time. The amount of composition remaining on the skin after a preset amount of time can then be evaluated and compared. For example, a composition can be waterproof if most of the product stays on the user, eg on the eyelashes, skin, etc. In a preferred embodiment of the present invention, little or no composition is transferred from the user.

The cosmetic compositions and methods of the present invention may comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, or limitations described herein or useful in any case in personal care compositions intended for topical application to the skin.

According to certain aspects of the present invention, the phrase liquid fatty phase is understood to mean a fatty phase, which is liquid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg), and which comprises one or more fatty substances that They are liquid at room temperature, also known as oils, which are compatible with each other.

According to certain aspects of the present invention, the phrase "structured liquid fatty phase" is understood to mean that this structured phase does not slide between the fingers and is at least thickened.

ES 2 365 754 T3

When the liquid fatty phase is structured, it is possible to limit the exudation of the fatty phase of the solid compositions, and furthermore, to limit, after deposition on the skin or lips, its migration to wrinkles and fine lines, which is You want for compositions such as a lipstick or an eye shadow. Significant migration of the liquid fatty phase, loaded with coloring materials, leads to an unsightly effect around the lips or eyes, which can accentuate wrinkles and fine lines. Women often cite this migration as the main flaw in conventional lipsticks and eyeshadows. The term "migration" is understood to mean the sliding of the deposited composition on the lips or skin beyond its initial profile.

The term gloss essentially refers to the nature of the liquid fatty phase. Therefore, it is possible to reduce the level of waxes and fillers in the composition in order to increase the gloss of a lipstick, but then the migration of the liquid fat phase increases. In other words, the levels of waxes and / or fillers necessary for the preparation of a stick of adequate hardness have been a limiting factor in the gloss of the deposition.

Tack, as used herein, refers to a measurement of the maximum tensile force, Fmax, required while separating two surfaces. Depending on the intended application and the formulation being designed, the desirable value for Fmax may vary. In some embodiments, the substantially non-tacky compositions have an F_max less than about 4 Newton (N), less than about 1 N, less than about 0.5 N, less than about 0.3 N, less than about 0.2 N, or less than 0.1 N. the technique can determine the Fmax of the composition, for example, by determining the maximum tensile force, measured with a model LLOYD type IR5K extensometer, necessary to separate two surfaces.

For example, two 38mm surfaces are mounted², A and B, which are solid, rigid, inert and non-absorbent, on mobile supports, oriented towards each other. Surfaces can move either toward or away from each other, or surface A can move independently of surface B or vice versa. Before insertion into the extensometer, surface A is coated with the composition to be measured, which can be dissolved in a solvent such as aqueous, hydroalcoholic, hydrocarbon, silicone and alcoholic solvents in a concentration of from about 10 to about 30%, preferably 20%, the surface A is coated in a thickness of from 1 to 10 mil, preferably 1 mil, and the surface is dried for 24 hours at room temperature, for example, 22 to 25 ° C, at a relative humidity of about 50%. Once inserted into the extensometer, surface A is subjected for 20 seconds to a compressive force of 3 N against surface B and then subjected to a tensile force for 30 seconds at a rate of 20 mm / minute. The amount of force, Fmax, necessary to obtain the initial separation is then noted. Determine an F_max mean by performing the procedure with multiple pairs, preferably at least six pairs, of surface A and surface B.

The cosmetic product system of the present invention can be in any form. For example, it can be a paste, a solid, a gel or a cream. It can be an emulsion, such as an oil-in-water or water-in-oil emulsion, a multiple emulsion, such as an oil-in-water or water-in-oil-in-water emulsion, or a solid, rigid or soft gel, including anhydrous gels. The system can also be in a form selected from a translucent anhydrous gel and a transparent anhydrous gel. The system of the invention can comprise, for example, an external or continuous fatty phase. The system can be anhydrous. In another embodiment, the system of the invention can be transparent or clear, including, for example, a non-pigment composition. The system can also be a molded or cast composition such as a bar or a disk. The compositions in one embodiment are solid such as a molded stick or a flowable stick. The compositions of the present invention may also be in the form of a lip composition such as a lipstick or liquid lip color, foundation, or mascara, exhibiting excellent and improved transfer resistance properties, flexibility, malleability, adhesion and lack of tack.

When the composition of the invention is not liquid, the structuring of the liquid fatty phase can be controlled by the type of polyorganosiloxane-containing polymer (or structuring polymer) used and it is so that a rigid structure in the form of a rod can be obtained. , of good mechanical resistance. Rigid compositions, when colored, allow smooth, luminous, non-transfer, non-migration and / or long-lasting applications on a keratinous surface. Such compositions can contain one or more structuring polymers.

As defined herein, stability is tested by placing the composition in a controlled environment chamber for 8 weeks at 25 ° C. In this test, the physical state of the sample is inspected when it is placed in the chamber. The sample is then inspected again at 24 hours, 3 days, 1 week, 2 weeks, 4 weeks, and 8 weeks. At each inspection, the sample is examined for compositional anomalies such as phase separation if the composition is in the form of an emulsion, curvature or inclination if the composition is in the form of stick, melting, or syneresis. (or exudation). Stability is further tested by repeating the test at 8 weeks at 40 ° C, 37 ° C, 45 ° C, 50 ° C and at

ES 2 365 754 T3 freeze-thaw conditions. A composition is considered to be lacking in stability if an abnormality is observed in any of these tests that prevents the composition from functioning. The skilled person will readily recognize an anomaly that prevents the performance of a composition based on the intended application.

Polymer containing polyorganosiloxane

According to the present invention, compositions are provided that comprise at least one polyorganosiloxane-containing polymer selected from homopolymers and copolymers, preferably with a weight average molecular mass ranging from about 500 to about 2.5 x 10⁶ or more, comprising at least one residue comprising: at least one polyorganosiloxane group preferably comprising from 1 to about 10,000 organosiloxane units in the chain of the residue or in the form of a graft, and at least two groups that can establish hydrogen interactions.

According to preferred embodiments of the present invention, the polymers containing polyorganosiloxane used in the composition of the invention may belong to the following two families:

a) polyorganosiloxanes comprising at least two groups that can establish hydrogen interactions, these two groups being located in the polymer chain; me

b) polyorganosiloxanes comprising at least two groups that can establish hydrogen interactions, these two groups being located in grafts or branches.

The polyorganosiloxane-containing polymers of the present invention can be liquid or solid at room temperature. Preferably the polymers are solid. When the polymers are solid, it is preferable that they can be dissolved before or during use in a hydrogen-interacting solvent that can disrupt the hydrogen interactions of the polymers, for example C2 to C8 lower alcohols and especially ethanol, n-propanol or isopropanol. It is also possible to use these solvents that break the hydrogen interaction as cosolvents in the compositions of the present invention. These solvents can then be stored in the composition or can be removed by selective evaporation, which is well known to those skilled in the art.

Polymers that comprise two groups that can establish hydrogen interactions in the polymer chain can be polymers that comprise at least one residue that corresponds to the formula:

<img file="ES2365754T3_D0003.tif" />

(I »in which:

1) R¹, R², R³ and R⁴, which may be identical or different, represent a group selected from:

- C1 to C40 hydrocarbon-based groups, saturated or unsaturated, linear, branched or cyclic, possibly containing in their chain one or more oxygen, sulfur and / or nitrogen atoms, and possibly being partially or totally substituted with atoms of fluorine,

- C6 to C10 aryl groups, optionally substituted with one or more C1 to C4 alkyl groups,

- polyorganosiloxane chains possibly containing one or more oxygen, sulfur and / or nitrogen atoms;

2) the groups x, which may be identical or different, represent a linear or branched C1 to C30 alkylene diyl group, possibly containing in its chain one or more oxygen and / or nitrogen atoms;

3) Y is a divalent, linear or branched, C1 to C50 alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, saturated or unsaturated, possibly comprising one or more oxygen, sulfur and / or nitrogen atoms, and / or which carries as a substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, cycloalkyl of

ES 2 365 754 T3

C₃ a Ce, Ci to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C alkyl groups₃, C hydroxyalkyl₁ to C₃ and aminoalkyl of C₁ to C₆, or

4) Y represents a group that corresponds to the formula:

<img file="ES2365754T3_D0004.tif" />

in which

- T represents a group based on trivalent or tetravalent hydrocarbon, of C₃ to C24, saturated or unsaturated, straight or branched, optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and A1 , Y

R⁵ represents a linear or branched C1 to C50 alkyl group or a polyorganosiloxane chain, possibly comprising one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide groups, which may be linked to another chain of the polymer;

5) G groups, which may be identical or different, represent divalent groups selected from:

<img file="ES2365754T3_D0005.tif" />

<td>C—— N (R^and) - II</td><td>--Ν (| Λ_ $ Ο, -</td><td>--- SO] -</td><td>—.N (R⁶)</td>

<td>il 0</td><td></td><td></td><td></td>

<img file="ES2365754T3_D0006.tif" />

<img file="ES2365754T3_D0007.tif" />

<img file="ES2365754T3_D0008.tif" />

<img file="ES2365754T3_D0009.tif" />

s in which R⁶ represents a hydrogen atom or a linear or branched C1 to C20 alkyl group, provided that at least 50% of the R groups⁶ of the polymer represents a hydrogen atom and that at least two of the G groups of the polymer are a group other than:

<img file="ES2365754T3_D0010.tif" />

6) n is an integer of at least 1, for example ranging between 2 and 500 and preferably between 2 and 200, and m is an integer of at least one, ranging between 1 and 35,000, for example between 1 and 10,000 and between 1 and 2,500, between 1 and 700 and between 6 and 200, including all values ​​and subintervals between them.

According to the invention, 80% of the R groups¹, R², R³ and R⁴ of the polymer are preferably selected from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.

ES 2 365 754 T3

According to the invention, Y can represent various divalent groups, optionally further comprising one or two free valences to establish bonds with other moieties of the polymer or copolymer. Preferably, Y represents a group selected from:

a) linear alkylene groups from Ci to C20 and preferably from C1 to C10,

b) C30 to Cse branched alkylene groups possibly comprising unconjugated rings and unsaturations,

c) C cycloalkylene groups₅-C₆,

d) phenylene groups optionally substituted with one or more C1 to C40 alkyl groups,

e) C1 to C20 alkylene groups comprising from 1 to 5 amide groups,

f) C1 to C20 alkylene groups comprising one or more substituents selected from hydroxyl groups, C3 to Ce cycloalkane, C1 to C3 hydroxyalkyl and C1 to Ce alkylamine,

g) polyorganosiloxane chains of formula:

<img file="ES2365754T3_D0011.tif" />

in which R¹, R², R³, R⁴, T and m are as defined above, and

h) polyorganosiloxane chains of formula:

R²

------ Yes ------ O-

<img file="ES2365754T3_D0012.tif" />

R⁴

The polyorganosiloxanes of the second family can be polymers comprising at least one residue corresponding to formula (II)

<img file="ES2365754T3_D0013.tif" />

in which

R¹ and R³, which may be identical or different, are as defined above for formula (I),

R⁷ represents a group as defined above for R¹ and R³, or represents a group of formula -X-GR⁹ where X and G are as defined above for formula (I) and R⁹ represents a hydrogen atom or a hydrocarbon-based group, from C1 to C50, saturated or unsaturated, linear, branched or cyclic, optionally comprising in its chain one or more atoms selected from among O, S and N, optionally

ES 2 365 754 T3 substituted with one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted with one or more C alkyl groups₁ to C₄,

R⁸ represents a group of formula -XGR⁹ where X, G and R⁹ are as defined above, mi is an integer of at least one between 1 and 35,000, for example, between 1 and 10,000 and between 1 and 2,500, between 1 and 700, and between 6 and 200, including all values and subintervals between them; Y

- rri2 is an integer of at least one between 1 and 35,000, for example, between 1 and 10,000 and between 1 and 2,500, between 1 and 700, and between 6 and 200, including all values ​​and sub-ranges between them.

According to the invention, the polyorganosiloxane-containing polymer can be a homopolymer, that is to say a polymer comprising several identical moieties, in particular moieties of formula (I) or of formula (II).

According to the invention, it is also possible to use a polymer consisting of a copolymer comprising several different moieties of formula (I), that is to say a polymer in which at least one of the R groups¹, R², R³, R⁴, X, G, Y, m and n is different in one of the remains. The copolymer can also be formed of several moieties of formula (II), in which at least one of the R groups¹, R³, R⁷, R⁸, mi and rri2 is different in at least one of the remains.

It is also possible to use a copolymer comprising at least one residue of formula (I) and at least one residue of formula (II), the residues of formula (I) and residues of formula (II) being possibly identical or different from each other .

According to preferred embodiments, it is also possible to use a copolymer comprising at least one hydrocarbon-based moiety comprising two groups that can establish hydrogen interactions, selected from ester, amide, sulfonamide, carbamate, thiocarbamate, urea and thiourea groups. , and combinations thereof.

According to a first embodiment of the invention, the groups that can establish hydrogen interactions are amide groups of formulas -C (O) NH- and -HN-C (O) -.

These copolymers can be block copolymers or graft copolymers.

In this case, the polymer can comprise at least one residue of formula (III) or (IV)

<img file="ES2365754T3_D0014.tif" />

in which R¹, R², R³, R⁴, X, Y, m and n are as defined above.

Such a remainder can be obtained:

- or by means of a condensation reaction between a silicone containing α, ω -carboxylic acid endings and one or more diamines, according to the following reaction scheme:

ES 2 365 754 T3

<img file="ES2365754T3_D0015.tif" />

- or by reacting two molecules of α-unsaturated carboxylic acid with a diamine according to the following reaction scheme:

CH₂-CH-X¹-COOH + H2N-Y-NH2 -&gt; CH2 = CH-X¹-CO-NH-Y-NH-CO-X¹-CH = CH2 followed by the addition of a siloxane to the ethylenic unsaturations, according to the following scheme: CH₂= CH-X¹CO-NH-Y-NH-CO-X¹-CH = CH₂

<img file="ES2365754T3_D0016.tif" />

<img file="ES2365754T3_D0017.tif" />

CO --- NH

Y — NH where X¹- (CH₂)₂- corresponds to X defined above and Y, R¹, R², R³, R⁴ and m are as defined above;

- or by reacting a silicone containing α, ω-ΝΗ endings₂ and a diacid of formula HOOC-YCOOH according to the following reaction scheme:

<img file="ES2365754T3_D0018.tif" />

<img file="ES2365754T3_D0019.tif" />

In these polyamides of formula (III) or (IV), m is an integer of at least one as defined above, and preferably in the range of from 1 to 700, for example, from 15 to 500 and from 15

ES 2 365 754 T3 up to 45, including all values ​​and sub-ranges between them; and n is in particular in the range from 1 to 500, for example, from 1 to 100 and from 4 to 25, including all values ​​and sub-ranges therebetween; X is preferably a straight or branched alkylene chain containing from 1 to 30 carbon atoms and in particular from 3 to 10 carbon atoms, and Y is preferably an alkylene chain that is straight or branched or possibly comprising rings and / or unsaturations, containing from 1 to 40 carbon atoms, including from 1 to 20 carbon atoms and from 2 to 6 carbon atoms, including all values ​​and sub-ranges therebetween, for example, 6 carbon atoms.

In formulas (III) and (IV), the alkylene group represented by X or Y may optionally contain in its alkylene part at least one of the following elements:

1) 1 to 5 amide, urea or carbamate groups,

2) a C5 or Ce cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical or different C1 to C3 alkyl groups.

In formulas (III) and (IV), the alkylene groups can also be substituted with at least one element selected from the group consisting of:

a hydroxyl group, a C cycloalkyl group₃ to C₈, one to three C1 to C40 alkyl groups, a phenyl group optionally substituted with one to three C1 to C3 alkyl groups, a C1 to C3 hydroxyalkyl group, and a C1 to Ce aminoalkyl group.

In these formulas (III) and (IV), Y can also represent:

<img file="ES2365754T3_D0020.tif" />

in which R⁵ represents a polyorganosiloxane chain and T represents a group of formula:

r ____ (CHj, ---- C ---- (CHjJi ---- o ---- (CHj) .---- N ---- (CHA— (CHA, ^{, α4}Λ where a, b and c are, independently, integers ranging from 1 to 10, and R¹⁰ is a hydrogen atom or a group such as those defined for R¹, R², R³ and R⁴.

In formulas (III) and (IV), R¹, R², R³ and R⁴ preferably represent, independently, a linear or branched C1 to C40 alkyl group, preferably an isopropyl group or CH3, C2H5, n-CsEE, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups .

As noted above, the polymer can comprise identical or different moieties of formula (III) or (IV).

Therefore, the polymer can be a polyamide containing several moieties of formula (III) or (IV) of different lengths, that is, a polyamide corresponding to the formula:

<img file="ES2365754T3_D0021.tif" />

(V) in which X, Y, ny of R¹ to R⁴ have the meanings given above, mi and ΠΙ2, which are different, are as defined above, and are preferably chosen in the range from 1 to 1000, and p is at

ES 2 365 754 T3 minus one for example ranging between 2 and 500 and preferably between 2 and 200.

In this formula, the moieties can be structured to form either a block copolymer, a raised copolymer, or an alternate copolymer. In this copolymer, the residues can be not only of different lengths, but also of different chemical structures, containing for example different Y groups. In this case, the copolymer can correspond to the formula:

<img file="ES2365754T3_D0022.tif" />

IV »in which R¹ to R⁴, X, Y, mi, rrt, n and p have the meanings provided above and Y¹ is different from Y but is selected from the groups defined for Y. As discussed above, the various moieties can be structured to form either a block copolymer, a random copolymer, or an alternate copolymer.

In one embodiment of the invention, the polyorganosiloxane-containing polymer may also contain a graft copolymer. Thus, the polyamide-containing silicone units can optionally be grafted and cross-linked with silicone chains containing amide groups. Such polymers can be synthesized with trifunctional amines.

In this case, the copolymer can comprise at least one moiety of the formula:

<img file="ES2365754T3_D0023.tif" />

in which X¹ and X², which may be identical or different, have the meanings given for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), de R¹¹ to R¹⁸ are groups selected from the same group as R¹ to R⁴, πη and m₂ are numbers in the range of 1 to 1,000, and p is an integer of at least one, for example, p can range from 2 to 500.

In the formula (Vil), it is preferred that:

p is in the interval between 1 and 25, including between 1 and 7, including all values ​​and subintervals between them,

R¹¹ to R¹⁸ are methyl groups,

- T corresponds to one of the following formulas:

ES 2 365 754 T3 r²L_.

in which R¹⁹ is a hydrogen atom or a group selected from the groups defined for R¹ to R⁴, and R²⁰, R²¹ and R²² they are, independently, linear or branched alkylene groups, and more preferably correspond to the formula:

R²⁰

N ____R²¹

R²²

twenty-one 22 in particular with R, R and R representing -CH2-CH2-,

- mi and mi2 are in the interval between 15 and 500, including between 15 and 45 and including all values ​​and subintervals between them,

- X¹ and X² represent - (CH₂) io-, θ

- Y represents -CH2-.

These polyamides containing a grafted silicone moiety of formula (Vil) can be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternate copolymers or random copolymers. The percentage by weight of the grafted silicone residues (Vil) in the copolymer can range between 0.5% and 30% by weight.

According to the invention, as noted above, the siloxane units can be in the main chain or backbone of the polymer, but can also be present in grafted or pendant chains. In the backbone, the siloxane units can be in the form of segments as described above. In pendant or grafted chains, the siloxane units can appear individually or in segments.

According to the invention, the preferred siloxane-based polyamides are:

polyamides of formula (III) in which m is from 15 to 300, for example, from 15 to 100, including all values ​​and sub-ranges therebetween;

mixtures of two or more polyamides in which at least one polyamide has a value of m in the range between 15 and 50, including all values ​​and sub-ranges between them and at least one polyamide has a value of m in the range of from 30 to 300, including all values ​​and subintervals between them;

polymers of formula (V) selecting πη in the range between 15 and 50 and selecting m₂ in the range between 30 and 500 representing the part corresponding to πη from 1% to 99% by weight of the total weight of the polyamide and representing the part corresponding to πη from 1% to 99% by weight of the total weight of the polyamide;

ES 2 365 754 T3

- polyamide blends of formula (III) combining

1) 80% to 99% by weight of a polyamide in which n is equal to 2 to 10 and in particular 3 to 6, and

2) from 1% to 20% of a polyamide in which n is in the range from 5 to 500 and in particular from 6 to 100;

- polyamides corresponding to formula (VI) in which at least one of the groups Y and Y¹ contains at least one hydroxyl substituent;

- polyamides of formula (III) synthesized with at least a part of an activated diacid (diester, dianhydride or diacid chloride) instead of the diacid;

- polyamides of formula (III) in which X represents - (CH2) 3- or - (CH2) 10; Y

- polyamides of formula (III) in which the polyamides end with a monofunctional chain selected from the group consisting of monofunctional amines, monofunctional acids, monofunctional alcohols, including fatty acids, fatty alcohols and fatty amines, such as, for example, octylamine , octanol, stearic acid and stearyl alcohol.

According to the invention, the end groups of the polymer chain can end with:

- a C1 to C50 alkyl ester group by introducing a C1 to C50 monoalcohol during the synthesis,

- a C1 to C50 alkylamide group taking as a stopping group a mono acid if the silicone is α, ω diamine, or a monoamine if the silicone is an α, ω-dicarboxylic acid.

According to an embodiment of the invention, it is possible to use a silicone-polyamide and a hydrocarbon-based polyamide copolymer, that is to say a copolymer comprising moieties of formula (III) or (IV) and hydrocarbon-based polyamide moieties . In this case, the polyamide-silicone moieties can be arranged at the ends of the hydrocarbon-based polyamide.

Silicones containing polyamide-based polymers can be produced by silyl amidation of fatty acid-dimer-based polyamides. This approach involves the reaction of free acidic sites on a polyamide as end sites, with organosiloxane-monoamines and / or organosiloxane-diamines (amidation reaction), or alternatively with oligosiloxane alcohols or oligosiloxane diols (esterification reaction). The esterification reaction requires the presence of acid catalysts, as is known in the art. It is desirable for the polyamide to contain free acid sites, used for the amidation or esterification reaction, to have a relatively high number of acid end groups (eg polyamides with high acid numbers, eg from 15 to 20).

For the amidation of the free acidic sites of the hydrocarbon-based polyamides, siloxane diamines with 1 to 300, more particularly 2 to 50 and for example 2, 6, 9.5, 12, 13.5 , 23 or 31 siloxane groups, for reaction with hydrocarbon-based polyamides based on fatty acid dimers. Siloxane diamines containing 13.5 siloxane groups are preferred, and the best results are obtained with siloxane diamine containing 13.5 siloxane groups and polyamides containing a high number of carboxylic acid end groups.

Reactions can be carried out in xylene to extract the water produced from solution by azeotropic distillation, or at higher temperatures (approximately 180 to 200 ° C) without solvent. Normally, the efficiency of the amidation and the reaction rates decrease when the siloxane diamine is longer, that is when the number of siloxane groups is higher. Free amine sites can be blocked after the initial amidation reaction of diaminosiloxanes by reacting them with either a siloxane acid or an organic acid such as benzoic acid.

For the esterification of the free acidic sites in the polyamides, this can be carried out in boiling xylene with about 1% by weight, relative to the total weight of the reactants, of para-toluenesulfonic acid as a catalyst.

These reactions carried out at the carboxylic acid end groups of the polyamide lead to the incorporation of silicone moieties only at the ends of the polymer chain.

It is also possible to prepare a polyamide-silicone copolymer, using a polyamide containing free amine groups, by amidation reaction with a siloxane containing an acid group.

ES 2 365 754 T3

It is also possible to prepare a gelling agent based on a copolymer between a hydrocarbon-based polyamide and a silicone-polyamide, by transamidation of a polyamide having, for example, an ethylene-diamine constituent, with an oligosiloxane-a, ®-diamine, at high temperature (for example 200 to 300 ° C), to carry out a transamidation so that the ethylenediamine component of the original polyamide is replaced with the oligosiloxane diamine.

The hydrocarbon-based polyamide and polyamide-silicone copolymer may also be a graft copolymer comprising a hydrocarbon-based polyamide backbone with pendant oligosiloxane groups.

This can be obtained, for example:

- by hydrosilylation of unsaturated bonds in polyamides based on fatty acid dimers;

- by silylation of the amide groups of a polyamide; or

- by silylation of unsaturated polyamides by means of oxidation, that is by oxidation of unsaturated groups in alcohols or diols, to form hydroxyl groups which are reacted with siloxane carboxylic acids or siloxane alcohols. The olefinic sites of the unsaturated polyamides can also be epoxidized and the epoxy groups can then be reacted as siloxane amines or siloxane alcohols.

The polyorganosiloxane-containing polymers used in the composition of the invention are most preferably polymers of the polyorganosiloxane type such as those described in US Patents No. 5,874,069, US No. 5,919,441, US No. 6,051,216 and US Pat. No. 5,981,680, the full disclosures of which are incorporated herein by reference.

According to another embodiment of the invention, the polyorganoxyloxane-containing polymer is a homopolymer or a copolymer comprising urethane or urea groups.

As discussed above, the polymer can comprise polyorganosiloxane moieties containing two or more urethane and / or urea groups, either in the backbone of the polymer or in side chains or as pendant groups.

Polymers that comprise at least two urethane and / or urea groups in the main structure can be polymers that comprise at least one moiety that corresponds to the following formula:

<img file="ES2365754T3_D0024.tif" />

in which R¹, R², R³, R⁴, X, Y, m and n have the meanings given above for formula (I), and U represents -O- or -NH-, in such a way that:

U - C - NH-O corresponds to a urethane or urea group.

In this formula (VIII), Y may be a linear or branched C1 to C40 alkylene group, optionally substituted with a C alkyl group.₁ to C₁₅ or an aryl group of C₅ to C₁₀. Preferably, a group - (CH₂)₆-.

And it can also represent a cycloaliphatic or aromatic group of C₅ to C₁₂ which may be substituted with an alkyl group of C₁ to C₁₅ or an aryl group of C₅ to C₁₀, for example a radical selected from the radical methylene-4,4biscyclohexyl, the radical derived from isophorone diisocyanate, 2,4- and 2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4'biphenylenemethane . Generally, it is preferred that Y represents a linear or branched C1 to C40 alkylene radical or a C4 to C12 cycloalkylene radical.

ES 2 365 754 T3

And it can also represent a polyurethane or polyurea block that corresponds to the condensation of several diisocyanate molecules with one or more molecules of coupling agents of the diol or diamine type. In this case, Y comprises several urethane or urea groups in the alkylene chain.

It can correspond to the formula:

<img file="ES2365754T3_D0025.tif" />

in which B¹ is a group selected from the groups given above for Y, U is -O- or -NH- and B² is selected from:

linear or branched C1 to C40 alkylene groups, which may optionally carry an ionizable group such as a carboxylic acid or sulfonic acid group, or a neutralizable or quaternizable tertiary amine group, C5 to C12 cycloalkene groups, optionally bearing alkyl substituents, for example of one to three methyl or ethyl groups, or alkylene, for example the diol radical: cyclohexanedimethanol, phenylene groups that may optionally carry C1 to C3 alkyl substituents, and groups of the formula:

<img file="ES2365754T3_D0026.tif" />

where T is a trivalent hydrocarbon-based radical possibly containing one or more heteroatoms such as oxygen, sulfur and nitrogen and R⁵ is a polyorganosiloxane chain or a straight or branched C1 to C50 alkyl chain.

T can represent, for example:

---- (CH₂)_w ---- CH

---- CH₂

---- (CH₂)_W ---- O ---- CH ---- CH₂ where w is an integer ranging from 1 to 10 and where R⁵ a polyorganosiloxane chain.

When Y is a linear or branched C1 to C40 alkylene group, the groups - (CH2) 2- and - (CH2) 6- are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to 5, preferably from 0 to 3, and more preferably equal to 1 or 2.

Preferably, B² is a linear or branched C1 to C40 alkylene group, in particular - (CH2) 2- or - (CH2) 6- or a group:

<img file="ES2365754T3_D0027.tif" />

ES 2 365 754 T3 where R⁵ a polyorganosiloxane chain.

As discussed above, the polyorganosiloxane-containing polymer can be formed from silicone urethane and / or silicone urea moieties of different length and / or constitution, and can be in the form of block or random copolymers.

According to the invention, the silicone can also comprise urethane and / or urea groups not only in the main structure but in the side branches.

In this case, the polymer can comprise at least one moiety of the formula:

<img file="ES2365754T3_D0028.tif" />

in which R¹, R², R³, m₁ and m₂ have the meanings given above for formula (I),

- U represents O or NH,

- R²³ represents a C1 to C40 alkylene group, optionally comprising one or more heteroatoms selected from O and N, or a phenylene group, and

- R²⁴ it is selected from linear, branched or cyclic, saturated or unsaturated C1 to C50 alkyl groups, and phenyl groups optionally substituted with one to three C1 to C3 alkyl groups.

Polymers comprising at least one moiety of formula (X) contain siloxane units and urea or urethane groups, and can be used, for example, as gelling agents in the compositions of the invention.

Siloxane polymers may have a single urea or urethane group per branch or they may have branches containing two urea or urethane groups, or alternatively they may contain a mixture of branches containing one urea or urethane group and branches containing two urea or urethane groups. .

They can be obtained from branched polysiloxanes, which comprise one or two amino groups per branch, by reacting these polysiloxanes with monoisocyanates.

As examples of starting polymers of this type containing amino and diamino branches, the polymers corresponding to the following formulas may be mentioned:

<img file="ES2365754T3_D0029.tif" />

ES 2 365 754 T3

<img file="ES2365754T3_D0030.tif" />

ky = 56;

NH ---- (CRJjNHj

In these formulas, the symbol indicates that the segments can be of different lengths and in random order, and R represents a linear aliphatic group preferably containing 1 to 6 carbon atoms, including 1 to 3 carbon atoms.

Such branching-containing polymers can be formed by reacting a siloxane polymer, containing at least three amino groups per polymer molecule, with a compound containing only one monofunctional group (eg, an acid, an isocyanate, or an isothiocyanate) to react this monofunctional group with one of the amino groups and to form groups that can establish hydrogen interactions. The amino groups can be on side chains that extend from the main chain of the siloxane polymer, such that groups that can establish hydrogen interactions are formed on those side chains, or alternatively the amino groups can be on the ends of the main chain, such that the groups that can establish a hydrogen interaction will be terminal groups of the polymer.

As a process for forming a polymer containing siloxane units and groups that can establish hydrogen interactions, the reaction of a siloxane-diamine and a diisocyanate in a silicone solvent to directly provide a gel can be mentioned. The reaction can be carried out in a silicone fluid, the resulting product dissolving in the silicone fluid, at a high temperature, then reducing the temperature of the system to form the gel.

Polymers that are preferred for incorporation into compositions according to the present invention are siloxane-urea copolymers which are linear and which contain urea groups as groups that can establish hydrogen interactions in the polymer backbone.

As an illustration of a polysiloxane ending with four urea groups, mention may be made of the polymer of formula:

<img file="ES2365754T3_D0031.tif" />

(Pt »= Phenyl)

<img file="ES2365754T3_D0032.tif" />

CjHí

N____CiH «---- NHCíO) N (») H

CjUa _C; H₄---- N

C (O | N (Ph) H

C (01NÍPhlH in which Ph is a phenyl group and n is a number greater than 0, which includes, at least 1, from 2 to 500, from 2 to 200, from 1 to 300, in particular from 1 to 100, and all the values ​​and sub-ranges between them, for example 50.

ES 2 365 754 T3

This polymer is obtained by reacting the following polysiloxane-containing amino groups:

<img file="ES2365754T3_D0033.tif" />

<td></td><td></td><td>CHj</td><td>CjHí</td>

<td></td><td>1 - --NH</td><td></td><td>1 NH --- CjH, ----^NHj</td>

<td></td><td></td><td>(n-50)</td><td></td>

with phenyl isocyanate.

Polymers of formula (VIII) comprising urea or urethane groups in the silicone polymer chain can be obtained by reaction between a silicone containing end groups q, w-NH₂ or -OH, of formula:

<img file="ES2365754T3_D0034.tif" />

in which m, R¹, R², R³, R⁴ and X are as defined for formula (I) and an OCN-Y-NCO diisocyanate in which Y has the meaning given in formula (I); and optionally a diol or diamine coupling agent of formula H2N-B²-NH2 or HO-B²-OH, where B² it is as defined in formula (IX).

According to the stoichiometric proportions between the two reagents, diisocyanate and coupling agent, Y can have the formula (IX) with d equal to 0 or d equal to 1 to 5.

As in the case of polyamide silicones of formula (II) or (III), it is possible to use in the invention polyurethane or polyurea silicones containing residues of different length and structure, in particular residues whose lengths differ in the number of silicone units. In this case, the copolymer may correspond, for example, to the formula:

<img file="ES2365754T3_D0035.tif" />

in which R¹, R², R³, R⁴, X, Y and U are as defined for formula (VIII) and m1, m₂, n and p are as defined for formula (V).

Branched polyurethane or polyurea silicones can also be obtained by using, instead of OCN-YNCO diisocyanate, a triisocyanate of the formula:

ES 2 365 754 T3

<img file="ES2365754T3_D0036.tif" />

Thus, a polyurethane or polyurea silicone is obtained that contains branches that comprise an organosiloxane chain with groups that can establish hydrogen interactions. Such a polymer comprises, for example, a residue corresponding to the formula;

<img file="ES2365754T3_D0037.tif" />

As in the case of polyamides, this copolymer can also comprise non-branched polyurethane silicone moieties.

In another embodiment of the invention, preferred polyurethanes and siloxane-based polyureas are:

- polymers of formula (VIII) in which m is from 15 to 300, for example, from 15 to 100 and all values ​​and sub-ranges therebetween;

- mixtures of two or more polymers in which at least one polymer has a value of m in the range between 15 and 50 and at least one polymer has a value of m in the range between 30 and 300, including all values and subintervals between them;

- polymers of formula (XII) with m1 chosen in the range between 15 and 50 and m2 chosen in the range between 30 and 500 representing the part corresponding to m1 from 1% to 99% by weight of the total weight of the polymer and representing the part corresponding to m2 from 1% to 99% by weight of the total weight of the polymer;

- polymer blends of formula (VIII) combining

1) 80% to 99% by weight of a polymer in which n is equal to 2 to 10 and in particular 3 to 6, and

2) from 1% to 20% of a polymer in which n is in the range between 5 and 500 and in particular between 6 and 100,

- copolymers comprising two moieties of formula (VIII) in which at least one of the Y groups contains at least one hydroxyl substituent;

- polymers of formula (VIII) synthesized with at least a part of an activated diacid (diacid chloride, dianhydride or diester) instead of the diacid;

ES 2 365 754 T3

- polymers of formula (VIII) in which X represents - (CH₂)₃- or - (CH₂)₁₀-; Y

- polymers of formula (VIII) in which the polymers end with a multifunctional chain selected from the group consisting of monofunctional amines, monofunctional acids, monofunctional alcohols, including fatty acids, fatty alcohols and fatty amines, such as, for example, octylamine , octanol, stearic acid and stearyl alcohol.

As in the case of polyamides, silicone copolymers of polyurethane or polyurea and hydrocarbon-based polyurethane or polyurea can be used in the invention by carrying out the reaction to synthesize the polymer in the presence of an α, ^ - difunctional block of a different nature. silicone, for example a polyester, a polyether or a polyolefin.

As seen above, homopolymers or copolymers of the invention can contain siloxane residues in the main chain of the polymer and groups that can establish hydrogen interactions, either in the main chain of the polymer or at its ends, either in side chains or branches of the main chain. This can correspond to the following five provisions:

<img file="ES2365754T3_D0038.tif" />

in which the solid line is the main chain of the siloxane polymer and the squares represent the groups that can establish hydrogen interactions.

In case (1), the groups that can establish hydrogen interactions are arranged at the ends of the main chain.

In case (2), two groups that can establish hydrogen interactions are arranged at each end of the main chain.

In case (3), the groups that can establish hydrogen interactions are arranged within the main chain in repeating residues.

In cases (4) and (5), they are copolymers in which the groups that can establish hydrogen interactions are arranged in branches of the main chain of a first series of residues that are copolymerized with residues that do not comprise groups that can establish hydrogen interactions. Preferably, the n, x and y values ​​are such that the polymer exhibits the desired properties as an agent for gelling fatty phases, preferably silicone oil-based fatty phases.

ES 2 365 754 T3

As examples of polymers that can be used, mention may be made of the silicone polyamides obtained according to the description in US-A-5,981,680, the entire description of which is incorporated by reference herein.

Additional examples of polyorganosiloxane-containing polymers are set forth in US Patent Nos. 6,503,632 and 6,569,955, both of which are incorporated by reference herein in their entirety.

As indicated above, the polymers of the present invention can be solid or liquid at room temperature. When solid, the polymers preferably have a softening point of from 50 to 130 ° C. Most preferably, they have a softening point of between 65 and 150 ° C, including from 70 ° C to 130 ° C. This softening point is lower than that of other structuring polymers, which facilitates the use of the polymers that are the object of the invention, and limits the deterioration of the liquid fatty phase.

As indicated above, the polyorganosiloxane-containing polymers of the present invention contain both siloxane units and at least two groups that can establish hydrogen interactions such as amide bonds. Siloxane units can provide compatibility with a silicone fluid, if present, (for example with cyclomethicones), while groups that can establish hydrogen interactions and the separation and selection of the locations of the amide bonds can facilitate the gelling and the formation of cosmetic products.

In one embodiment, the polyorganosiloxane-containing polymer of the present invention is present in an amount effective to provide transfer resistant properties, and may also provide at least one of the following properties: malleability, softness, and wearing comfort. Furthermore, it is preferred that the compositions of the invention show flexibility and / or good adhesion on the keratinous substance to which the compositions have been applied. In another preferred embodiment, the compositions of the present invention when applied to the keratinous substance are substantially non-tacky.

In the composition of the present invention, the polyorganosiloxane-containing polymers are preferably present in an amount of 0.1-80 percent by weight, more preferably 0.5 to 30 percent by weight, and most preferably from 0.1 to 80 percent by weight. 1 to 20 percent by weight of the total weight of the composition.

Depending on the intended application, such as a stick, the hardness of the composition can also be considered. The hardness of a composition can be expressed, for example, in grams force (gf). The composition of the present invention may have, for example, a hardness ranging between 20 gf and 2,000 gf, such as between 20 gf and 900 gf and further such as between 20 gf and 600 gf.

This hardness is measured in one of two ways. A first test to determine the hardness is according to a procedure for penetrating a probe into the composition and in particular using a texture analyzer (for example TA-XT2i from Rheo) equipped with an ebonite cylinder with a height of 25 mm and a diameter of 8 mm. The hardness measurement is carried out at 20 ° C in the center of 5 samples of the composition. The cylinder is introduced into each composition sample at a preliminary speed of 2 mm / s and then at a speed of 0.5 mm / s and finally at a subsequent speed of 2 mm / s, the total displacement being 1 mm. The hardness value recorded is that of the maximum peak observed. The measurement error is ± 50 gf.

The second test to determine hardness is the metallic wire procedure for cheese, which involves cutting a stick composition of 8.1 mm or preferably 12.7 mm in diameter and measuring its hardness at 20 ° C using a cutting machine. Indelco-Chatillon Co. tensile tests DFGHS 2 at a speed of 100 mm / minute. The hardness value of this procedure is expressed in grams as the shear force required to cut a bar under the above conditions. According to this method, the hardness of compositions according to the present invention which may be in stick form can range, for example, between 30 gf and 300 gf, such as between 30 gf and 250 gf, for a stick sample of 8.1 mm in diameter, and further such as between 30 gf and 200 gf, and also further such as between 30 gf and 120 gf for a 12.7 mm diameter bar sample.

The hardness of the composition of the present invention can be such that the compositions are self-supporting, self-supporting and can easily disintegrate to form a satisfactory deposit on a keratinous material. Furthermore, this hardness can confer good impact resistance to the compositions of the invention, which can be molded or cast, for example, in the form of a stick or disk.

The person skilled in the art may choose to evaluate a composition using at least one of the hardness tests set forth above based on the intended application and the desired hardness. If an acceptable hardness value is obtained, in view of the intended application, from at least one of these hardness tests, the composition is within preferred embodiments of the invention.

ES 2 365 754 T3

As is evident, the hardness of the composition according to preferred embodiments of the invention can be such, for example, that the composition is advantageously self-supporting and can easily disintegrate to form a satisfactory deposit on the skin and / or lips and / or parts that grow on the surface of the body, such as keratinous fibers. Furthermore, with this hardness, the composition of the invention can have good impact resistance.

According to preferred embodiments of the present invention, the composition in the form of a stick can also exhibit the behavior of a deformable, flexible, elastic solid, providing a remarkable elastic softness when applied. The stick-shaped compositions of the prior art do not exhibit these elasticity and flexibility properties.

LIQUID FAT PHASE

According to preferred embodiments of the present invention, cosmetic compositions are provided that comprise at least one polymer containing polyorganosiloxane and a liquid fatty phase, Preferably, the liquid fatty phase comprises at least one volatile oil, for example, a volatile silicone oil , a volatile hydrocarbon oil, or a mixture thereof.

According to this embodiment, the liquid fatty phase may contain, independently or in combinations, volatile silicone oils, non-volatile silicone oils, volatile non-silicone oils and non-volatile non-silicone oils. In one embodiment, the compositions of the present invention are substantially free of silicone oils (ie, they contain less than about 0.1% silicone oils). In another embodiment, the compositions are substantially free of non-silicone oils (ie, they contain less than about 0.1% non-silicone oils). In another embodiment, the compositions are substantially free of non-volatile oils (ie, they contain less than about 0.1% non-volatile oils).

According to the invention, when volatile oils are present, these volatile oils allow easier application of the composition on the skin, lips or keratinous fibers.

According to one embodiment, the composition can contain one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils that have a viscosity at room temperature less than or equal to 6 cSt and that have from 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that can be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that can be used include KF 96A with a viscosity of 6 cSt, a commercial product from Shin Etsu that has a flash point of 94 ° C. Preferably, the volatile silicone oils have a flash point of at least 40 ° C.

Non-limiting examples of volatile silicone oils are listed in Table 1 below.

Table 1

<td>Compound</td><td>Flash point (° C)</td><td>Viscosity (cSt)</td>

<td>Octyltrimethicone</td><td> 93</td><td> 1,2</td>

<td>Hexyltrimethicone</td><td> 79</td><td> 1,2</td>

<td>Decamethylcyclopentasiloxane (cyclopentasiloxane or D5)</td><td> 72</td><td> 4,2</td>

<td>Octamethylcyclotetrasiloxane (cyclotetradimethylsiloxane or D4)</td><td> 55</td><td> 2,5</td>

<td>Dodecamethylcyclohexasiloxane (D6)</td><td> 93</td><td> 7</td>

<td>Decamethyltetrasiloxane (L4)</td><td> 63</td><td> 1,7</td>

<td>KF-96 A by Shin Etsu</td><td> 94</td><td> 6</td>

<td>PDMS (Polydimethylsiloxane) DC 200 (1.5 cSt) from Dow Corning</td><td> 56</td><td> 1,5</td>

<td>PDMS DC 200 (2 cSt) from Dow Corning</td><td> 87</td><td> 2</td>

<td>PDMS DC 200 (5 cSt) from Dow Corning</td><td> 134</td><td> 5</td>

<td>PDMS DC 200 (3 St) from Dow Corning</td><td> 102</td><td> 3</td>

Examples of other silicone oils that can be used in the invention include non-volatile linear polydimethylsiloxanes (PDMS), which are liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent and / or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms; phenylsilicones, for example phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl-dimethicones, diphenyl-methyldiphenyl-trisiloxanes and 2-phenylethyl-trimethylsiloxysilicates.

In addition, a volatile linear silicone oil can be employed in the compositions of the present invention. Suitable volatile linear silicone oils include those described in US Patent No. 6,338,839 and

ES 2 365 754 T3

WO 03/042221, the contents of which are incorporated herein by reference. In one embodiment the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

Solvent / oil volatility can be determined using evaporation rate as set forth in US Patent No. 6,338,839.

According to other preferred embodiments, the composition may contain one or more volatile oils other than silicone and may be selected from volatile hydrocarbon oils, alcohols, volatile esters, and volatile ethers. Examples of such volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof and in particular branched C8 to C16 alkanes such as C8 to C16 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane, and for example, the oils sold under the trade names Isopar or Permethyl, branched C8 to C16 esters such as isohexyl or isodecyl neopentanoate and mixtures thereof. Preferably, the volatile non-silicone oils have a flash point of at least 40 ° C.

Non-limiting examples of volatile oils other than silicone are given in Table 2 below.

Table 2

<td>Compound</td><td>Flash point (° C)</td>

<td>Isododecane</td><td> 43</td>

<td>Isohexadecane</td><td> 102</td>

<td>Isodecyl neopentanoate</td><td> 118</td>

<td>Propylene glycol n-butyl ether</td><td> 60</td>

<td>Ethyl 3-Ethoxypropionate</td><td> 58</td>

<td>Propylene Glycol Acetate Methyl Ether</td><td> 46</td>

<td>Isopar L (C11-C13 isoparaffin)</td><td> 62</td>

<td>Isopar H (C11-C12 isoparaffin)</td><td> 56</td>

Examples of other oils than silicone that can be used in the compositions of the present invention include polar oils such as:

- vegetable oils based on hydrocarbons with a high content of triglycerides consisting of esters of glycerol fatty acids, whose fatty acids can have varied chain lengths, these chains being possibly linear or branched, and saturated or unsaturated; These oils are especially wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, seed oil cotton wool, alfafa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, avocado oil, hazelnut oil, grapeseed oil, blackcurrant seed oil, evening primrose oil , millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candela nut oil, passion fruit oil or rosehip oil; or caprylic / capric acid triglycerides, for example those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

- synthetic oils or esters of formula R5COOR6 in which R5 represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R6 represents a hydrocarbon-based chain branched containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms, with R6 + R7 10, such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12 to C15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, for example isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

- synthetic ethers containing from 10 to 40 carbon atoms;

- C8 to C26 fatty alcohols, for example oleyl alcohol; Y

- mixtures thereof.

Preferably, the liquid fatty phase, when present, represents from 5% to 98.4% of the total weight of the composition, more preferably from 10% to 80% of the total weight of the composition, and most preferably from 20% to 75%.

ES 2 365 754 T3

FILM FORMING COMPOUNDS

The composition of the present invention also advantageously includes one or more film-forming agents. Film-forming agents are known in the art.

According to preferred embodiments of the present invention, compositions are provided comprising at least one polyorganosiloxane-containing polymer and at least one silicone film-forming agent, preferably a MK or MQ resin or mixtures thereof.

The silicone resin nomenclature is known in the art as the MDTQ nomenclature, whereby a silicone resin is described according to the various monomeric siloxane units that make up the polymer.

Each letter in MDTQ represents a different type of drive. The letter M represents the monofunctional unit (CH3) 3SiO1 / 2. This unit is considered to be monofunctional because the silicon atom only shares an oxygen when the unit is part of a polymer. Unit M can be represented by the following structure:

<img file="ES2365754T3_D0039.tif" />

At least one of the methyl groups of unit M can be substituted for another group, for example, to give a unit with the formula [R (CH3) 2] SiOv2, as represented in the following structure:

<img file="ES2365754T3_D0040.tif" />

wherein R is selected from groups other than methyl groups. Non-limiting examples of such groups other than methyl groups include alkyl groups other than methyl groups, alkene groups, alkyne groups, hydroxyl groups, thiol groups, ester groups, acid groups, ether groups, in which the groups other than methyl groups may be additionally substituted.

Symbol D represents the difunctional unit (CH3) 2SiO₂/ 2 in which two oxygen atoms attached to the silicon atom are used to bind to the rest of the polymer. Unit D, which is the main structural element of dimethicone oils, can be represented as:

<img file="ES2365754T3_D0041.tif" />

At least one of the methyl groups in unit D can be substituted for another group, for example, to give a unit with the formula [R (CH3) 2] SiOv2.

The symbol T represents the functional unit t , (CH3) SiO3 / 2 and can be represented as:

<img file="ES2365754T3_D0042.tif" />

At least one of the methyl groups of unit T can be substituted for another group, for example, to give a unit with the formula [R (CH3) 2] SiOv2.

Similarly, the symbol Q represents the tetrafunctional unit, SiO4 / 2 in which the four oxygens attached to the silicon atom are attached to the rest of the polymer.

ES 2 365 754 T3

Thus, a wide number of different silicone polymers can be manufactured. Furthermore, it will be apparent to a person skilled in the art that the properties of each of the possible silicone polymers will vary depending on the type (s) of monomer (s), the type (s) of substitution / substitutions, the size of the polymer chain, the degree of crosslinking, and the size of any side chains.

Non-limiting examples of silicone polymers include silanes, siloxanes, siloxysilicates, and silsesquioxanes. A non-limiting example of such a siloxane is polydimethylsiloxane (PDMS). Polydimethylsiloxanes are generally composed of long linear chains of (CH3) 2SiO2 / 2 (ie, D units) and exhibit viscosities that depend both on the size of the polymer and on the presence and nature of any substituents on the polymer. A non-limiting example of a siloxysilicate is trimethylsiloxysilicate, which can be represented by the following formula:

[(CH3) 3-Si-O]_x-(SW₄/ 2) y (ie MQ units) where x and y can range, for example, from 50 to 80. Silsesquioxanes, on the other hand, can be represented by the following formula:

(CH₃SW₃/ 2) x (that is, T units) where x can be, for example, a value of up to several thousand.

Polymethylsilsesquioxanes are silsesquioxanes that do not have a substituent to replace the methyl groups. Certain polymethylsilsesquioxanes have previously been used in hair care compositions. See, for example, US Patent No. 5,246,694, the disclosure of which is incorporated herein by reference, which discloses a shampoo composition comprising a surfactant, an aqueous emulsion of highly viscous silicone in volatile silicone and a cationic polymer that is a derivative of guar gum. The highly viscous silicone disclosed therein may be chosen from silicone resins including a polymethylsilsesquioxane such as Resin MK (also referred to as SiliconHarz MK) which is available from Wacker, and a syloxysilicate such as Resin MQ which is available from General Electric and Dow Corning.

Resin MK and Resin MQ silicone resins can form a film after a volatile vehicle has evaporated. MQ film is generally hard and brittle at room temperature, while MK film is generally continuous and flexible, that is, not brittle. Depending on the application, plasticizers can be added to help obtain a more flexible film, and therefore more comfortable.

In one embodiment, the silicone film-forming compound can be a polymethylsilsesquioxane film-forming compound such as Belsil PMS MK, also referred to as Resin MK, available from Wacker Chemie. This polymethylsilsesquioxane film-forming compound is a polymer comprising polymerized repeating units of CH₃Yes₃/ 2 (T units) and may also contain up to 1% by weight or mole of units of the formula (CH₃) 2SiO2 / 2 (D units). The weight average molecular weight of this polymer has been estimated to be 10,000. The polymers are believed to be in a cage and ladder configuration, as shown by way of example in the following figures. Most of the polymer is in the ladder configuration, in which the ends of the polymer are occupied with ethoxyl groups (CH₃CH₂OR). Ethoxy groups are generally present in an amount of 4.5% by weight and the mole percentage is generally 7% (silicone units). Since ethoxy groups can react with water, a small and variable amount of SiOH may also be present in the polymer.

<img file="ES2365754T3_D0043.tif" />

Cage

ES 2 365 754 T3

<img file="ES2365754T3_D0044.tif" />

minus one polymethylsilsesquioxane film-forming compound

Another non-limiting example of said one suitable for use in the present invention is KR-220L, which is available from SHIN-ETSU. This polymethylsilsesquioxane film-forming compound is composed of silicone T units (ie those of formula CH3SÍO3 / 2) and has Si-OH (or silanol) end units. There are no D units in KR-220L.

Other non-limiting examples of said at least one polymethylsilsesquioxane film-forming compound that may be useful in the practice of the invention include KR-242A (which is composed of methyl T units (98%) and dimethyl D units (2%). ) and have Si-OH end units) and KR-251 (which is composed of methyl T units (88%) and dimethyl D units (12%) and present Si-OH end units), both of all of which are available from SHIN-ETSU.

Depending on the application, the concentration of said at least one polymethylsilsesquioxane film-forming compound in the presently claimed composition can vary considerably. One skilled in the art will be able to routinely determine the amount of said at least one polymethylsilsesquioxane film-forming compound depending on the desired application.

In another embodiment, the silicone film-forming compound can be chosen from siloxysilicates. Preferably, the siloxysilicate is trimethylsiloxysilicate, which may or may not be in powder form. Trimethylsiloxysilicate (TMS) is commercially available from General Electric under the trade name SR1000 and from Wacker under the trade name TMS 803. TMS is also commercially available from Dow Chemical in a solvent, such as, for example, cyclomethicone. However, according to the present invention, TMS can be used in the form of a 100% active material, that is, not in a solvent.

Additional non-limiting examples of silicone film-forming compounds include silicone / (meth) acrylate copolymers, such as those described in US Patent Nos. 5,061,481, 5,219,560, and 5,262,087, the disclosures of which are incorporated herein by reference. Still further non-limiting examples of silicone film-forming compounds are non-polar silicone copolymers comprising repeating units of at least one polar (meth) acrylate unit and vinyl copolymers grafted with at least one non-polar silicone chain. Non-limiting examples of such copolymers are acrylates / dimethicone copolymers such as those commercially available from Shin-Etsu, for example the product sold under the trade name KP545, or acrylates / stearyl acrylate / dimethicone acrylates copolymers, such as commercially available from Shin-Etsu, for example, the product sold under the trade name KP-561, and acrylates / behenyl acrylate / dimethicone acrylates copolymer, such as those commercially available from Shin-Etsu, for example the product sold under the trade name KP-562.

Other non-limiting examples of silicone film-forming compounds suitable for use in the present invention are silicone esters comprising units of formulas (XIV) and (XV), disclosed in US Patent Nos. 6,045,782, n 5,334,737 and 4,725,658, the descriptions of which are incorporated herein by reference:

RaR^ANDbSiO [4- (_to+ b) / 2] (XIV);

Y

R '_xR^AND_YSiOi /₂ (XV) where R and R ', which may be identical or different, are each selected from optionally substituted hydrocarbon groups;

a and b, which can be identical or different, are each a number ranging from 0 to 3, provided that the sum of a and b is a number ranging from 1 to 3,

ES 2 365 754 T3 x and y, which may be identical or different, are each a number ranging from 0 to 3, provided that the sum of x and y is a ranging from 1 to 3;

R^AND, which may be identical or different, each is selected from groups comprising at least one carboxylic ester.

In one embodiment, the RE groups are selected from groups comprising at least one ester group formed from the reaction of at least one acid and at least one alcohol. In another embodiment, said at least one acid comprises at least two carbon atoms. In another embodiment, said at least one alcohol comprises at least ten carbon atoms. Non-limiting examples of said at least one acid include branched acids such as isostearic acid, and linear acids such as behenic acid. Non-limiting examples of said at least one alcohol include monohydric alcohols and polyhydric alcohols, such as n-propanol and branched etherealkanols such as (3,3,3-trimethylolpropoxy) propane.

Additional non-limiting examples of said at least one silicone film-forming compound include liquid siloxysilicates and silicone esters such as those described in the U: S patent. No. 5,334,737, the disclosure of which is incorporated herein by reference, such as diisostearoyl trimethylolpropane siloxysilicate and dilauroyl trimethylolpropane siloxysilicate, which are commercially available from General Electric under the trade names MQ 1318 and MQ 1312, respectively.

Still further non-limiting examples of said at least one silicone film-forming compound include polymers comprising a backbone selected from vinyl polymers, methacrylic polymers, and acrylic polymers and at least one chain selected from pendant siloxane groups and fluorochemical groups. pendants. Non-limiting examples of such polymers comprise at least one unit derived from at least one monomer A, at least one unit derived from at least one monomer C, at least one unit derived from monomers D, and optionally at least one unit derived from at least one monomer B, in which:

A, which may be identical or different, are each selected from free radically polymerizable acrylic esters of at least one alcohol selected from 1,1, -dihydroperfluoroalkanols, omegahydridofluoroalkanols, fluoroalkylsulfonamide alcohols, cyclic fluoroalkyl alcohols, and fluoroether alcohols , and analogues of any of the above at least one alcohol, and free radically polymerizable methacrylic esters of at least one alcohol selected from 1,1, -dihydroperfluoroalkanols, omegahydridofluoroalkanols, fluoroalkylsulfonamide alcohols, cyclic fluoroalkyl alcohols, and fluoroether alcohols, and analogs of any of the foregoing at least one alcohol;

B, which may be identical or different, are each selected from reinforcing monomers that can be copolymerized with at least one monomer A;

C, which may be identical or different, are each selected from monomers having the formula:

X (Y) nSiMQ3-m Zm where

X is selected from vinyl groups that can be copolymerized with at least one monomer A and at least one monomer B,

Y is selected from among divalent alylene groups, divalent arylene groups, divalent alkarylene groups, and divalent aralkylene groups, in which the groups comprise from 1 to 30 carbon atoms, and in which the groups also optionally further comprise at least one group selected from ester groups, amide groups, urethane groups, and urea groups;

n is zero or 1;

m is a number ranging from 1 to 3;

R, which may be identical or different, are each selected from hydrogen, C1-C4 alkyl groups, aryl groups, and alkoxy groups; Y

Z, which may be identical or different, are each selected from monovalent siloxane polymeric groups; Y

D, which may be identical or different, are each selected from free radically polymerizable acrylate copolymers and free radically polymerizable methacrylate copolymers. Such polymers and their preparation are disclosed in US Patent Nos. 5,209,924 and 4,972,037, and WO 01/32737, the disclosures of which are incorporated herein by reference.

ES 2 365 754 T3

Other non-limiting examples of said at least one silicone film-forming compound include silicone / acrylate graft terpolymers, for example those having the formula:

<img file="ES2365754T3_D0045.tif" />

CH₃

I (CH₂C)_c ch₃ ch₃ch

CH₃CH₂CH₂CH₂—Si [o - Si-I — o — Si — ch₃ch₂ch₂ooc i ri ch₃ ch₃ch in which a, b and c are present in a weight ratio of 69.9: 0.1: 30 respectively,

R and R1, which may be identical or different, are each selected from hydrogen and C1-C6 alkyl groups; and m is a number that ranges from 100 - 150.

In one embodiment, m is chosen to provide a macromer having a molecular weight of between 8,000 and 12,000, such as 10,000. In another embodiment, m is a number ranging from 124-135, such as 130. Non-limiting examples of these copolymers are described in WO 01/32727 A1, the disclosure of which is incorporated herein by reference.

Still other examples of suitable silicone film-forming compounds include copolymers comprising a backbone selected from vinyl backbones, methacrylic backbones, and acrylic polymer backbones and further comprising at least one pendant siloxane group. Non-limiting examples of such polymers are disclosed in US Patents No. 4,693,935, No. 4,981,903, No. 4,981,902, the disclosures of which are incorporated herein by reference.

In one embodiment, said at least one copolymer comprises at least one A monomer, at least one C monomer, and optionally at least one B monomer, wherein said at least one A monomer is selected from polymerizable vinyl monomers free radicals, free radical polymerizable methacrylate monomers, and free radical polymerizable acrylate monomers; said at least one monomer B, if present, is selected from at least one reinforcing monomer copolymerizable with at least one monomer A, and said at least one monomer C is selected from monomers having the formula:

X (Y) nSiMQ3-_mZ_m in which:

X is selected from vinyl groups that can be copolymerized with said at least one monomer A and with said at least one monomer B;

Y is selected from divalent groups;

n is zero or 1;

m is a number between 1 and 3;

R, which may be identical or different, are each selected from hydrogen, C alkyl groups₁-C₁₀optionally substituted, optionally substituted phenyl groups, and C alkoxy groups₁-C₁₀ optionally substituted; and z, which may be identical or different, are each selected from monovalent siloxane polymeric groups.

Non-limiting examples of monomers A include methacrylic acid esters of C1-C22 linear alcohols, methacrylic acid esters of C branched alcohols₁-C₁₂, styrene monomers, vinyl esters, vinyl chloride monomers, vinylidene chloride monomers, and acryloyl monomers.

ES 2 365 754 T3

Non-limiting examples of monomers B include acrylic monomers comprising at least one group selected from hydroxyl, amino, and ionic groups, and methacrylic monomers comprising at least one group selected from hydroxyl, amino, and ionic groups. Non-limiting examples of ionic groups include quaternary ammonium groups, carboxylate salts, and sulfonic acid salts.

The C monomers are the same as those described for the C monomers in the previous paragraphs.

Other non-limiting examples of the silicone film-forming compound include a copolymer selected from vinyl-silicone graft copolymers having the following formula and vinyl silicone block copolymers having the following formula:

<img file="ES2365754T3_D0046.tif" />

in which

G5, which may be identical or different, are each selected from alkyl groups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups, fluoroalkyl groups, hydrogen, and -ZSA groups, where A is selected from polymeric segments of vinyl comprising at least one polymerized free radically polymerizable monomer, and

Z is selected from divalent C1-C10 alkylene groups, divalent aralkylene groups, divalent arylene groups, and divalent alkoxylalkylene groups. In one embodiment Z is selected from methylene groups and propylene groups.

G6, which may be identical or different, are each selected from alkyl groups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups, fluoroalkyl groups, hydrogen, and -ZSA groups, as defined above;

G2 comprises A;

G4 comprises A;

R1, which may be identical or different, are each selected from alkyl groups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups, fluoroalkyl groups, hydrogen and hydroxyl. In one embodiment, R1 is selected from C1-C4 alkyl groups, such as methyl, and hydroxyl groups.

R2, which may be identical or different, are each selected from divalent C1-10 alkylene groups, divalent arylene groups, divalent aralkylene groups, and divalent alkoxyalkylene groups. In one embodiment, R2 is selected from divalent C1-C3 alkylene groups and divalent C7-C10 aralkylene groups. In another embodiment, R2 is selected from divalent -CH2- and 1,3-propylene groups.

R3, which may be identical or different, are each selected from alkyl groups, aryl groups, aralkyl groups, alkoxy groups, alkylamino groups, fluoroalkyl groups, hydrogen and hydroxyl. In one embodiment, R3 is selected from C1-C4 alkyl and hydroxyl groups. In another embodiment, R3 is selected from methyl groups.

R4, which may be identical or different, are each selected from divalent C1-C10 alkylene groups, divalent arylene groups, divalent aralkylene groups, and divalent alkoxyalkylene groups. In one embodiment, R4 is selected from divalent C1-C3 alkylene groups and divalent C7-C10 aralkylene groups. In another embodiment, R4 is selected from divalent -CH2- groups and divalent 1,3-propylene groups.

x is a number ranging from 0 to 3;

y is a number greater than or equal to 5. In one embodiment, y ranges from 10 to 270, and in another embodiment, y ranges from 40 to 270.

ES 2 365 754 T3 q is a number ranging from 0 to 3.

Non-limiting examples of these polymers are described in US Patent No. 5,468,477, the disclosure of which is incorporated herein by reference. A non-limiting example of such polymers is poly (dimethylsiloxane) -g-poly (butyl methacrylate), which is commercially available from 3M under the trade name VS 70 IBM.

According to preferred embodiments, the silicone film-forming compound is present in the composition in an amount ranging from 0.1% to 30% by weight relative to the total weight of the composition. Preferably, the silicone film-forming compound is present in an amount ranging from 0.5% to 20% by weight relative to the total weight of the composition, and more preferably from 1% to 10%. One skilled in the art will recognize that the silicone film-forming compound of the present invention may be commercially available, and may come from suppliers in the form of a dilute solution. The amounts of the silicone film-forming compound disclosed herein therefore reflect the percent by weight of active material.

In a preferred embodiment, the polyorganosiloxane polymer and the film-forming agent are solid. The composition is prepared by heating the solids sufficiently to combine and form compositions as described herein. This combination of solid polyorganosiloxane polymer and film-forming agent provides beneficial, long-lasting transfer resistant compositions.

According to preferred embodiments, cosmetic compositions are provided that comprise at least one polymer containing polyorganosiloxane and at least one coloring agent. Preferably, such colored cosmetic compositions are lip compositions (eg, lipstick or liquid lip stains) or foundation.

According to this embodiment, said at least one coloring agent is preferably selected from among pigments, dyes, such as fat-soluble dyes, pearlescent pigments and pearlizing agents.

Representative fat-soluble dyes that can be used in accordance with the present invention include Sudan red, DC red 17, DC green 6, β-carotene, soybean oil, Sudan brown, DC yellow 11, DC violet 2, DC orange 5, annatto, and DC yellow. quinoline. Fat-soluble dyes, when present, generally have a concentration ranging up to 20% by weight of the total weight of the composition, such as between 0.0001% and 6%.

The pearlescent pigments that can be used according to the present invention can be chosen from white pearlescent pigments such as titanium or bismuth oxychloride coated mica, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or iron oxide. chromium, titanium mica with an organic pigment selected from those mentioned above, and pearlescent pigments based on bismuth oxychloride. Pearlescent pigments, if present, are present in the composition in a concentration ranging up to 50% by weight of the total weight of the composition, such as between 0.1% and 20%, preferably between 0.1%. % and 15%.

The pigments that can be used according to the present invention can be chosen from white, colored, inorganic, organic, polymeric, non-polymeric, coated and uncoated pigments. Representative examples of mineral pigments include titanium dioxide, optionally surface treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, and ferric blue. . Representative examples of organic pigments include carbon black, type D and C pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, and aluminum.

Pigments may be present in the composition in a concentration ranging up to 50% by weight of the total weight of the composition, such as between 0.5% and 40%, and further such as between 2% and 30%. %. In the case of certain products, pigments, including pearlescent pigments, can represent, for example, up to 50% by weight of the composition.

According to preferred embodiments of the present invention, compositions comprising at least one polyorganosiloxane-containing polymer are anhydrous. By anhydrous, it is meant that the composition contains substantially no water (ie, less than about 0.1% by weight of the water composition).

According to other preferred embodiments, compositions comprising at least one polyorganosiloxane-containing polymer further comprise water. In this embodiment, the water is preferably present in an amount ranging from about 0.1 to about 70%, preferably from about 0.5 to 50%, and more preferably from about 1 to about 70%. 30% with respect to the total weight of the composition. Preferably, such water-containing cosmetic compositions are lip compositions (eg, lipstick or liquid lip stains), foundation or mascara, and are emulsions or dispersions.

ES 2 365 754 T3

Additional components that offer cosmetic properties similar to those of short chain esters are short chain ethers that can be represented as JOK in which J and K are identical or different and represent a linear or branched alkyl radical of from 1 to 40 atoms of carbon, preferably 7 to 19 carbon atoms, possibly including one or more double bonds. An example of such an ether includes dicapryl ether.

LIPOSOLUBLE OR DISPERSABLE POLYMERS

Basecoat compositions of the invention may also contain at least one polymer that is fat soluble or dispersible in the medium, other than polymer containing polyorganosiloxane, and may exhibit film-forming properties and may exhibit, for example, a weight average molecular weight of from 500 to 1,000,000, such as from 1,000 to 500,000, and for example, such as further from 5,000 to 100,000, and even further such as from 5,000 to 20,000. This at least one fat-soluble polymer can contribute to increasing the viscosity and / or improving the stability of the film. Said at least one fat-soluble polymer can have a softening point of no more than 30 ° C.

As examples of fat-soluble polymers that can be used in the invention, there may be mentioned: polyalkylenes, in particular polybutene, poly (meth) acrylates, alkylcelluloses with a linear or branched, saturated or unsaturated C1 to C8 alkyl radical, such as ethylcellulose and propylcellulose, polymers silicone that are compatible with the fatty phase, as well as vinylpyrrolidone (VP) copolymers, and mixtures thereof.

Copolymers of vinylpyrrolidone, copolymers of a C2 to C30 alkene, such as C3 to C22, and combinations thereof can be used. As examples of VP copolymers that can be used in the invention, there can be mentioned VP / vinyl acetate, VP / ethyl methacrylate, butylated polyvinylpyrrolidone (PVP), VP / ethyl methacrylate / methacrylic acid, VP / eicosen, VP / hexadecene, VP / triacontene, VP / styrene or VP / acrylic acid / lauryl methacrylate copolymer.

Not only for stability properties but also for film consistency and feel properties, the PVP / hexadecene copolymer having an average molecular weight of from 7,000 to 7,500 can be used or alternatively the PVP / eicosenic copolymer having a average molecular weight of from 8,000 to 9,000.

The fat-soluble or dispersible polymers in the composition of the invention can also be used in an amount of from 0.01% to 20% (as active material) with respect to the total weight of the composition, such as, for example, from the 1% to 10%, if present.

The basecoat composition according to the invention may be in the form of a tinted or untinted dermatological composition or a care composition for keratin materials such as the skin, lips and / or anatomical parts that grow on the surface, in the form of a composition. against the Sun or makeup removal product in the form of a stick. They can be used in particular as a care base for the skin, anatomical parts that grow superficially or the lips (lip balms, to protect the lips against cold and / or sunlight and / or wind, or care cream for skin, nails or hair). As defined herein, a deodorant product is a personal hygiene product and does not refer to the care, makeup, or treatment of keratin materials, including keratinous fibers.

The base coat composition of the invention may also be in the form of a colored make-up product for the skin, in particular a base, optionally exhibiting care or treatment properties, a blush, a face powder, an eye shadow, a concealer product, an eyeliner, a makeup product for the body; a lip makeup product such as a lipstick, optionally exhibiting care or treatment properties; a makeup product for parts that grow on the surface of the body such as nails or eyelashes, in particular in the form of a mascara, or for the eyebrows or hair, in particular in the form of a pencil.

It goes without saying that the basecoat composition of the invention must be cosmetically and dermatologically acceptable, that is, it must contain a non-toxic, physiologically acceptable medium and must be capable of being applied to the skin, parts that grow on the surface of the body or the lips of human beings. For the purposes of the invention, the term "cosmetically acceptable" means a composition with a pleasant appearance, smell, feel and / or taste.

Basecoat compositions of the present invention comprising at least one polyorganosiloxane-containing polymer, preferably a silicone-polyamide copolymer, are applied topically to the desired area of ​​the skin in an amount sufficient to make up the keratinous material. , to cover or hide defects associated with keratinous material, skin blemishes or discolorations, or to enhance the appearance of the keratinous material.

ES 2 365 754 T3

Examples

Lip gloss compositions according to the present invention were prepared according to the following formula: all values ​​are expressed in% w / w. The following Examples 1-7 were prepared as follows:

- The oil of phase A was preheated to 100 ° C for 10 minutes, with medium mixing, using a propeller mixer.

- Phase B (KRATON G1675 M) was added to phase A at 100 ° C.

- Phase B and phase A were mixed at high speed for 30 minutes until phase B was completely dissolved in phase A.

- Phase C (Regalite R1100) was then slowly added to phase (A + B) with medium mixing at 95 ° C until the solution became homogeneous.

- The temperature was reduced to 90 ° C and phase D containing oil mixtures was added to phase (A + B + C), and mixed at low speed.

- In a separate beaker, phase E components were mixed manually until the pigments were completely wetted with oil to form a pigment mixture.

- The pigment mixture was then transferred to a three-roll mill and ground until the colors became homogeneous to form a milled pigment mixture.

- The ground pigment mixture was then transferred to a beaker containing the phase (A + B + C + D) and mixed, at medium speed, for approximately 5 minutes.

- Phase F was then slowly added to the beaker and mixed for 10 minutes at high speed.

- Then the mixing speed was reduced and the resulting fluid was transferred to individual containers at 90 ° C.

- Then the samples contained in the containers were cooled to room temperature.

- The samples showed desirable shine and wear properties.

Example 1

<td>PHASE</td><td>TRADENAME</td><td>% p / p</td>

<td>TO</td><td>FINSOLV TN ¹</td><td> 25,43</td>

<td>B</td><td>KRATON G1657 M</td><td> 8,00</td>

<td>C</td><td>REGALITE R1100</td><td> 24,00</td>

<td>D</td><td>PRISORINE 3631 ²</td><td> 10,00</td>

<td></td><td>CRODAMOL STS</td><td> 24,26</td>

<td></td><td>TITANIUM DIOXIDE</td><td> 0,15</td>

<td></td><td>IRON OXIDE</td><td> 0,13</td>

<td></td><td>RED D&amp;C RED N ° 7</td><td> 0,10</td>

<td>AND</td><td>LAKE BLUE 1</td><td> 0,01</td>

<td></td><td>BLACK IRON OXIDE</td><td> 0,04</td>

<td></td><td>FINSOLV TN ¹</td><td> 0,88</td>

<td></td><td>MICA</td><td> 3,00</td>

<td>F</td><td>AMIHOPE LL ³</td><td> 1,00</td>

<td></td><td>AEROSIL R972</td><td> 3,00</td>

<td></td><td>TOTAL</td><td> 100,00</td>

1: C12-15 alkyl benzoate available from Finetex.

2: Pentaerythrityl Tetrasostearate available from Uniqema.

3: Lauroyl-lysine powder available from Ajinomoto.

ES 2 365 754 T3

Rheology of Example 1

- The elastic / storage modulus G ', at a frequency of 0.01 rad / s, at a temperature of 25 ° C, was 26.5 Pa, for the formulation of example 1.

- The sliding viscosity, at a constant tension of 0.8 Pa, at a temperature of 25 ° C, was 5.43x10³ Pa.s, for the formulation of Example 1.

Example 2

<td>PHASE</td><td>TRADENAME</td><td>% p / p</td>

<td rowspan="3">TO</td><td>PURESYN¹2</td><td> 25,76</td>

<td>ISOPROPYL PALMITATE</td><td> 10,00</td>

<td>FINSOLV TN ²</td><td> 2,50</td>

<td>B</td><td>KRATON G1657 M</td><td> 8,00</td>

<td>C</td><td>REGALITE R1100</td><td> 24,0</td>

<td rowspan="2">D</td><td>PURESYN¹ 150</td><td> 15,0</td>

<td>PURESYN 4E68 3</td><td> 7,00</td>

<td rowspan="5">AND</td><td>TITANIUM DIOXIDE</td><td> 0,15</td>

<td>IRON OXIDE</td><td> 0,31</td>

<td>RED D&amp;C N ° 7</td><td> 0,23</td>

<td>BLACK IRON OXIDE</td><td> 0,05</td>

<td>PURESYN 2</td><td> 1,00</td>

<td rowspan="3">F</td><td>MICA</td><td> 2,00</td>

<td>AMIHOPE LL ⁴</td><td> 1,00</td>

<td>AEROSIL R972</td><td> 3,00</td>

<td></td><td>TOTAL</td><td> 100,00</td>

1: Hydrogenated polydecenes available from ExxonMobilo.

2: C12-15 alkyl benzoate available from Finetex.

3: Pentaerythrityl tetraoleate available from ExxonMobilo.

4: Lauroyl-lysine powder available from Ajinomoto.

Rheology of Example 2

- The elastic / storage modulus G ', measured at a frequency of 0.01 rad / s and at a temperature of 25 ° C, was 14.4 Pa for the formulation of Example 2.

- The sliding viscosity, at a constant tension of 0.8 Pa, at a temperature of 25 ° C, was 1.55x10³ Pa.s, for the formulation of Example 2.

Example 3

<td>PHASE</td><td>TRADENAME</td><td>% p / p</td>

<td rowspan="3">TO</td><td>POLYSYNLANE LITE</td><td> 25,71</td>

<td>PURESYN¹6</td><td> 12,00</td>

<td>ISOPROPYL PALMITATE</td><td> 8,00</td>

<td>B</td><td>KRATON G1657 M</td><td> 9,00</td>

<td>C</td><td>REGALITE R1100</td><td> 18,00</td>

<td rowspan="3">D</td><td>PURESYN¹ 150</td><td> 6,00</td>

<td>DC 556</td><td> 8,00</td>

<td>DC 555</td><td> 4,00</td>

(continuation)

<td>PHASE</td><td>TRADENAME</td><td>% p / p</td>

<td rowspan="8">AND</td><td>TITANIUM DIOXIDE</td><td> 0,15</td>

<td>IRON OXIDE</td><td> 0,31</td>

<td>RED D&amp;C N ° 7</td><td> 0,23</td>

<td>BENTONE VCG</td><td> 0,50</td>

<td>PROPYLENE CARBONATE</td><td> 0,05</td>

<td>BLACK IRON OXIDE</td><td> 0,05</td>

<td>POLYSYNLANE LITE</td><td> 2,00</td>

<td>POLYHYDROXIESTEARIC ACID</td><td> 1,00</td>

ES 2 365 754 T3

<td rowspan="3">F</td><td>MICA</td><td> 2,00</td>

<td>AEROSIL R972</td><td> 2,00</td>

<td>AMIHOPE LL ²</td><td> 1,00</td>

<td></td><td>TOTAL</td><td> 100,00</td>

<td colspan="3">1: Hydrogenated polydecenes available from ExxonMobilo. 2: Lauroyl-lysine powder available from Ajinomoto.</td>

Rheology of Example 3

The elastic / storage modulus G ', at a frequency of 0.01 rad / s, at a temperature of 25 ° C, was 5 18.3 Pa, for example 3.

The sliding viscosity, at a constant tension of 0.8 Pa, 2 Pa, 5 Pa, and 7 Pa, at a temperature of 25 ° C, was 2.32x10⁴ Pa.s, 4.32x10² Pa.s, 7.98x10¹ Pa.sy 5.60x10¹ Pa.s, for example 3.

Example 4

<td>PHASE</td><td>TRADENAME</td><td>% p / p</td>

<td>TO</td><td>PURESYN¹2</td><td> 25,26</td>

<td></td><td>ISOPROPYL PALMITATE</td><td> 8,00</td>

<td>B</td><td>KRATON G1657 M</td><td> 8,00</td>

<td>C</td><td>REGALITE R1100</td><td> 24,00</td>

<td>D</td><td>PURESYN¹ 150</td><td> 16,00</td>

<td></td><td>KF6038 ²</td><td> 3,00</td>

<td>AND</td><td>TITANIUM DIOXIDE</td><td> 0,15</td>

<td></td><td>IRON OXIDE</td><td> 0,31</td>

<td></td><td>RED D&amp;C N ° 7</td><td> 0,23</td>

<td></td><td>BLACK IRON OXIDE</td><td> 0,05</td>

<td></td><td>PURESYN ¹ 2</td><td> 1,00</td>

<td>F</td><td>MICA</td><td> 2,00</td>

<td></td><td>AEROSIL R972</td><td> 3,00</td>

<td></td><td>AMIHOPE LL ³</td><td> 1,00</td>

<td></td><td>TOTAL</td><td> 100,00</td>

1: Hydrogenated polydecenes available from ExxonMobilo.

2: Polyether / alkyl commodified silicone available from Shin-Etsu.

3: Lauroyl-lysine powder available from Ajinomoto.

Rheology of Example 4

The elastic / storage modulus G ', at a frequency of 0.01 rad / s, at a temperature of 25 ° C, was 28.6 Pa for Example 4.

The sliding viscosity, at a constant tension of 0.8 Pa, at a temperature of 25 ° C, was 1

5.34x10⁴ Pa.s for example 4.

ES 2 365 754 T3

Examples 5, 6 and 7:

<td>PHASE</td><td>TRADENAME</td><td>EXAMPLE 5</td><td>EXAMPLE 6</td><td>EXAMPLE 7</td>

<td>TO</td><td>PURESYN¹2</td><td> 28,00</td><td> 28,00</td><td> 28,00</td>

<td></td><td>ISOPROPYL PALMITATE</td><td> 11,74</td><td> 6,74</td><td> 6,74</td>

<td>B</td><td>KRATON G1657 M</td><td> 8,00</td><td> 8,00</td><td> 8,00</td>

<td>C</td><td>REGALITE R1100</td><td> 24,00</td><td> 24,00</td><td> 24,00</td>

<td></td><td>PURESYN ¹ 150</td><td> 15,00</td><td> 15,00</td><td> 15,00</td>

<td>D</td><td>DC 555</td><td> 0,00</td><td> 0,00</td><td> 5,00</td>

<td></td><td>DC 554</td><td> 0,00</td><td> 5,00</td><td> 0,00</td>

<td></td><td>TITANIUM DIOXIDE</td><td> 1,40</td><td> 1,40</td><td> 1,40</td>

<td></td><td>IRON OXIDE RED</td><td> 0,71</td><td> 0,71</td><td> 0,71</td>

<td>AND</td><td>RED D&amp;C N ° 7</td><td> 0,96</td><td> 0,96</td><td> 0,96</td>

<td></td><td>YELLOW FD&amp;C N ° 5</td><td> 0,86</td><td> 0,86</td><td> 0,86</td>

<td></td><td>BLACK IRON OXIDE</td><td> 0,08</td><td> 0,08</td><td> 0,08</td>

<td></td><td>FINSOLV TN ²</td><td> 3,25</td><td> 3,25</td><td> 3,25</td>

<td>F</td><td>MICA</td><td> 3,00</td><td> 3,00</td><td> 3,00</td>

<td></td><td>AEROSIL R972</td><td> 3,00</td><td> 3,00</td><td> 3,00</td>

<td></td><td>TOTAL</td><td> 100,00</td><td> 100,00</td><td> 100,00</td>

1: Hydrogenated polydecenes available from ExxonMobilo.

2: C12-15 alkyl benzoate available from Finetex.

Rheology of Examples 5-7

The elastic / storage modulus G ', at a frequency of 0.01 rad / s, at a temperature of 25 ° C, was 35.3 Pa, 88.8 Pa, and 63.4 Pa, for examples 5 -7, respectively.

The sliding viscosity, at a constant tension of 0.8 Pa, at a temperature of 25 ° C, was 1.25X10⁴ Pa.s, 5.54 X10⁴ Pa.s, and 2.73 X10⁴ Pa.s, for Examples 5-7, respectively.

Example 8

An experiment was carried out to determine both the degree of gloss and the gloss utilization of a cosmetic product according to the present invention.

Base coat composition

<td>INCI name of the United States</td><td>Concentration</td>

<td>PROPYLENE CARBONATE</td><td> 0,8</td>

<td>ISODODECANE</td><td> 59,7</td>

<td>NYLON-611 / DIMETICONE COPOLYMER</td><td> 11</td>

<td>LAUROIL-LYSINE</td><td> 1,5</td>

<td>Colorants</td><td> 7,5</td>

<td>TRIMETHYLSILOXYSILICATE</td><td> 17</td>

<td>DIESTEARDIMONIO HECTORITE</td><td> 2,5</td>

<td>Total:</td><td> 100</td>

Finish coat composition

<td>INCI name of the United States</td><td>Concentration</td>

<td>HYDROGENATED STYRENE / METHYLSTYRENE / INDENE COPOLYMER</td><td> 21</td>

<td>ISOPROPYL PALMITATE</td><td> 9</td>

<td>TRIMETHYL-PENTAPHENYL-TRISYLOXANE</td><td> 5</td>

Topcoat Composition (continued)

<td>INCI name of the United States</td><td>Concentration</td>

<td>HYDROGENATED STYRENE / BUTADIENE COPOLYMER</td><td> 11</td>

<td>HYDROGENATED POLYDECENE</td><td> 21</td>

<td>PHENYL-TRIMETICONE</td><td> 9</td>

<td>POLYISOBUTENE</td><td> 24</td>

<td>Total:</td><td> 100</td>

ES 2 365 754 T3

The experiment involved applying a basecoat composition, followed by a topcoat composition, to a person's lips. Gloss measurements were then taken at T0 (initial); T1 (after 1 hour); and T2 (after 2 hours) to determine brightness utilization using the protocol identified below.

Gloss measurement protocol

In order to measure the gloss of the aforementioned cosmetic product, the intensity of the light used to perform the measurement was first determined and then its reflection from the surface of the lips was measured. This was done by presenting a first vertically oriented polarizer in front of the light source, and a second vertically oriented polarizer in front of a video camera. The video camera first recorded the reflection from the surface along with the vertical light that arises from any light that passes through the gloss and onto the lip.

The polarizer was then rotated in front of the camera 90 degrees (at video speed) in order to record the intensity of any vertical light transmitted below the surface. Next, the horizontal intensity of the light transmitted below the surface was measured. The second horizontal measurement was a correction representing any subsurface contribution to the desired surface signal (the gloss). The second number was then subtracted from the first to provide the brightness value.

Gloss kinetics table

Gloss measurement (± 2)

T0181

T1183

T2172

As can be seen from the above data, the degree of gloss exhibited by the cosmetic product of the present invention when applied for the first time is high. However, surprisingly, after 1 hour the degree of gloss remained fairly constant and even after 2 hours it was extremely high, demonstrating an exceptional gloss duration over time.