FR3152122A3 - COMPOSITION IN THE FORM OF A WATER-IN-OIL EMULSION AND ASSOCIATED PROCESSES - Google Patents

Abstract

COMPOSITION IN THE FORM OF A WATER-IN-OIL EMULSION AND RELATED METHODS The present disclosure relates to a composition in the form of a water-in-oil emulsion, preferably in a physiologically acceptable medium, said composition comprising, i) a continuous oil phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4.9% relative to the total weight of the composition; e) at least one hydrophobic silica aerogel in a weight range of 1% to 5% relative to the total weight of the composition; f) at least one silicone emulsifier having an HLB of less than 8; and g) at least one pigment; and ii) an aqueous phase. Figure for abstract: none

Description

COMPOSITION IN THE FORM OF A WATER-IN-OIL EMULSION AND ASSOCIATED PROCESSES FIELD OF INVENTION

This disclosure relates to the field of personal care products, specifically makeup compositions in the form of water-in-oil emulsions. This disclosure also relates to a process for applying makeup and caring for keratinous materials, preferably skin.

CONTEXT OF THE INVENTION

Foundation is the cornerstone of any makeup bag for achieving a natural and stunning look. Among the various foundation products available, liquid foundations are widely preferred because they offer buildable coverage. A consumer's favorite liquid foundation should be lightweight, easy to apply, transfer-resistant, provide excellent coverage, and have a long-lasting effect.

Liquid foundations that offer the best coverage with a long-lasting effect are achieved using higher amounts of fillers and polymers. The use of such polymers/fillers tends to result in a less-than-ideal buildup and makes the product expensive. Furthermore, the use of oil-based UV filters for additional sun protection compromises the long-lasting effect of the liquid foundation. Therefore, developing a liquid foundation that offers long-lasting coverage with sun protection at an affordable price is a significant challenge.

Therefore, there is a need to optimize the concentration of fillers/polymers with UV filters to obtain a liquid foundation with a desirable texture, satisfactory buildable coverage, long-lasting, transfer-resistant and affordable for consumers.

In one aspect of this disclosure, a composition is proposed in the form of a water-in-oil emulsion, preferably in a physiologically acceptable medium, said composition comprising: i) a continuous oil phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4.9% relative to the total weight of the composition; e) at least one hydrophobic silica aerogel in a weight range of 1% to 5% relative to the total weight of the composition; f) at least one silicone emulsifier having a hydrophilic-lipophilic balance (HLB) of less than 8; and g) at least one pigment; and ii) an aqueous phase, in which the at least one non-volatile hydrocarbon oil is selected from non-UV-blocking synthetic ester oils, lipophilic liquid organic UV filters, or mixtures thereof.

In another aspect of this disclosure, a kit is proposed comprising (a) the composition as disclosed herein; (b) a container; and (c) optionally, an applicator.

In another aspect of this disclosure, a process for coating keratinous material, preferably for makeup and/or care of keratinous material, preferably skin, is proposed, characterized in that said process includes the application of said composition as disclosed herein to the keratinous material, preferably skin.

These features, aspects, and advantages, as well as others, of the subject matter will be better understood with reference to the following description and the attached claims. This summary is provided to present a selection of concepts in a simplified form. This summary is not intended to identify key features or essential characteristics of the claimed subject matter, nor to be used to limit the scope of the claimed subject matter.

The following drawings form part of this descriptive memorandum and are included to further illustrate aspects of this disclosure. The disclosure can be better understood by referring to the drawings in conjunction with the detailed description of the specific embodiments presented herein.

FIG. 1 FIG. 1 FIG. 1 FIG. 1 FIG. 1 FIG. 1 FIG. 1 FIG. 1 Figures 1 (AH) illustrate the long-term test results of compositions applied to a sample card and dried at 37 °C for 20 hours, A) C(1); B) C(2); C) C(3); D) C(4); E) C(5); F) C(6); G) C(7) and H) C(8), in accordance with one embodiment of this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

Those skilled in the art will be aware that this disclosure is subject to variations and modifications other than those specifically described. It should be understood that this disclosure includes all such variations and modifications. The disclosure also includes all the steps, features, compositions, and compounds designated or indicated in this descriptive memorandum, individually or collectively, and any combination of one or more of these steps or features.

Definitions

For convenience, before describing this disclosure in more detail, certain terms used in the descriptive memorandum and examples are defined here. These definitions should be read in conjunction with the rest of the disclosure and understood as by a person skilled in the art. The terms used here have meanings recognized and known to persons skilled in the art; however, for convenience and completeness, specific terms and their meanings are provided below.

The terms "understand" and "comprising" are used in an inclusive and open sense, meaning that additional elements may be included. It is not meant to be interpreted as "consisting solely of".

The expression "at least one" is used to mean one or more and therefore includes individual components as well as mixtures/combinations.

Throughout this descriptive memorandum, unless the context requires otherwise, the term "understand," and variations such as "includes" and "including," shall be understood as implying the inclusion of any stated element or step or group of stated elements or steps, but not the exclusion of any other element or step or group of elements or steps.

The term "including" is used to mean "including, not limited to". "Including" and "including, but not limited to" are used interchangeably.

The term "INCI" is an abbreviation for International Nomenclature of Cosmetic Ingredients, which is a system of names provided by the International Nomenclature Committee of the Personal Care Products Council to identify ingredients in cosmetic or personal care products.

The term "keratinous material" as used here refers to the skin and more specifically the skin of areas such as the face, cheeks, hands, body, legs and thighs, the area around the eyes and eyelids.

The term "physiologically acceptable medium" as used here means a medium that is compatible with the skin and/or its superficial body growths, has a pleasant color, odor, and feel, and does not cause unacceptable discomfort (tingling or tightness) that would discourage the consumer from using the composition.

The term "water-in-oil emulsion" as used here refers to a composition comprising a continuous oily phase and an aqueous phase, which are immiscible; the aqueous phase being dispersed as droplets in the continuous oily phase so as to obtain a macroscopically homogeneous composition.

The term “transfer resistant” as used here refers to the property of a composition to remain on the keratinous material to which it is applied for a long time.

All percentages, parts, and ratios are based on the total weight of the composition of this disclosure, unless otherwise stated. Ratios, concentrations, quantities, and other numerical data may be presented here in a range format. It should be understood that this range format is used solely for convenience and conciseness and should be interpreted flexibly as including not only the numerical values explicitly stated as the range limits, but also all individual numerical values or subranges encompassed within that range as if each numerical value and subrange were explicitly stated. For example, a percentage range of approximately 1% to 5% should be interpreted as including not only the explicitly stated limits of approximately 1% to approximately 5%, but also subranges, such as 2% to 3%, 3% to 4%, and so on, as well as individual quantities, including fractional quantities, within the specified ranges, such as 2.84% and 3%, for example.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as that commonly understood by a person in the field to which this disclosure pertains. Although all processes and materials similar or equivalent to those described herein may be used in the practice or testing of the disclosure, preferred processes and materials are described hereafter.

This disclosure should not be limited in scope by the specific embodiments described herein, which are intended for illustrative purposes only. Functionally equivalent products, compositions, and processes clearly fall within the scope of this disclosure, as described herein.

The present embodiments propose a composition, in the form of a water-in-oil emulsion, preferably in a physiologically acceptable medium for coating keratinous materials. The disclosed embodiments include a composition, a kit containing the composition, a method for coating keratinous material using said composition, and a process for preparing the composition. In various embodiments herein, the composition is a liquid foundation composition with improved cosmetic properties, which addresses the drawbacks of existing liquid foundation products. Generally, liquid foundations tend to contain a higher quantity of film-forming polymers to provide buildable coverage. Such high polymer quantities negatively impact consumers in terms of sensory aspects and the product's purchase price. Furthermore, the use of lipophilic organic UV filters compromises the coverage provided by the polymers and results in poor durability. Therefore, the composition according to the embodiments presented here is a water-in-oil emulsion, which provides long-lasting coverage and is transfer-resistant. Furthermore, the composition offers sun protection due to the presence of UV filters.

Composition

The embodiments presented herein provide a composition for coating a keratinous material. According to one embodiment, the composition offers a durable, transfer-resistant, made-up appearance. Furthermore, the composition, according to one embodiment, provides enhanced benefits to the keratinous material, such as sun protection, radiance, and sebum control. In one embodiment, a water-in-oil emulsion composition is proposed, preferably in a physiologically acceptable medium. This composition comprises: i) a continuous oil phase including: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer; e) at least one hydrophobic silica aerogel; f) at least one silicone emulsifier; and g) at least one pigment; and ii) an aqueous phase. In other embodiments, the composition further includes at least one additive selected from salts, solvents, fillers, gelling agents, preservatives or mixtures thereof.

In another embodiment, a composition is proposed comprising: i) a continuous oily phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4.9% relative to the total weight of the composition; e) at least one hydrophobic silica aerogel in a weight range of 1% to 5% relative to the total weight of the composition; f) at least one silicone emulsifier having an HLB of less than 8; and g) at least one pigment; and ii) an aqueous phase, wherein the at least one non-volatile hydrocarbon oil is selected from non-UV-blocking synthetic ester oils, lipophilic liquid organic UV filters, or mixtures thereof.

In yet another embodiment, a composition is proposed comprising: i) a continuous oily phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4% relative to the total weight of the composition; e) at least one hydrophobic silica aerogel in a weight range of 1% to 2% relative to the total weight of the composition; f) at least one silicone emulsifier having an HLB of less than 8; and g) at least one pigment; and ii) an aqueous phase, wherein the at least one non-volatile hydrocarbon oil is selected from non-UV-blocking synthetic ester oils, lipophilic liquid organic UV filters, or mixtures thereof.

continuous oily phase

The composition according to the embodiments herein comprises a continuous oily phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4.9% relative to the total weight of the composition; e) at least one hydrophobic silica aerogel in a weight range of 1% to 5% relative to the total weight of the composition; f) at least one silicone emulsifier having an HLB of less than 8; and g) at least one pigment.

The oily phase of this disclosure is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg). It is organic, comprising at least carbon and hydrogen atoms, and is immiscible in water.

The term "oil" refers to a fatty substance, which is liquid at room temperature (25°C) and atmospheric pressure (760 mmHg, or ^10⁵ Pa).

The total amount of oil phase in the composition of this disclosure preferably ranges from 30% to 80% by weight and, more particularly, ranges from 50% to 75% by weight, relative to the total weight of the composition.

volatile hydrocarbon oil

The continuous oily phase of the composition according to the embodiments herein includes at least one volatile hydrocarbon oil.

The term "hydrocarbon oil" is used to designate an oil comprising mainly carbon and hydrogen atoms and optionally one or more functional groups chosen from among the hydroxyl, ester, ether or carboxyl functional groups.

The term "volatile oil," as used here, refers to any oil capable of evaporating upon contact with the skin in less than one hour at room temperature (25°C) and atmospheric pressure (760 mmHg). Volatile oil is a volatile cosmetic compound that is liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, having in particular a vapor pressure ranging from 0.13 Pa to 40,000 Pa ( ^10⁻³ to 300 mmHg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

Non-limiting examples of volatile hydrocarbon oils that can be used in the present invention include hydrocarbon oils containing 8 to 16 carbon atoms, and in particular petroleum-derived _C8 - _C16 isoalkanes (also known as isoparaffins), for example isododecane (also known as 2,2,4,4,6-pentamethylheptane) and isohexadecane, and for example, oils sold under the trade names Isopar® or Permethyl®, branched _C8 - _C16 esters and isohexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils, such as petroleum distillates, particularly those sold under the name Shell Solt by Shell, can also be used; volatile linear alkanes, such as those described in Cognis patent application DE102008012457.

In one embodiment of this disclosure, at least one volatile hydrocarbon oil is preferably isododecane.

The amount of volatile hydrocarbon oil in the composition, according to the embodiments herein, may vary. The volatile hydrocarbon oil, according to the embodiments herein, may be present in the composition in a weight range of 8% to 40%, preferably in a weight range of 10% to 30%, and more preferably from 10% to 20% relative to the total weight of the composition.

volatile silicone oil

The oily phase of the composition according to the embodiments herein includes at least one volatile silicone oil.

The term "silicone oil" is used to refer to an oil comprising at least one silicon atom, and in particular at least one Si-O group, and more specifically an organopolysiloxane.

Examples of volatile silicone oils that may be used in this disclosure include linear, non-cyclic volatile silicone oils, those having a viscosity ≤ 8 centistokes (8× ^{10⁻⁶ m²} /s) and in particular having 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having 1 to 20 carbon atoms.

In one embodiment of this disclosure, the volatile silicone oil is selected from linear volatile silicone oils with a viscosity ranging from 1 to 8 cSt (1 × ^10⁻⁶ to 8 × ^{10⁻⁶ m²} /s), such as dimethicones, trisiloxane, and dodecamethyl pentasiloxane. For example, the volatile silicone oil is dodecamethyl pentasiloxane, available under the names KF-96L-2CS® and DM-Fluid-2CS® by Shin Etsu, Berb-DM2® by BRB International, or Xiameter PMX-200 Silicone Fluid 2CS® by Dow Corning.

In another embodiment of this disclosure, the volatile silicone oil is dimethicone, which corresponds to a compound with the chemical name polydimethylsiloxane.

The amount of volatile silicone oil present in the composition, according to the embodiments herein, may vary. The volatile silicone oil, according to the embodiments herein, may be present in the composition in a weight range of 10% to 40%, preferably in a weight range of 15% to 30%, and more preferably from 15% to 20% relative to the total weight of the composition.

Non-volatile hydrocarbon oil

The oily phase of the composition according to the embodiments herein includes at least one non-volatile hydrocarbon oil selected from non-UV-blocking synthetic ester oils, lipophilic liquid organic UV filters or mixtures thereof.

• les huiles hydrocarbonées d’origine animale,
• les hydrocarbures linéaires ou ramifiés d’origine minérale ou synthétique, tels que gelée de pétrole, polydécènes, polyisobutène hydrogéné tel que Parleam®, et squalane et leurs mélanges,
• les alcanes non volatils, de préférence avec une viscosité inférieure à 20 mPa.s à 20 °C mesurée avec un viscosimètre Rheomat RM100® de Lamy Rheology.

Non-volatile hydrocarbon oils, particularly non-UV-shielding synthetic ester oils, include:

• hydrocarbon oils of animal origin,
• linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, and squalane and their mixtures,
• non-volatile alkanes, preferably with a viscosity of less than 20 mPa.s at 20 °C measured with a Rheomat RM100® viscometer from Lamy Rheology.

The term "non-volatile alkane" refers to a hydrocarbon cosmetic oil, which is liquid at room temperature, having in particular a vapor pressure at 20 °C of less than 0.01 kPa, according to the definition of a Volatile Organic Compound (VOC) in Article 2 of Directive 1999/13/EC of the European Council of 11 March 1992: "Any organic compound having, at a temperature of 293.15 K, a vapor pressure equal to or greater than 0.01 kPa".

• les esters synthétiques, tels que les huiles de formule R₁COOR₂, dans laquelle R₁représente un résidu d’acide gras linéaire ou ramifié comprenant de 1 à 40 atomes de carbone et R₂représente une chaîne hydrocarbonée qui est notamment ramifiée, contenant de 1 à 40 atomes de carbone, à condition que R₁+ R₂soit supérieur ou égal à 10, par exemple huile de purcelline (octanoate de cétostéaryle), myristate d’isopropyle, myristate de myristyle, palmitate d’isopropyle, les benzoates d’alkyle ayant entre 12 et 15 atomes de carbone, tels que le produit vendu sous le nom commercial Finsolv TN ou Witconol TN par la société Witco ou Tegosoft TN par la société Evonik Goldschmidt, le benzoate de 2-éthylphényle, tels que le produit commercial vendu sous le nom X-Tend 226 par la société ISP, le lanolate d’isopropyle, le laurate d’hexyle, l’adipate de diisopropyle, l’isononanoate d’isononyle, l’érucate d’oléyle, le palmitate de 2-éthylhexyle, l’isostéarate d’isostéaryle, le sébacate de diisopropyle, tel que le produit vendu sous le nom DUB DIS par la société Stéarinerie Dubois, les octanoates d’alcool ou de polyalcool, les décanoates ou ricinoléates, tels que le dioctanoate de propylène glycol ; les esters hydroxylés, tels que le lactate d’isostéaryle, le malate de diisostéaryle ; et les esters de pentaérythritol, en particulier le tétraoctanoate de pentaérythrityle (nom INCI : Pentaerythrityl Tetraethylhexanoate) ; l'hexacaprylate/hexacaprate de dipentaérythrityle, les citrates, tels que l’ester d’acide tricarboxylique en C3-C22 et d’alcools en C1-C6 de nom INCI Triethyl Citrate, par exemple celui vendu sous le nom Citrofol AI Extra® par la société Jungbunzlauer ; les tartrates, tels que les tartrates de dialkyle linéaires ayant 12 ou 13 atomes de carbone, par exemple ceux vendus sous le nom Cosmacol ETI® par la société Enichem Augusta Industriale, ainsi que les tartrates de dialkyle linéaires ayant entre 14 et 15 atomes de carbone, par exemple ceux vendus sous le nom Cosmacol ETL® par la même société, et les acétates ;
• les esters de polyol et les esters de pentaérythritol, par exemple le tétrahydroxystéarate/tétrastéarate de dipentaérythrityle,
• les esters de dimère de diol et dimère de diacide, le cas échéant estérifiés sur leur(s) fonction(s) alcool libre(s) ou acide(s) avec des radicaux acides ou alcools, en particulier les esters de dilinoléate dimère ; plus particulièrement choisis parmi les esters de nomenclature INCI suivante : bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G®), phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H® ou Plandool S), et leurs mélanges,
• ainsi que des mélanges de ces diverses huiles.

Non-volatile hydrocarbon oils also include non-UV-screening synthetic ester oils such as vegetable-derived hydrocarbon oils, such as glyceride triesters, which are generally fatty acid and glycerol triesters, whose fatty acids can have varying chain lengths from 4 to 24 carbon atoms, these chains being saturated or unsaturated and linear or branched; These oils include, in particular, wheat germ oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea butter, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin seed oil, pumpkin seed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, and oil of musk rose and Limnanthes alba seed oil (INCI name: Limnanthes Alba (Meadowfoam) Seed Oil); or caprylic/capric acid triglycerides, such as those sold by Stéarinerie Dubois or those sold under the names MIGLYOL 810®, 812® and 818® by Dynamit Nobel;

• synthetic esters, such as oils with the formula _R1COOR2 , in which _R1 represents a linear or branched fatty acid residue comprising 1 to 40 carbon atoms and _R2 represents a hydrocarbon chain _, which is notably branched, containing 1 to 40 carbon atoms, provided that _R1 + _R2 is greater than or equal to 10, for example, purcelline oil (cetostearyl octanoate), isopropyl myristate, myristyle myristate, isopropyl palmitate; alkyl benzoates having between 12 and 15 carbon atoms, such as the product sold under the trade name Finsolv TN or Witconol TN by Witco or Tegosoft TN by Evonik Goldschmidt; 2-ethylphenyl benzoate, such as the commercial product sold under the name X-Tend 226 by ISP; isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, such as the product sold under the name DUB DIS by the company Stéarinerie Dubois, alcohol or polyalcohol octanoates, decanoates or ricinoleates, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters, in particular pentaerythrityl tetraoctanoate (INCI name: Pentaerythrityl Tetraethylhexanoate); dipentaerythrityl hexacaprylate/hexacaprate, citrates, such as the C3-C22 tricarboxylic acid ester of C1-C6 alcohols with the INCI name Triethyl Citrate, for example that sold under the name Citrofol AI Extra® by Jungbunzlauer; tartrates, such as linear dialkyl tartrates having 12 or 13 carbon atoms, for example those sold under the name Cosmacol ETI® by Enichem Augusta Industriale, as well as linear dialkyl tartrates having between 14 and 15 carbon atoms, for example those sold under the name Cosmacol ETL® by the same company, and acetates;
• polyol esters and pentaerythritol esters, for example dipentaerythrityl tetrahydroxystearate/tetrastearate,
• diol dimer and diacid dimer esters, where appropriate esterified on their free alcohol or acid function(s) with acid radicals or alcohols, in particular dimer dilinoleate esters; more particularly selected from the esters with the following INCI nomenclature: bis-behenyl/isostearyl/phytosteryl dimer dilinoleyl dimer dilinoleate (Plandool G®), phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate (Plandool H® or Plandool S), and mixtures thereof,
• as well as mixtures of these various oils.

Liquid lipophilic organic UV filters can also be mentioned as examples of non-volatile hydrocarbon oils.

The term “liquid lipophilic organic UV filters” refers to any organic chemical molecule capable of absorbing at least one type of UV radiation in the wavelength range of 280 to 400 nm, said molecule being in liquid form at room temperature (20–25 °C) and atmospheric pressure (760 mmHg) and miscible in an oil phase. The terms “liquid lipophilic organic UV filter” and “liquid organic UV shielding agents” are used interchangeably throughout this disclosure.

• les composés lipophiles liquides β,β-diphénylacrylate,
• les composés lipophiles liquides salicylate,
• les composés lipophiles liquides cinnamate – et leurs mélanges.

Liquid organic UV-blocking agents that may be used according to this disclosure may be selected from

• liquid lipophilic compounds β,β-diphenylacrylate,
• liquid lipophilic compounds such as salicylate,
• Liquid lipophilic compounds cinnamate – and their mixtures.

β,β-Diphenylacrylate compounds

Among the liquid lipophilic organic UV-blocking agents that may be used according to this disclosure are the liquid lipophilic alkyl β,β-diphenylacrylate or α-cyano-β,β-diphenylacrylate compounds of formula (I) below:

• R₁et R'₁, qui peuvent être identiques ou différents, représentent un atome d’hydrogène, un radical alcoxy en C1-C8 à chaîne droite ou ramifiée ou un radical alkyle en C1-C4 à chaîne droite ou ramifiée ;
• R₁et R'₁étant en position para ou méta ;
• R₂représente un radical alkyle en C1-C12 à chaîne droite ou ramifiée ;
• R₃représente un atome d’hydrogène ou le radical CN.

in which R ₁ to R ₃ can have the following meanings:

• _R1 and _R'1 , which may be identical or different, represent a hydrogen atom, a straight-chain or branched-chain C1-C8 alkoxy radical, or a straight-chain or branched-chain C1-C4 alkyl radical;
• _R1 and _R'1 being in para or meta position;
• R ₂ represents a straight-chain or branched C1-C12 alkyl radical;
• R ₃ represents a hydrogen atom or the CN radical.

Among the straight-chain or branched C1-C8 alkoxy radicals, examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-amyloxy, isoamyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy and 2-ethylhexyloxy.

Among the straight-chain or branched C1-C4 alkyl radicals, we can mention in particular the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl radicals.

For C1-C12 alkyl radicals, examples include, in addition to those mentioned above, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, decyl and lauryl radicals.

• 2-éthylhexyl α-cyano-β,β-diphénylacrylate ou Octocrylène vendu notamment sous le nom commercial Uvinul N539® par BASF ;
• éthyl α-cyano-β,β-diphénylacrylate tel que l’Étocrylène vendu en particulier sous le nom commercial Uvinul N35® par BASF ;
• 2-éthylhexyl β,β-diphénylacrylate ; ou
• éthyl β,β-di(4'-méthoxyphényl)acrylate.

Among the compounds with general formula (I), the following compounds are particularly preferred:

• 2-ethylhexyl α-cyano-β,β-diphenylacrylate or Octocrylene sold notably under the trade name Uvinul N539® by BASF;
• ethyl α-cyano-β,β-diphenylacrylate such as Etocrylene sold in particular under the trade name Uvinul N35® by BASF;
• 2-Ethylhexyl β,β-diphenylacrylate; or
• ethyl β,β-di(4'-methoxyphenyl)acrylate.

Among the compounds of general formula (I), the compound 2-ethylhexyl 2-cyano3,3-diphenylacrylate or octocrylene is even more particularly preferred.

Salicylate compounds

• Homosalate vendu sous le nom Eusolex HMS® par Rona/EM 15 Industries et salicylate d’éthylhexyle, vendu sous le nom Neo Heliopan OS® par Symrise.

Examples of liquid lipophilic salicylate compounds used according to this disclosure include:

• Homosalate sold under the name Eusolex HMS® by Rona/EM 15 Industries and ethylhexyl salicylate, sold under the name Neo Heliopan OS® by Symrise.

Cinnamate compounds

• Méthoxycinnamate d’éthylhexyle vendu en particulier sous le nom commercial Parsol MCX® par DSM Nutritional Products, méthoxycinnamate d’isopropyle et méthoxycinnamate d’isoamyle, vendu sous le nom commercial Neo Heliopan E 1000 par Symrise.

Examples of liquid lipophilic cinnamate compounds that may be used according to this disclosure include:

• Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX® by DSM Nutritional Products, isopropyl methoxycinnamate and isoamyl methoxycinnamate, sold under the trade name Neo Heliopan E 1000 by Symrise.

In one embodiment of this disclosure, the non-volatile hydrocarbon oil is selected from liquid lipophilic screening agents, preferably the compound 2-ethylhexyl 2-cyano3,3-diphenylacrylate or octocrylene.

In one embodiment of this disclosure, the non-volatile hydrocarbon oil comprises at least one synthetic ester, preferably of isononyl isonanoate.

In another embodiment of this disclosure, the non-volatile hydrocarbon oil comprises at least one non-UV-blocking synthetic ester oil and at least one liquid lipophilic organic UV filter, and more preferably a mixture of isononyl isononanoate and octocrylene.

The amount of non-volatile hydrocarbon oil present in the composition, according to the embodiments herein, may vary. The non-volatile hydrocarbon oil, according to the embodiments herein, may be present in the composition in a weight range of 5% to 25%, preferably in a weight range of 5% to 15%, and more preferably from 5% to 10% relative to the total weight of the composition.

Hydrophobic silicone film-forming polymer

The oily phase of the composition according to the embodiments herein includes at least one hydrophobic silicone film-forming polymer.

The term "polymer" is used to designate a compound corresponding to the repetition of one or more motifs (these motifs resulting from compounds known as monomers). This motif or these motifs are repeated at least twice and, preferably, at least three times.

According to this disclosure, the term “hydrophobic film-forming polymer” is used to refer to a film-forming polymer that lacks affinity for water and, as such, is unsuitable for formulation as a solute in aqueous media. Specifically, the term “hydrophobic polymer” is used to refer to a polymer with a water solubility at 25°C of less than 1% by weight.

The term “film-forming polymer” means a polymer capable of forming, alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on keratinous materials, preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that said film can be isolated and handled in isolation, for example when said film is prepared by pouring it onto a non-adhesive surface, such as a surface coated with Teflon or coated with silicone.

In particular, the hydrophobic film-forming polymer is a polymer selected from the group of film-forming polymers that are soluble in an organic solvent medium, especially liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and will form a single homogeneous phase when incorporated into the medium.

As used here, "silicone film-forming polymer" refers to a film-forming agent that contains silicone. In one or more embodiments, a "silicone-containing film-forming agent" includes polymers that contain at least about 2.5%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% silicone by weight of the silicone film-forming polymer.

Examples include, as hydrophobic silicone film-forming polymers, silicone resins; vinyl polymers comprising at least one motif derived from the carbosiloxane dendrimer; silicone-acrylate copolymers; copolymers of silicone polyamide and hydrocarbon polyamide, or mixtures thereof.

I. SILICONE RESINS

The term "resin" is used to refer to a compound with a three-dimensional structure. The terms "silicone resins" and "siloxane resins" are used interchangeably in this document. Therefore, for the purposes of this disclosure, polydimethylsiloxane is not a silicone resin.

The nomenclature for silicone resins (also referred to as siloxane resins) is known as "MDTQ", the resin being described according to the various siloxane monomer motifs it comprises, each of the letters "MDTQ" characterizing a type of motif.

The letter "M" represents the monofunctional motif of formula R ₁ R ₂ R ₃ SiO _1/2 , the silicon atom being bonded to a single oxygen atom in the polymer comprising this motif.

The letter "D" denotes a difunctional motif R ₁ R ₂ SiO _2/2 in which the silicon atom is bonded to two oxygen atoms.

The letter "T" represents a trifunctional motif of formula R ₁ SiO _3/2 .

These resins are described, for example, in Encyclopedia of Polymer Science and Engineering , vol. 15, John Wiley and Sons, New York, (1989), pp. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

In the M, D and T motifs defined above, R, namely R ₁ and R ₂ , represents a hydrocarbon radical (in particular an alkyl radical) comprising 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.

Finally, the letter Q designates a tetrafunctional SiO _4/2 motif in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer.

Various silicone resins with different properties can be obtained from these different patterns, the properties of these polymers varying according to the type of monomer (or patterns), the nature and number of the R radical, the length of the polymer chain, the degree of branching and the size of the dangling chains.

Silicone resins that can be used in compositions according to this disclosure may include, for example, MQ type, T type or MQT type silicone resins.

Examples of MQ type silicone resins include alkylsiloxysilicates of formula [(R1)3SiO1/2]x(SiO4/2)y (MQ motifs) in which x and y are integers between 50 and 80, and such that the R1 group represents a radical as defined above, and is preferably an alkyl group containing 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.

Examples of MQ type trimethylsiloxysilicate solid silicone resins include those sold under the reference SR1000® by General Electric, under the reference TMS 803® by Wacker and under the names KF-7312®J by Shin-Etsu and DC 749® and DC 593® by Dow Corning.

Phenylalkylsiloxysilicate resins, such as phenylpropyldimethyl siloxysilicate (Silshine 151® sold by General Electric), can also be mentioned as silicone resins containing MQ siloxysilicate motifs. The preparation of these resins is described in particular in US patent 5,817,302.

T Resins

Examples of T-type silicone resins include polysilsesquioxanes of formula (RSiO _3/2 ) _x (T motifs) in which x is greater than 100 and such that the R group is an alkyl group comprising 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

• par Wacker sous la référence Resin MK®, telle que Belsil PMS MK® : polymère comprenant des motifs répétés CH₃SiO_3/2(motifs T), qui peuvent également comprendre jusqu’à 1 % en poids de (CH₃)₂SiO_2/2(motifs D) et ayant un poids moléculaire moyen d’environ 10 000 g/mol, ou
• par Shin-Etsu sous la référence KR-220L® qui sont composées de motifs T de formule CH₃SiO_3/2et contiennent des groupes d'extrémité Si-OH (silanol), sous la référence KR-242A® qui comprennent 98 % de motifs T et 2 % de motifs D diméthyle et contiennent des groupes d'extrémité Si-OH, ou également sous la référence KR-251®, comprenant 88 % de motifs T et 12 % de motifs D diméthyle et contient des groupes d'extrémité Si-OH.

Preferably, polymethylsilsesquioxane resins can be used in which R represents a methyl group, such as, for example, those sold:

• by Wacker under the reference Resin MK®, such as Belsil PMS MK®: a polymer comprising repeating _{CH3SiO3 /2} motifs (T motifs), which may also comprise up to 1 wt% of ( _CH3 ) _{2SiO2/ 2} (D motifs) and having an average molecular weight of about 10,000 g/mol, or
• by Shin-Etsu under the reference KR-220L® which are composed of T motifs of formula CH ₃ SiO _3/2 and contain Si-OH (silanol) end groups, under the reference KR-242A® which comprise 98% T motifs and 2% D dimethyl motifs and contain Si-OH end groups, or also under the reference KR-251®, comprising 88% T motifs and 12% D dimethyl motifs and contains Si-OH end groups.

MQT resins

Resins containing MQT motifs that are particularly known are those mentioned in US document 5,110,890.

A preferred form of MQT-type resins is MQT-propyl resins (also known as MQTPr). These resins, which may be used in the compositions according to this disclosure, are in particular those described and prepared in application WO 2005/075542.

MQT-propyl resin preferably includes the following motifs:

(i) (R1 ₃ SiO _1/2 ) _a ;

(ii) (R2 ₂ SiO _2/2 ) _b ;

(iii) (R3SiO _3/2 ) _c ; and

(iv) (SiO _4/2 ) _d ;

with :

• a étant compris entre 0,05 et 0,5,
• b étant compris entre zéro et 0,3,
• c étant supérieur à zéro,
• d étant compris entre 0,05 et 0,6,
• a + b + c + d = 1, et a, b, c et d étant des fractions molaires,
  à condition que plus de 40 % en mol des groupes R3 de la résine siloxane soient des groupes propyle.

R1, R2 and R3 independently represent a hydrocarbon radical (in particular alkyl) comprising 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical comprising 1 to 8 carbon atoms or a phenyl group,

• a being between 0.05 and 0.5,
• b being between zero and 0.3,
• where c is greater than zero,
• d being between 0.05 and 0.6,
• a + b + c + d = 1, and a, b, c and d are mole fractions,
  provided that more than 40% by mol of the R3 groups of the siloxane resin are propyl groups.

Preferably, the siloxane resin includes the following patterns:

(i) (R1 ₃ SiO _1/2 ) _a ;

(iii) (R3SiO _3/2 ) _c ; and

(iv) (SiO _4/2 ) _d ;

• R1 et R3 représentant indépendamment un groupe alkyle comportant de 1 à 8 atomes de carbone, R1 étant de préférence un groupe méthyle et R3 de préférence un groupe propyle,
• a étant compris entre 0,05 et 0,5 et de préférence entre 0,15 et 0,4,
• c étant supérieur à zéro, de préférence compris entre 0,15 et 0,4,
• d étant compris entre 0,05 et 0,6, de préférence entre 0,2 et 0,6 ou également entre 0,2 et 0,55,
• a + b + c + d = 1 et a, b, c et d étant des fractions molaires, à condition que plus de 40 % en mol des groupes R3 de la résine siloxane soient des groupes propyle.

with :

• R1 and R3 independently represent an alkyl group comprising 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably a propyl group,
• a being between 0.05 and 0.5 and preferably between 0.15 and 0.4,
• c being greater than zero, preferably between 0.15 and 0.4,
• d being between 0.05 and 0.6, preferably between 0.2 and 0.6 or also between 0.2 and 0.55,
• a + b + c + d = 1 and a, b, c and d being mole fractions, provided that more than 40% by mol of the R3 groups of the siloxane resin are propyl groups.

The siloxane resins that can be used according to the disclosure can be obtained by a process including the reaction of:

• R1 représentant un groupe alkyle comportant de 1 à 8 atomes de carbone, un groupe aryle, un groupe carbinol ou un groupe amino,
• a et d étant supérieurs à zéro,
• le rapport a/d étant compris entre 0,5 et 1,5 ;

A) an MQ resin comprising at least 80 mol% of (R1 ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d motifs; with

• R1 represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group.
• a and d being greater than zero,
• the a/d ratio being between 0.5 and 1.5;

and of:

• R3 représentant un groupe alkyle comportant de 1 à 8 atomes de carbone, un groupe aryle, un groupe carbinol ou un groupe amino,
• c étant supérieur à zéro, à condition qu’au moins 40 % en mol des groupes R3 soient des groupes propyle, où le rapport en poids A/B est compris entre 95:5 et 15:85 et de préférence le rapport en poids A/B est de 30:70.

B) a T-propyl resin comprising at least 80 mol% of (R3SiO3 _/2 )c motifs; with

• R3 represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group.
• c being greater than zero, provided that at least 40% by mol of the R3 groups are propyl groups, where the weight ratio A/B is between 95:5 and 15:85 and preferably the weight ratio A/B is 30:70.

Advantageously, the A/B weight ratio is between 95:5 and 15:85. Preferably, the A/B ratio is less than or equal to 70:30. These preferred ratios have been shown to allow comfortable deposition due to the absence of percolation of rigid MQ resin particles into the deposit.

1. les alkylsiloxysilicates, qui peuvent être des triméthylsiloxysilicates, de formule [R1₃SiO_1/2]_x(SiO_4/2)_y, dans laquelle x et y sont des nombres entiers allant de 50 à 80, et tels que le groupe R1 représente un radical hydrocarboné ayant de 1 à 10 atomes de carbone, un groupe phényle, un groupe phénylalkyle ou encore un groupe hydroxyle, et est de préférence un groupe alkyle ayant de 1 à 8 atomes de carbone, de préférence un groupe méthyle, et
2. les résines de phénylalkylsiloxysilicate, telles que la résine de phénylpropyldiméthylsiloxysilicate.

Therefore, preferably, the silicone resin is chosen from among the MQ type resins, specifically chosen from

1. alkylsiloxysilicates, which may be trimethylsiloxysilicates, of the formula [R1 ₃ SiO _1/2 ] _x (SiO _4/2 ) _y , in which x and y are integers from 50 to 80, and such that the group R1 represents a hydrocarbon radical having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and is preferably an alkyl group having from 1 to 8 carbon atoms, preferably a methyl group, and
2. phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate resin.

In one embodiment of this disclosure, the composition includes a hydrophobic film-forming polymer, at least one trimethylsiloxysilicate resin, such as those sold under the name Silsoft 74® by Momentive Performance Materials, SR1000® by General Electric, under the name TMS 803® by Wacker and under the names KF-7312®J by Shin-Etsu and DC 749® and DC 593® by Dow Corning.

Silsesquioxane resins

Examples of silsesquioxane resins that may be used in compositions in accordance with this disclosure include alkylsilsesquioxane resins that are homopolymers of silsesquioxane and/or copolymers having an average siloxane motif of formula R1 _n SiO( _4-n)/2 , where each R1 independently designates a hydrogen atom or a C1-C10 alkyl group, where more than 80 mol% of the R1 radicals represent a _C3 - _C10 alkyl group, and n is a number from 1.0 to 1.4, and particular use will be made of a silsesquioxane copolymer in which more than 60 mol% comprises R1SiO _3/2 motifs in which R1 has the definition indicated above.

Preferably, the silsesquioxane resin is chosen such that R1 is a C1 _- C10 alkyl group _, preferably a _C1 - _C4 alkyl group, and more particularly a propyl group. Polypropylsilsesquioxane or t-propylsilsesquioxane resin (INCI name: polypropylsilsesquioxane (and) isododecane) is preferred, such as the product sold under the trade name Dow Corning® 670 Fluid by Dow Corning.

II. VINYL POLYMERS COMPRISING AT LEAST ONE MOTIFY DERIVED FROM A CARBOSILOXANE DENDRIMER

The hydrophobic silicone film-forming polymer can also be selected from vinyl polymers comprising at least one motif derived from a carbosiloxane dendrimer.

The vinyl polymer(s) in particular have(s) a backbone and at least one side chain, wherein the side chain comprises a motif derived from a carbosiloxane dendrimer having a carbosiloxane dendrimer structure. The carbosiloxane dendrimer motif is as described in Dow Corning applications WO03/045337 and EP 963 751.

In the context of the present invention, the term "carbosiloxane dendrimer structure" represents a molecular structure possessing branched groups with high molecular weights, said structure exhibiting high regularity in the radial direction from the bond to the backbone. These carbosiloxane dendrimer structures are described as highly branched siloxane-silylalkylene copolymers.

• 0,1 à 99,9 parties en poids d’un monomère de vinyle ; et
• 99,9 à 0,1 parties en poids d’un dendrimère de carbosiloxane contenant un groupe organique polymérisable par radicaux, représenté par la formule générale :

A vinyl polymer having at least one motif derived from a carbosiloxane dendrimer has a side chain containing a carbosiloxane dendrimer structure and can result from the polymerization of:

• 0.1 to 99.9 parts by weight of a vinyl monomer; and
• 99.9 to 0.1 parts by weight of a carbosiloxane dendrimer containing a radically polymerizable organic group, represented by the general formula:

in which Y represents an organic group polymerizable by radicals,

^R1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms, and ^Xi represents a silylalkyl group which, when i = 1, is represented by the formula:

in which R1 is as defined above, R2 represents an alkylene group having from 2 to 10 carbon atoms, R3 represents an alkyl group having from 1 to 10 carbon atoms, X i+1  represents a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, an aryl group, or the silylalkyl group as defined above with i = i + 1; i is an integer from 1 to 10 representing the generation of said silylalkyl group, and ai is an integer from 0 to 3; where said radically polymerizable organic group contained in component (A) is chosen from: organic groups containing a methacrylic group or an acrylic group and represented by the following formulas:

And

in which R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents an alkylene group containing from 1 to 10 carbon atoms and organic groups containing a styryl group and which are represented by the following formula:

• (R⁸)_c- représente une liaison.

in which ^R6 represents a hydrogen atom or an alkyl group, ^R7 represents an alkyl group with 1 to 10 carbon atoms, ^R8 represents an alkylene group with 1 to 10 carbon atoms, b is an integer from 0 to 4 and ca is the value 0 or 1, so that, if c is 0,

• (R ⁸ ) _c - represents a bond.

The vinyl-like monomer that is component (A) in the vinyl polymer is a vinyl-like monomer that contains radically polymerizable vinyl groups.

There are no particular limitations to this type of monomer.

Examples of this vinyl-type monomer include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a methacrylate of a lower alkyl analogue; glycidyl methacrylate; butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-hexyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a methacrylate of a higher analogue; vinyl acetate, vinyl propionate, or a vinyl ester of a lower fatty acid analogue; vinyl caproacrylate, vinyl caproacrylate, vinyl ethylethylethylhexoacrylate, vinyl laurate, vinyl stearate, or an ester of a higher fatty acid analogue; styrene, vinyltotoluene, benzyl acrylate, vinyl phoxyacrylate, vinylethylethyl, vinylylhydroxylone or a similar monopolymer; methacrylamide, N-methylolmethacrylamide, N-methoxymethacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylmethacrylamide or similar vinyl-type monomers containing amide groups; hydroxyethyl methacrylate, hydroxypropyl methacrylate or similar vinyl-type monomers containing hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or similar vinyl-type monomers containing a carboxylic acid group; tetrahydrofuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl, cetyl ether, 2-ethylethylethyl vinyl ether, or a similar vinyl-type monomer with oxide; methacryloxypropyltrimethoxysilane, polydimethylsiloxane containing a methacrylic group on one of its molecular ends, polydimethylsiloxane containing a styrene group on one of its molecular ends, or a similar silicone compound containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl glycidyl ether; An organic salt of an amine, an ammonium salt, and an alkali salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid; a radically polymerizable unsaturated monomer containing a sulfonic acid group such as styrene sulfonic acid; a quaternary ammonium salt, such as 2-hydroxyhydroxyhydroxyhydroxy-methacryloxy-propylpropyltrimethylammonium chloride; and a methacrylic acid ester containing a tertiary amine group, such as a diethylamine methacrylic acid ester. Multifunctional vinyl-type monomers may also be used.

The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythrityl trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl methacrylate, tris(2-hydroxyethyl)isocyanurate dimethacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups having divinylbenzene groups at both ends, or analogous silicone compounds having unsaturated groups.

To facilitate the preparation of a raw material blend for cosmetic products, the number-average molecular weight of the vinyl polymer containing a carbosiloxane dendrimer can be chosen from the range of 3000 g/mol to 2,000,000 g/mol, and preferably from 5000 g/mol to 800,000 g/mol. It can be in liquid, gum, paste, solid, powder, or any other form. Preferred forms are solutions formed by diluting a dispersion or powder in solvents, such as silicone oil or an organic oil.

A vinyl polymer contained in the dispersion or solution may have a concentration in the range of 0.1% to 95% by weight, and preferably between 5% and 70% by weight. However, to facilitate handling and preparation of the mixture, the range should preferably be between 10% and 60% by weight.

In a preferred form, a vinyl polymer suitable for this disclosure may be any of the polymers described in the examples in EP 0 963 751.

• de 0,1 à 99,9 parties en poids d’un ou plusieurs monomère(s) d’acrylate ou de méthacrylate ; et
• de 99,9 à 0,1 parties en poids d’un monomère d’acrylate ou de méthacrylate d’un dendrimère tris[tri(triméthylsiloxy)silyléthyldiméthylsiloxy]silylpropylcarbosiloxane.

According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer can result from the polymerization:

• from 0.1 to 99.9 parts by weight of one or more acrylate or methacrylate monomer(s); and
• from 99.9 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropylcarbosiloxane dendrimer.

According to one embodiment, a vinyl polymer having at least one motif derived from a carbosiloxane dendrimer may include a motif derived from a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer corresponding to one of the formulas below.

According to a preferred form, a vinyl polymer having at least one motif derived from a carbosiloxane dendrimer used in this disclosure comprises at least one butyl acrylate monomer.

According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group. A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03/045337.

According to a preferred embodiment, a grafted vinyl polymer as described in this disclosure can be conveyed in an oil or mixture of oils, which is/are preferably volatile, selected in particular from silicone oils and hydrocarbon oils and their mixtures.

Vinyl polymers grafted with at least one carbosiloxane dendrimer-derived motif that may be particularly suitable for this disclosure are the polymers sold by Dow Corning under the names TIB 4-100®, TIB 4-101®, TIB 4-120®, TIB 4-130®, TIB 4-200®, FA 4002 ID® (TIB 4-202®), TIB 4-220®, and FA 4001 CM® (TIB 4-230®). Preferably, the polymers sold by Dow Corning under the names FA 4002 ID® (TIB 4-202) and FA 4001 CM® (TIB 4-230®) are preferred.

Preferably, the vinyl polymer grafted with at least one motif derived from a carbosiloxane dendrimer that may be used in a composition of this disclosure is an acrylate/polytrimethylsiloxymethacrylate copolymer of INCI name: acrylates/polytrimethyl siloxymethacrylate copolymer, in particular that is sold in isododecane under the name Dow Corning FA 4002 ID® Silicone Acrylate by Dow Corning.

III. Silicon Acrylate Copolymers

According to a specific embodiment, a composition used according to this disclosure may include, as a hydrophobic silicone film-forming polymer, at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups.

For the purposes of this disclosure, "copolymer comprising carboxylate groups and polydimethylsiloxane groups" means a copolymer obtained from (a) one or more carboxylic monomers (acid or ester), and (b) one or more polydimethylsiloxane (PDMS) chains.

In this disclosure, the term “carboxylic monomer” refers to both carboxylic acid monomers and carboxylic acid ester monomers. Thus, monomer (a) may be selected, for example, from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters, and mixtures of these monomers.

The following monomers can be mentioned as esters: acrylate, methacrylate, maleate, fumarate, itaconate and/or crotonate. According to a preferred embodiment of this disclosure, the monomers in the form of esters are more particularly chosen from linear or branched alkyl acrylates and methacrylates, preferably in _C1 - _C24 and, more preferably, in _C1 - _C22 , the alkyl radical being preferably chosen from the methyl, ethyl, stearyl, butyl and 2-ethylhexyl radicals, and mixtures thereof.

Thus, according to a specific embodiment of this disclosure, the copolymer comprises, as carboxylate groups, at least one group selected from acrylic acid, methacrylic acid, methyl, ethyl, stearyl, butyl or 2-ethylhexyl acrylate or methacrylate, and mixtures thereof.

In this disclosure, the term "polydimethylsiloxanes" (also called organopolysiloxanes or, for short, PDMS) refers, in accordance with generally accepted practice, to any linear organosilicon polymer or oligomer of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consisting essentially of repeating principal motifs in which silicon atoms are linked together by oxygen atoms comprising methyl radicals directly bonded via a carbon atom to said silicon atoms. The PDMS chains that can be used to obtain the copolymer used according to this disclosure comprise at least one polymerizable radical group, preferably located on at least one end of the chain; that is, the PDMS may, for example, have a polymerizable radical group at both ends of the chain or have a polymerizable radical group at one end of the chain and a trimethylsilyl terminal group at the other end of the chain. The polymerizable radical group can notably be an acrylic or methacrylic group, in particular a _CH2 = _CR1 -CO-OR2 group _, where _R1 represents a hydrogen or a methyl group and _R2 represents _-CH2- , -( _CH2 ) _n- with n = 3, 5, 8 or 10, _-CH2 -CH( _CH3 )-CH2-, _-CH2 - _CH2 -O- _{CH2 -CH2- , -CH2-CH2 -} O-CH2- _CH2 - _CH2 -CH( _CH3 ) _-CH2- , _-CH2 - _CH2 -O- _CH2 or _-CH2 -O- _CH2 - _CH2 - _CH2- .

The copolymers used in the composition of this disclosure are generally obtained by the usual polymerization and grafting processes, for example by radical polymerization (A) of a PDMS comprising at least one radically polymerizable group (e.g. on one or both ends of the chain) and (B) of at least one carboxylic monomer, as described, for example, in US-A-5,061,481 and US-A-5,219,560.

The copolymers obtained generally have a molecular weight ranging from about 3,000 g/mol to 200,000 g/mol and preferably from about 5,000 g/mol to 100,000 g/mol.

The copolymer used in the composition of this disclosure may be supplied as is or dispersed in a solvent, such as lower alcohols comprising 2 to 8 carbon atoms, e.g. isopropyl alcohol, or oils, e.g. volatile cyclic silicone oils (e.g. cyclopentasiloxane).

Examples of copolymers that may be used in the composition of this disclosure include, for example, copolymers of acrylic acid and stearyl acrylate with polydimethylsiloxane grafts, copolymers of stearyl methacrylate with polydimethylsiloxane grafts, copolymers of acrylic acid and stearyl methacrylate with polydimethylsiloxane grafts, or copolymers of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Notable examples of copolymers that may be used in the composition of this disclosure include the copolymers sold by Shin-Etsu under the names KP-561® (CTFA name: acrylates/dimethicone), KP-541®, where the copolymer is dispersed at 60% by weight in isopropyl alcohol (CTFA name: acrylates/dimethicone and isopropyl alcohol), and KP-545®, where the copolymer is dispersed at 30% in cyclopentasiloxane (CTFA name: acrylates/dimethicone and cyclopentasiloxane).

According to a preferred embodiment of this disclosure, KP561® is preferably used; this copolymer is not dispersed in a solvent but is supplied in waxy form, its melting point being approximately 30 °C.

We can also mention the acrylic acid copolymer grafted by polydimethylsiloxane dissolved in isododecane sold by Shin-Etsu under the name KP-550®.

According to a particularly preferred form, a composition according to this disclosure comprises, as a hydrophobic film-forming polymer, at least one trimethylsiloxysilicate resin, such as those sold under the name SR1000® by General Electric, under the name TMS 803® by Wacker and under the names KF-7312®J by Shin-Etsu and DC 749® and DC 593® by Dow Corning.

IV. SILICONE POLYAMIDE COPOLYMERS

Silicone polyamides and their copolymers are preferably solid at room temperature (25 °C) and atmospheric pressure (760 mmHg).

The silicone polyamides in the composition of this disclosure may be polyorganosiloxane polymers, for example, those described in US-A-5,874,069, US-A-5,919,441, US-A-6,051,216, and US-A-5,981,680. According to this disclosure, the silicone polymers may belong to the following two families:

(1) polyorganosiloxanes including at least two amide groups, these two groups being located in the polymer chain, and/or (2) polyorganosiloxanes including at least two amide groups, these two groups being located on grafts or branches.

A) According to the first variant, silicone polymers are polyorganosiloxanes as defined above in which the motifs capable of establishing hydrogen interactions are located in the polymer chain.

Silicone polymers can be more specifically polymers comprising at least one motif corresponding to the general formula (I):

in which: G' represents C(O) when G represents -C(O)-NH-Y-NH-, and G' represents -NH- when G represents -NH-C(O)-YC(O)-, R4, R5, R6 and R7, which may be identical or different, represent a group chosen from: saturated or unsaturated, linear, branched or cyclic hydrocarbon groups in C1 to C40, which may contain in their chain one or more oxygen, sulfur and/or nitrogen atoms, and which may be partially or totally substituted by fluorine atoms, aryl groups in C6 to C10, optionally substituted by one or more alkyl groups in C1 to C4, polyorganosiloxane chains optionally containing one or more oxygen, sulfur and/or nitrogen atoms, the X groups, which may be identical or different, represent a linear or branched C1 to C30 alkylenediyl group, containing optionally in its chain one or more oxygen and/or nitrogen atoms, Y is a linear or branched C1-C50 saturated or unsaturated divalent alkylene, arylene, cycloalkylene, alkylarylene, or arylalkylene group, which may include one or more oxygen, sulfur, and/or nitrogen atoms, and/or may bear as a substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C3-C8 cycloalkyl, C1-C40 alkyl, C5-C10 aryl, phenyl optionally substituted by one to three C1-C3 alkyl, C1-C3 hydroxyalkyl, and C1-C6 aminoalkyl groups, or Y represents a group corresponding to the formula:

in which T represents a linear or branched hydrocarbon group, saturated or unsaturated, trivalent in C3 to C24 or tetravalent, optionally substituted by a polyorganosiloxane chain, and optionally containing one or more atoms selected from O, N, and S, or T represents a trivalent atom selected from N, P, and Al, and
R ⁸ represents a linear or branched C1-C50 alkyl group or a polyorganosiloxane chain, optionally comprising one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfamide groups, which may optionally be linked to another chain of the polymer, n is an integer from 2 to 500 and preferably from 2 to 200, and m is an integer from 1 to 1000, preferably from 1 to 700 and even better from 6 to 200. Preferably, m is an integer from 50 to 150.

According to one embodiment of this disclosure, 80% of the ^R4 , ^R5 , _R6 , and _R7 groups of the polymer are preferably selected from methyl, ethyl, phenyl, and 3,3,3-trifluoropropyl groups. According to another embodiment, 80% of the ^R4 , ^R5 , ^R6 , and ^R7 groups of the polymer are methyl groups.

According to this disclosure, Y can represent various divalent groups, furthermore, optionally including one or two free valences to establish bonds with other motifs of the polymer or copolymer. Preferably, Y represents a group selected from: linear alkylene groups in C1 to C20 and preferably alkylene groups in C1 to C10, branched alkylene groups in C30 to C56 optionally including non-conjugated rings and unsaturations, cycloalkylene groups in C5-C6, phenylene groups optionally substituted by one or more alkyl groups in C1 to C40, alkylene groups in C1 to C20 including 1 to 5 amide groups, alkylene groups in C1 to C20 including one or more substituents selected from hydroxyl groups, cycloalkane groups in C3 to C8, hydroxyalkyl groups in C1 to C3 and alkylamine groups in C1 to C6, polyorganosiloxane chains of formula:

Or

in which ^R4 , ^R5 , ^R6 , ^R7 , T and m are as defined above.

According to the second variant, polyorganosiloxanes can be polymers comprising at least one motif corresponding to formula (II):
(II)

in which ^R4 and ^R6 , which may be identical or different, are as defined above for formula (I), ^R10 represents a group as defined above for ^R4 and ^R6 , or represents a group of formula -XGR12 in which X and G are as defined above for formula (I) and ^R12 represents a hydrogen atom or a linear, branched, or cyclic, saturated or unsaturated hydrocarbon group, in C1-C50, optionally including in its chain one or ^more atoms selected from O, S, and N, optionally substituted by one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more alkyl groups in C1-C4, ^R11 represents a group of formula ^-XGR12 in which X, G, and ^R12 are as defined above, m1 is an integer from 1 to 998 and m2 is an integer ranging from 2 to 500.

According to this disclosure, the silicone polymer used as a structuring agent may be a homopolymer, i.e., a polymer comprising several identical motifs, in particular motifs of formula (I) or formula (II).

According to this disclosure, it is also possible to use a silicone polymer formed from a copolymer including several different motifs of formula (I), i.e. a polymer in which at least one of the groups R ⁴ , R ⁵ , R ⁶ , R ⁷ , X , G , Y , m and n is different in one of the motifs.

The copolymer can also be formed from several motifs of formula (II), in which at least one of the elements ^R4 , ^R6 , ^R10 , ^R11 , _m1 and _m2 is different in at least one of the motifs.

It is also possible to use a polymer including at least one formula motif (I) and at least one formula motif (II), the formula motifs (I) and the formula motifs (II) optionally being identical or different from each other.

According to one embodiment of this disclosure, it is also possible to use a polymer further comprising at least one hydrocarbon-based motif comprising two groups capable of establishing hydrogen interactions, selected from the ester, amide, sulfamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.

These copolymers can be sequenced or grafted polymers.

According to an advantageous embodiment of this disclosure, the groups capable of establishing hydrogen interactions are amide groups of formulas -C(O)NH- and -HN-C(O)-.

The amount of hydrophobic silicone film-forming polymer present in the composition, according to the embodiments herein, may vary. The hydrophobic silica aerogel, according to the embodiments herein, may be present in the composition in a weight range of 1% to 4.9%, preferably in a weight range of 1% to 4%, and more preferably from 1% to 3% relative to the total weight of the composition.

Hydrophobic silica aerogel

The oily phase of the composition according to the embodiments herein includes at least one hydrophobic silica aerogel.

The term "aerogels" refers to ultralight porous materials, first produced by Kristler in 1932.

The term "hydrophobic silica" refers to both pure hydrophobic silicas and particles that are entirely or partially coated with hydrophobic silica.

According to the embodiments shown here, the hydrophobic silicas are preferably amorphous and of sublimed origin. They are preferably supplied in powder form.

Amorphous hydrophobic silicas of sublimed origin are generally obtained from hydrophilic sublimed silicas. Hydrophilic sublimed silicas are produced by pyrolysis of silicon tetrachloride ( _SiCl₄ ) in a continuous flame at 1000 °C in the presence of hydrogen and oxygen. They are then rendered hydrophobic, for example, by treatment with halogenated silanes, alkoxysilanes, or silazanes. Hydrophobic silicas differ from the original hydrophilic silicas, among other things, by a lower density of silanol groups and by less water vapor adsorption.

Hydrophobic groups can be trimethylsiloxyl groups, which are obtained in particular by treating sublimed silica in the presence of hexamethyldisilazane, or dimethylsiloxyl groups, which are obtained in particular by treating sublimed silica in the presence of dimethyldichlorosilane.

In one embodiment of this disclosure, the composition comprises hydrophobically treated sublimated silicas, also known as hydrophobic silica aerogel.

In another embodiment of this disclosure, hydrophobic silica aerogel is preferably silylated silica aerogel particles (INCI name: Silica Silylate).

It will also be possible to use hydrophobic silica aerogel particles modified on the surface with trimethylsilyl groups, namely trimethylsiloxylated silica particles.

The hydrophobic silica aerogel particles that may be used in this disclosure preferably have a size, expressed as mean diameter (D[0,5]), of less than 1500 µm, and preferably in a range of 1 µm to 30 µm, more preferably from 2 µm to 25 µm, better still from 2 µm to 20 µm and even better from 2 µm to 15 µm.

Preference may be given to aerogel sold under the name VM-2270® (INCI name: Silica Silylate), by the company Dow Corning, whose particles have an average size ranging from 5 to 15 microns and a specific surface area per unit mass ranging from 600 ^m² /g to 800 ^m² /g.

As examples of hydrophobic silica aerogels that may be used in this disclosure, mention may also be made of the aerogel sold under the name VM-2260® (INCI name: Silica Silylate), by the company Dow Corning, whose particles have an average size of approximately 1000 microns and a specific surface area per unit mass ranging from 600 ^m² /g to 800 ^m² /g.

As hydrophobic silica aerogels that may be used in this disclosure, we may also mention the aerogels sold by Cabot under the references Aerogel TLD 201®, Aerogel OGD 201® and Aerogel TLD 203®, Enova Aerogel MT 1100® and Enova Aerogel MT 1200, as well as the references Airlica TL3® and Airlica TL5® sold by Toyukama.

The amount of hydrophobic silica aerogel present in the composition, according to the embodiments herein, may vary. The hydrophobic silica aerogel, according to the embodiments herein, may be present in the composition in a weight range of 1% to 5%, preferably in a weight range of 1% to 3%, and more preferably from 1% to 2% relative to the total weight of the composition.

silicone emulsifier

The oily phase of the composition according to the embodiments herein includes at least one silicone emulsifier having an HLB of less than 8.

The term "silicone emulsifier" refers to a compound that stabilizes the silicone-rich oil phase of water-in-oil emulsions. Furthermore, silicone emulsifiers are amphiphilic, meaning they have two parts with different polarities. Typically, one part is lipophilic (soluble or dispersible in an oil phase), and the other is hydrophilic (soluble or dispersible in water). Silicone emulsifiers are characterized by their HLB (hydrophilic-lipophilic balance) value, where HLB is the ratio of the hydrophilic to the lipophilic parts in the molecule. The term "HLB" is well-known to those skilled in the art and is described, for example, in "The HLB System: A Time-Saving Guide to Emulsifier Selection" (published by ICI Americas Inc., 1984). For silicone emulsifiers, the HLB is generally less than 8 and should be between 3 and 8 for the preparation of water-in-oil emulsions. The HLB of the emulsifier(s) used according to this disclosure can be determined by the Griffin method or the Davies method.

According to embodiments shown here, silicone emulsifiers are chosen from polyether, polyglycerin-modified silicones, silicone elastomers or mixtures thereof.

Examples of polyethers include polyalkylene glycols, preferably polyethylene glycols.

Examples of silicone emulsifiers include silicone surfactants, such as dimethicone copolyols, such as those with INCI name dimethicone (and) PEG/PPG-18/18 dimethicone sold under the brand name X-22-6711D® by Shin-Etsu, the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C® by Dow Corning, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning; a cetyl dimethicone copolyol, such as cetyl PEG/PPG-10/1 dimethicone, such as the product sold under the name Abil EM 90® by the company Evonik Goldschmidt, and the mixture of cetyl dimethicone copolyol, polyglyceryl isostearate (4 mol) and hexyl laurate, sold under the name Abil WE 09® by the company Goldschmidt.

One or more co-emulsifiers may also be added, which can advantageously be chosen from the group comprising alkyl polyol esters. Other examples include non-silicone emulsifiers, particularly alkyl esters or ethers of sorbitan, glycerol, polyol, or sugars. Examples of alkyl polyol esters include polyethylene glycol esters, such as PEG-30 dipolyhydroxystearate, such as the product sold under the name Cithrol DPHS-SO-(MV) by Croda.

Examples of glycerol and/or sorbitan esters include polyglyceryl isostearate, such as the product sold under the name Isolan GI 34® by Evonik Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by ICI; the diester of a mixture of isostearic, polyhydroxystearic and sebacic acids with polyglycerin-4 (INCI name: polyglycery diisostearate/ polyhydroxystearate/ sebacate), such as the product sold under the name Isolan GPS® by Evonik; and mixtures thereof.

In some embodiments of this disclosure, silicone emulsifiers may be selected from emulsifying silicone elastomers.

1. Elastomères de silicone polyoxyalkylénés

The term "silicone elastomer" refers to a flexible and deformable organopolysiloxane with viscoelastic properties, particularly the consistency of a sponge or a soft sphere. Its modulus of elasticity is such that this material resists deformation and exhibits limited extensibility and contractility. This material is capable of returning to its original shape after stretching. The emulsifying silicone elastomer can be selected from polyoxyalkylated silicone elastomers and polyglycerol silicone elastomers, or mixtures thereof.

1. Polyoxyalkylated silicone elastomers

Polyoxyalkylated silicone elastomer is a crosslinked organopolysiloxane that can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and a polyoxyalkylene containing at least two ethylenically unsaturated groups.

Preferably, the polyoxyalkylened crosslinked organopolysiloxane is obtained by a crosslinking addition reaction (A1) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B1) of polyoxyalkylene containing at least two ethylenically unsaturated groups, particularly in the presence (C1) of a platinum catalyst, as described, for example, in US patents 5,236,986 and 5,412,004.

In particular, organopolysiloxane can be obtained by reaction of polyoxyalkylene (in particular polyoxyethylene and/or polyoxypropylene) terminated by dimethylvinylsiloxy and methylhydropolysiloxane terminated by trimethylsiloxy, in the presence of a platinum catalyst.

The organic groups bonded to the silicon atoms of the compound (A1) may be alkyl groups containing 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl (or lauryl), myristyle, cetyl, or stearyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group.

Compound (A1) can therefore be chosen from trimethylsiloxy-terminate methyl hydro polysiloxane copolymers, trimethylsiloxy-terminate dimethyl siloxane/methyl hydrosiloxane copolymers, cyclic dimethyl siloxane/methyl hydro siloxane copolymers and dimethyl siloxane/methyl hydrosiloxane/laurylmethyl siloxane copolymers terminated by trimethyl siloxy.

Compound (C1) is the catalyst for the crosslinking reaction, and is notably chosen from chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and platinum on a support.

Advantageously, polyoxyalkylated silicone elastomers can be formed from divinylic compounds, in particular polyoxyalkylenes containing at least two vinyl groups, reacting with the Si-H bonds of a polysiloxane.

The polyoxyalkylated silicone elastomer described in this disclosure is preferably mixed with at least one hydrocarbon oil and/or silicone oil to form a gel. In these gels, the polyoxyalkylated elastomer may be in the form of non-spherical particles. Polyoxyalkylated elastomers are described in particular in US patents 5,236,986, 5,412,004, 5,837,793, and 5,811,487.

Examples of polyoxyalkylated silicone elastomers include those with the following INCI names: dimethicone/PEG-10/15-crosspolymer, PEG-15/Lauryl dimethicone crosspolymer, PEG-10/lauryl dimethicone crosspolymer, PEG-12 dimethicone Crosspolymer, PEG-10 dimethicone crosspolymer, PEG-10 dimethicone/Vinyldimethicone crosspolymer, PEG-12 dimethicone/PPG-20 Crosspolymer, and their mixtures.

They are notably sold under the names KSG® by the company Shin-Etsu: KSG-210® (INCI name: dimethicone and dimethicone/PEG-10/15-crosspolymer; INCI name KSG-310®: PEG-15/lauryl dimethicone crosspolymer and mineral oil; KSG-320® INCI name: PEG-15/lauryl dimethicone crosspolymer and isododecane; KSG-330® INCI name: PEG-15/lauryl dimethicone crosspolymer and triethylhexanoin; KSG-340® INCI name: squalane and PEG-15/lauryl dimethicone crosspolymer.

They are notably sold by the company Dow Corning under the name Dow Corning 9011 Silicone Elastomer Blend ®; INCI name: cyclopentasiloxane and PEG-12 dimethicone crosspolymer.

We can also mention the product sold under the name Dow Corning EL7040 Hydro Elastomer Blend ® by the company Dow Corning for the compound which has the INCI name: PEG-12 dimethicone/PPG-20 crosspolymer.

Polyglycerol-coated silicone elastomers

Polyglycerol silicone elastomer is a crosslinked organopolysiloxane elastomer that can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and polyglycerol compounds containing ethylenically unsaturated groups, particularly in the presence of a platinum catalyst.

Preferably, the crosslinked organopolysiloxane elastomer is obtained by a crosslinking addition reaction (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) of glycerol compounds containing at least two ethylenically unsaturated groups, particularly in the presence (C) of a platinum catalyst.

In particular, organopolysiloxane can be obtained by reacting a dimethylvinylsiloxy-terminated polyglycerol compound with a trimethylsiloxy-terminated methylhydropolysiloxane in the presence of a platinum catalyst. Compound (A) is the basic reagent for the formation of the organopolysiloxane elastomer, and crosslinking is carried out by adding compound (A) to compound (B) in the presence of catalyst (C).

Compound (A) is in particular an organopolysiloxane containing at least two hydrogen atoms bonded to different silicon atoms in each molecule. Compound (A) can have any molecular structure, in particular a linear-chain, branched-chain, or cyclic structure.

Compound (A) may have a viscosity at 25 °C ranging from 1 to 50,000 centistokes, in particular so as to be easily miscible with compound (B).

The organic groups bonded to the silicon atoms of compound (A) may be alkyl groups containing from 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl (or lauryl), myristyle, cetyl, or stearyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. Preferably, said organic group is selected from among the methyl, phenyl, and lauryl groups.

Compound (A) can therefore be chosen from trimethylsiloxy-terminated methylhydropolysiloxane copolymers, trimethylsiloxane-terminated dimethylsiloxane/methylhydrosiloxane copolymers, dimethylsiloxane/methylhydrosiloxane cyclic copolymers, and trimethylsiloxane-terminated dimethylsiloxane/methylhydrosiloxane/laurylmethylsiloxane copolymers.

Compound (B) may be a polyglycerol compound corresponding to the formula (B') below:

C _m H _2m-1 -O-[ Gly] _n -C _m H _2m-1 (B')

in which m is an integer from 2 to 6, n is an integer from 2 to 200, preferably from 2 to 100, preferably from 2 to 50, more preferably from 2 to 20, always more preferably from 2 to 10, and always more preferably from 2 to 5, and in particular n is equal to 3; and Gly denotes: -CH ₂ -CH(OH)-CH ₂ -O- or -CH ₂ -CH(CH ₂ OH)-O.

Advantageously, the sum of the number of ethylenic groups per molecule of compound (B) and the number of hydrogen atoms bonded to silicon atoms per molecule of compound (A) is at least 4.

It is advantageous that compound (A) be added in such an amount that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in compound (A) and the total amount of all ethylenically unsaturated groups in compound (B) is in the range of 1:1 to 20:1.

Compound (C) is the catalyst for the crosslinking reaction, in particular chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and platinum on a support.

The catalyst (C) is preferably added in an amount of 0.1 to 1,000 parts by weight, and better still of 1 to 100 parts by weight, as clean platinum metal, for 1,000 parts by weight of the total amount of compounds (A) and (B).

The polyglycerol silicone elastomer according to this disclosure is generally mixed with at least one hydrocarbon oil and/or silicone oil to form a gel.

In these gels, the polyglycerol elastomer is often present in the form of non-spherical particles.

These elastomers are described in particular in patent application WO 2004/024798.

The following compounds with INCI names can be used as polyglycerol silicone elastomers: dimethicone/polyglycerin-3 crosspolymer, lauryl dimethicone/polyglycerin-3 crosspolymer, and their mixtures.

They are notably sold by the company Shin-Etsu under the following names: KSG-710®; INCI name: dimethicone/polyglycerin-3 crosspolymer and dimethicone; KSG-810®; INCI name: Mineral Oil and Lauryl dimethicone/polyglycerin-3 crosspolymer; KSG-820®; INCI name: isododecane and lauryl dimethicone/polyglycerin-3 crosspolymer; KSG-830®; INCI name: triethylhexanoin and lauryl dimethicone/polyglycerin-3 crosspolymer; KSG-840®; INCI name: squalane and lauryl dimethicone/polyglycerin-3 crosspolymer.

In one embodiment, the silicone emulsifiers are preferably selected from cetyl polyethylene glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone, polyglyceryl-4 isostearate, PEG-10 dimethicone, PEG-20, or mixtures thereof; more preferably, it is a combination of cetyl polyethylene glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone, polyglyceryl-4 isostearate, PEG-10 dimethicone and PEG-20.

The amount of silicone emulsifier in the composition, according to the embodiments described herein, may vary. The silicone emulsifier, according to the embodiments described herein, may be present in the composition in a weight range of 5% to 30%, preferably in a weight range of 8% to 15%, and more preferably from 8% to 10% relative to the total weight of the composition.

Pigment

The oily phase of the composition according to the embodiments here includes at least one pigment.

The term "pigments" is used to refer to white or colored particles, mineral or organic, insoluble in an aqueous medium, intended to color and/or opacify the composition and/or the resulting deposit. These pigments can be white or colored, mineral and/or organic.

Pigments can be chosen from mineral pigments, organic pigments, pearlescent pigments, or mixtures thereof.

In one embodiment of this disclosure, the pigment is chosen from mineral pigments.

The term "mineral pigment" refers to any pigment meeting the definition in Ullmann's Encyclopedia in the chapter on inorganic pigments. Examples of mineral pigments suitable for use in this disclosure include zirconium or cerium oxides, as well as zinc, iron (black, yellow, or red), or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metallic powders such as aluminum powder and copper powder. Mineral pigments such as _Ta₂O₅ , _Ti₃O₅ , _Ti₂O₃ , _TiO , _{and ZrO₂} mixed with _TiO₂ , _ZrO₂ , _Nb₂O₅ , _CeO₂ , _{and ZnS} may also be used in the composition of this disclosure.

The pigment size suitable for use in this disclosure is generally in a range of 0.1 μm to 10 μm, preferably in a range of 0.2 μm to 5 μm, more preferably in a range of 0.3 μm to 1 μm.

In one embodiment of this disclosure, the pigments have a size characterized by a D[50] in a range of 0.1 μm to 10 μm, preferably in a range of 0.2 μm to 5 μm, more preferably in a range of 0.3 μm to 1 μm.

D[50] refers to the median particle size and represents the maximum size that 50% by volume of the particles exhibit.

In one embodiment of this disclosure, the mineral pigment includes a lipophilic or hydrophobic coating.

In one or more embodiments of this disclosure, the pigments may be coated with at least one compound selected from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl tristearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; silicone surfactants such as organopolysiloxanes, alkylalkoxysilanes such as triethoxycaprylylsilane; fluorinated surfactants such as perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups; Fluorosilicone surfactants such as perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialcoxysilanes; and mixtures thereof.

In another embodiment of this disclosure, the pigments may be coated with an N-acylated amino acid or a salt thereof, which may include an acyl group having 8 to 22 carbon atoms, such as a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group. The amino acid could be, for example, lysine, glutamic acid, or alanine. The salts of these compounds could be aluminum, magnesium, calcium, zirconium, zinc, sodium, or potassium salts.

In yet another embodiment of this disclosure, the pigments may be coated with an N-acylated amino acid derivative, preferably a glutamic acid derivative and/or a salt thereof, more preferably a stearoyl glutamate, such as aluminum stearoyl glutamate.

Examples of pigments treated with aluminum stearoyl glutamate include titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the trade name NAI® by the company MIYOSHI KASEI.

According to the embodiments shown here, the pigments can be coated with isopropyl triisostearyl titanate. Examples of pigments treated with isopropyl titanium triisostearate (ITT) include those sold under the trade reference BWBO-I2® (iron oxide CI77499 and isopropyl titanium triisostearate), BWYO-I2® (iron oxide CI77492 and isopropyl titanium triisostearate) and BWRO-I2® (iron oxide CI77491 and isopropyl titanium triisostearate) by the company KOBO.

The pigments that may be used according to this disclosure may also be organic pigments.

The term "organic pigment" refers to any pigment that meets the definition in Ullmann's encyclopedia in the chapter on organic pigments. Organic pigments can include, among others, nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex compounds, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, or quinophthalone.

The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the color index under references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments coded in the color index under references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments coded in the color index under references CI 61565, 61570 and 74260, orange pigments coded in the color index under references CI 11725, 15510, 45370, and 71105, red pigments coded in the color index under references CI 12085, CI 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, and 75470, and pigments obtained by oxidative polymerization of indole derivatives or phenolic as described, for example, in French patent no. 2679 771.

These pigments can also take the form of composite pigments as described in patent EP1184426. These composite pigments can be composed in particular of particles comprising an inorganic core covered at least partially with an organic pigment and at least one binder ensuring the fixation of the organic pigments on the core.

The pigment can also be a lacquer. The term "lacquer" is used to refer to insolubilized tints adsorbed onto insoluble particles; the resulting mixture remains insoluble during use.

Examples of inorganic substrates on which tints are adsorbed include alumina, silica, calcium sodium borosilicate, or calcium aluminum borosilicate.

Organic dyes include cochineal carmine. Other examples include products known by the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 (CI 77 002), D&C Green 3 (CI 42 053) and D&C Blue 1 (CI 42 090).

Examples of lacquers include the product known as D&C red 7 (CI 15 850 :1).

Pearlescent materials can be chosen from white pearlescent pigments such as titanium-coated mica or bismuth oxychloride, coloured pearlescent pigments such as titanium mica with iron oxides, titanium mica with, in particular, ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type, as well as pearlescent pigments based on bismuth oxychloride.

Preferably, the composition according to this disclosure comprises at least one mineral-type pigment, in particular selected from metal oxides, and more particularly selected from titanium dioxide, iron oxides, more preferably selected from titanium dioxide comprising a lipophilic or hydrophobic coating, iron oxides comprising a lipophilic or hydrophobic coating, and mixtures thereof,

More specifically, the composition according to this disclosure includes at least one pigment selected from titanium dioxides, iron oxides and mixtures thereof, said metal oxides being coated with an N-acylated amino acid derivative, in particular a glutamic acid derivative and/or a salt thereof, and more specifically a stearoyl glutamate, such as aluminum stearoyl glutamate.

In one embodiment of this disclosure, the pigment is preferably selected from anatase titanium dioxide coated with aluminum stearoyl glutamate (hydrophobic), yellow iron oxide treated with disodium stearoyl glutamate (hydrophobic), red iron oxide treated with disodium stearoyl glutamate (hydrophobic), black iron oxide treated with disodium stearoyl glutamate (hydrophobic), or mixtures thereof.

The amount of pigment in the composition, according to the embodiments presented here, may vary. The pigment, according to the embodiments presented here, may be present in the composition in a weight range of 4% to 25%, preferably in a weight range of 7% to 15%, and more preferably from 8% to 10% relative to the total weight of the composition.

Aqueous phase

The composition according to the embodiments here includes an aqueous phase.

The term “aqueous phase” refers to a phase containing water and optionally other water-soluble or water-miscible ingredients.

The aqueous phase includes water.

The aqueous phase comprises water in a weight range of 20% to 70%, preferably in a weight range of 25% to 50%, and more preferably in a weight range of 28% to 32% relative to the total weight of the composition.

cosmetic compositions

This disclosure also relates to a cosmetic composition comprising, in a physiologically acceptable medium, a composition as defined above.

The physiologically acceptable medium is generally adapted to the nature of the substrate on which the composition is to be applied, as well as to the appearance in which the composition is to be packaged.

Additives

• les charges ;
• les agents gélifiants ;
• les conservateurs ;
• les solvants ;
• les sels ;
• et leurs mélanges.

The compositions described in this disclosure may also include additives commonly used in skincare and/or makeup products such as:

• the charges;
• gelling agents;
• the conservatives;
• solvents;
• salts;
• and their mixtures.

It is understood that a person skilled in the art will take care to select any optional additional additives and/or their quantity in such a way that the advantageous properties of the composition used according to the disclosure are not, or are not materially, adversely affected by the contemplated addition. All such embodiments, including the optional additives, are understood to be included within the scope of this disclosure.

Charges

The composition, according to the embodiments herein, includes at least one filler, other than hydrophobic silica aerogel particles, which provides complementary properties of matte finish, coverage, hold and/or improved stability.

The term "charge" is used to refer to colorless or white, solid particles of any shape, which are in an insoluble form and dispersed in the medium of the composition.

The fillers can be inorganic or organic.

According to the embodiments here, the loads are preferably chosen from natural loads or loads of natural origin.

The term “natural charge” refers to a compound obtained directly from the earth or soil, or from plants or animals, by means, where appropriate, of one or more physical processes, such as grinding, refining, distillation, purification or filtration.

The term "naturally derived ingredient" refers to a natural compound that has undergone one or more chemical or industrial treatments, resulting in modifications that do not affect the essential qualities of that compound and/or of a compound primarily composed of natural constituents, whether processed or not. Non-limiting examples of chemical or industrial treatments that result in modifications not affecting the essential qualities of a natural compound include those authorized by certification bodies such as Ecocert (Standards for Organic and Ecological Cosmetic Products, January 2003) or defined in recognized manuals in the field, such as "Cosmetics and Textiles Magazine," 2005, vol. 120, 9: 10.

In some embodiments of this disclosure, the fillers used may be of lamellar, globular, spherical, fibrous shape or any other intermediate shape between these defined shapes.

In some embodiments of this disclosure, the fillers may or may not be surface coated, and in particular they may be surface treated with amino acids, or any other substance, which promotes the dispersion and compatibility of the filler in the composition.

Mineral fillers

According to the embodiments herein, examples of mineral fillers include, but are not limited to, talc, natural or synthetic micas such as synthetic fluorphlogopites, silica, hollow silica microspheres, kaolin, calcium and magnesium carbonate, hydroxyapatite, boron nitride, bismuth oxychloride, glass, perlite or ceramic microcapsules, silica and titanium dioxide composites, such as the TSG® range marketed by Nippon Sheet Glass.

Organic charges

Examples of organic fillers include, but are not limited to, natural micronized waxes; metallic soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate; lauroyl lysine, cellulose powders such as those marketed by Daito in the Cellulobeads® range.

In one embodiment of this disclosure, the filler is a mineral filler, preferably selected from talcs.

The quantity of fillers present in the composition, according to the embodiments herein, may vary. The additional filler, according to the embodiments herein, may be present in the composition in a weight range of 1% to 10%, preferably in a weight range of 5% to 8%, and more preferably 7% to 8% relative to the total weight of the composition.

Gelling agents

The composition, according to the embodiments herein, includes one or more hydrophilic gelling agents, namely: soluble in water or dispersible in water and/or one or more lipophilic agents, namely: gelling agents soluble in oil or dispersible in oil, which provide the desired viscosity to the composition.

Hydrophilic gelling agents and/or lipophilic gelling agents are preferably chosen from natural gelling agents or from gelling agents of natural origin.

Examples of hydrophilic gelling agents include, but are not limited to, polysaccharide biopolymers such as starch, xanthan gum, guar gum, locust bean gum, acacia gum, scleroglucans, chitin and chitosan derivatives, carrageenans, gellans, alginates, celluloses such as cellulose gums, microcrystalline cellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose and mixtures thereof.

Lipophilic clays are examples of lipophilic gelling agents.

Lipophilic clay

According to embodiments herein, the composition of this disclosure further contains at least one lipophilic clay.

The term “lipophilic clay” is used to designate any fat-soluble or fat-dispersible clay in the oily phase of the composition, in which the term “clay” refers to a material based on hydrated silicates and/or aluminosilicates with a lamellar structure.

Clays can be natural or synthetic, and they are made lipophilic by treatment with an alkylammonium salt, such as a C10 to C22 ammonium chloride, in particular stearalconium chloride or distearyl dimethyl ammonium chloride.

In some embodiments of this disclosure, the clay may be selected from a group consisting of bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

In one embodiment of this disclosure, the gelling agent is a lipophilic gelling agent and is selected from hectorites and bentonites.

In another embodiment of this disclosure, the lipophilic clay is preferably selected from hydrophobic modified bentonites and hydrophobic modified hectorites, in particular by a C10 to C22 quaternary ammonium chloride, such as: a bentonite modified with stearalconium chloride, such as the commercial products sold under the name CLAYTONE AF®, GARAMITE VT®, TIXOGEL® LG-M, TIXOGEL® MP 250, TIXOGEL® VZ, TIXOGEL® VZ-V XR, by BYK Additives Inc; the commercial products marketed under the name VISCOGEL® B3, VISCOGEL® B4, VISCOGEL® B7, VISCOGEL® B8, VISCOGEL® ED, VISCOGEL® GM, VISCOGEL® S4, VISCOGEL® SD by Bentec S.P.A.; a bentonite modified with stearalconium chloride in the presence of at least propylene carbonate and at least one oil such as the commercial products DUB VELVET GUM® from STEARINERIE DUBOIS FILS, MYGLYOL GEL T® from Cremer Oleo, TIXOGEL® CGT 6030, TIXOGEL® DBA 6060, TIXOGEL® FTN, TIXOGEL® FTN 1564, TIXOGEL® IPM, TIXOGEL® LAN, TIXOGEL® LAN 1563 from BYK Additives Inc; a hectorite modified with distearyl dimethylammonium chloride (INCI name: disteardimonium hectorite) such as, for example, those marketed under the name BENTONE® 38V by Elementis Specialities; a hectorite modified by distearyl dimethylammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil, such as the commercial products sold under the name BENTONE® GEL DOA V, BENTONE® GEL EUG V, BENTONE® GEL IHD V, BENTONE® GEL ISD V, BENTONE® GEL MIO V® BENTONE® GEL PTM V® BENTONE® SS-71 V, BENTONE® VS-5 PC V, BENTONE® VS-5 by Elementis Specialities; the commercial products sold under the name CREAGEL BENTONE CPS/HECTONE CPS, CREAGEL BENTONE ID/HECTONE ID by the company Créations Couleurs; the commercial products sold under the name NS GEL DM1®, NS GEL PTIS®, NS MGEL 1152® by the company Next Step Laboratories Stop.

The quantity of hydrophilic and/or lipophilic gelling agent(s) present in the composition, according to the embodiments described herein, may vary. The hydrophilic and/or lipophilic gelling agent(s), according to the embodiments described herein, may be present in the composition in a weight range of 0.5% to 10%, preferably in a weight range of 0.5% to 6%, and more preferably from 0.5% to 2% relative to the total weight of the composition.

Solvents

The composition, according to the embodiments herein, includes one or more solvents, which are used to facilitate the deposition of ingredients of the composition onto the keratinous material.

According to embodiments herein, the solvent is a volatile solvent, soluble in water and forms part of the aqueous phase of the composition.

The term "water-soluble solvent" used here refers to a compound that is liquid at room temperature and miscible with water (miscibility with water greater than 50% by weight at 25°C and atmospheric pressure).

Examples of water-soluble solvents that may be appropriately used in the formulation in accordance with this disclosure include lower monoalcohols having 1 to 5 carbon atoms, such as ethanol and isopropanol; glycols having 2 to 8 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, propanediol, pentylene glycol, glycerol and dipropylene glycol; C3-C4 ketones; and C2-C4 aldehydes.

The quantity of solvents present in the composition, according to the embodiments herein, may vary. The solvents, according to the embodiments herein, may be present in the composition in a weight range of 1% to 15%, preferably in a weight range of 3% to 10%, and more preferably from 4% to 6% relative to the total weight of the composition.

Salts

The composition, according to the embodiments here, includes one or more salts, which are used to stabilize the water-in-oil emulsion.

According to the embodiments presented here, the salt is inorganic and forms part of the aqueous phase of the composition.

Examples of salts include, but are not limited to, magnesium sulfate, sodium chloride, potassium chloride, or mixtures thereof.

The amount of salt in the composition, according to the embodiments presented here, may vary. Salts, according to the embodiments presented here, may be present in the composition in a weight range of 1% to 5%, preferably in a weight range of 1% to 3%, and more preferably from 0.5% to 2% relative to the total weight of the composition.

Conservatives

The composition, according to the embodiments described herein, includes one or more preservatives, which are used to preserve the integrity and stability of cosmetic products that can be damaged by microorganisms. Preservatives are essential to ensure consumer safety and extend the shelf life of the cosmetic product. Examples of preservatives include, but are not limited to, phenoxyethanol, ethylhexylglycerin, or mixtures thereof.

The quantity of preservatives in the composition, according to the embodiments herein, may vary. The preservatives, according to the embodiments herein, may be present in the composition in a weight range of 0.1% to 3%, preferably in a weight range of 0.2% to 2%, and more preferably from 0.3% to 1% relative to the total weight of the composition.

Other additives

The composition also includes additives, such as perfumes, additional coloring materials and mixtures thereof.

Additional coloring agents

The composition according to the embodiments herein may further comprise at least one additional water-soluble or fat-soluble colorant, preferably in a weight range of at least 0.01% relative to the total weight of the composition.

For obvious reasons, this quantity is likely to vary significantly with respect to the intensity of the desired color effect and the color intensity provided by the coloring materials considered, and its adjustment clearly falls within the competence of a person skilled in the art.

In some embodiments of this disclosure, the additional colorants may be fat-soluble.

The term "liposoluble coloring matter" is used to designate any compound, generally organic, natural or synthetic, soluble in an oily phase or in solvents miscible with a fatty substance and suitable for coloring.

Examples of suitable fat-soluble tints for the disclosed composition include, but are not limited to, synthetic or natural fat-soluble tints such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red, carotene (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan Brown, quinoline yellow, annatto, curcumin.

In some embodiments of this disclosure, the additional colorants may be water-soluble.

The term "water-soluble coloring matter" is used to refer to any compound, generally organic, natural or synthetic, that is soluble in an aqueous phase or in solvents miscible in water and capable of coloring.

Examples of water-soluble tints include, but are not limited to, synthetic or natural water-soluble tints such as, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beetroot), carmine, copper chlorophyll, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, or riboflavin.

Preparation of compositions according to disclosure

The compositions disclosed can be prepared using known processes, generally used in the cosmetic or dermatological fields. Typically, the process involved adding a volatile silicone oil, a silicone emulsifier, a non-volatile hydrocarbon oil, and a pigment to a beaker and homogenizing them at 8000 rpm for 45 minutes to obtain a first mixture. A premix of a hydrophobic film-forming polymer and a volatile hydrocarbon oil, along with water, was added to the first mixture and homogenized at 6500 rpm for 15 minutes to obtain a second mixture. A hydrophobic silica aerogel, one or more additives, and a solvent were added to the second mixture, followed by homogenization at 3500 rpm for 3 to 4 minutes to obtain the composition.

Applications

A composition, according to the embodiments described herein, may be, more specifically, a composition for coating keratinous material such as skin. Preferably, the composition, according to the embodiments described herein, is a makeup and/or skincare composition. Therefore, the composition, in various embodiments described herein, may be in the form of a makeup base composition. Preferably, the composition is in the form of a foundation, more preferably a liquid foundation. The composition, according to the embodiments described herein, may optionally be applied to the skin with an applicator, and then worked to form a coating on the skin.

Although this disclosure has been described in great detail with reference to certain embodiments and their implementations, other embodiments are possible to cover modifications and variations to this disclosure.

Examples

The disclosure will now be illustrated by practical examples, which are intended to demonstrate how the disclosure works and are not intended to impose restrictive limitations on the scope of this disclosure. Unless otherwise defined, all technical and scientific terms used in this document have the same meaning as that commonly understood by a person skilled in the art relevant to this disclosure. Although processes and materials similar or equivalent to those described herein may be used in the practice of the disclosed processes and compositions, examples of such processes, devices, and materials are described herein. It should be understood that this disclosure is not limited to the particular processes and experimental conditions described, as these processes and conditions may be applicable.

The quantities of ingredients are indicated in the following examples as percentages by weight of active ingredient.

EXAMPLE 1 Preparation of compositions

The compositions C(1a), C(1b), C(2), C(3), C(4), C(5), C(6), C(7) and C(8) listed in Table 1 were prepared as described below.

A volatile silicone oil, a silicone emulsifier, a non-volatile hydrocarbon oil, and a pigment were added to a master beaker and homogenized at 8000 rpm for 45 minutes to obtain a first mixture. An additive, such as a gelling agent, was added to the first mixture and dispersed at 8000 rpm for 25 minutes. A hydrophobic silicone film-forming polymer was premixed with a volatile hydrocarbon oil and added to the first mixture. Water was then added to the first mixture and homogenized at 6500 rpm for 15 minutes to obtain a second mixture. Hydrophobic silica aerogel, along with a filler, preservatives, a salt, and a solvent, was added to the second mixture and homogenized at 3500 rpm for 3 to 4 minutes to obtain the final composition.

Phase Ingredients
INCI Name Content (% by weight relative to the total weight of the composition) C(1a) C(1b) C(2) C(3) C(4) C(5) C(6) C(7) C(8) HAS Dimethicone 2cSt (volatile silicone oil) 15 15 15 15 15 15 15 15 15 HAS Peg cetyl/ppg-10/1 dimethicone (silicone emulsifier) 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 HAS Polyglyceryl-4 isostearate (silicone emulsifier) 1 1 1 1 1 1 1 1 1 HAS PEG-10 dimethicone (silicone emulsifier) 3 3 3 3 3 3 3 3 3 B Octocrylene (non-volatile hydrocarbon oil) 4 4 4 4 4 4 4 0 4 B Isononyl isonanoate (non-volatile hydrocarbon oil) 5 5 5 5 5 5 5 0 5 B Phenyl trimethicone 0 0 0 0 0 0 0 9 0 B Trimethylsiloxysilicate (hydrophobic silicone film-forming polymer) 1 1 2 4 0.5 0.1 1 1 5.2 C Titanium dioxide (and) disodium stearoyl glutamate (and) aluminum hydroxide (pigment) 8.2 7.89 8.2 8.2 8.2 8.2 8.2 8.2 8.2 C Iron oxides (and) disodium stearoyl glutamate (and) aluminum hydroxide (pigment) 1.35 1.69 1.35 1.35 1.35 1.35 1.35 1.35 1.35 C Iron oxides (and) disodium stearoyl glutamate (and) aluminum hydroxide (pigment) 0.33 0.28 0.33 0.33 0.33 0.33 0.33 0.33 0.33 C Iron oxides (and) disodium stearoyl glutamate (and) aluminum hydroxide (pigment) 0.12 0.15 0.12 0.12 0.12 0.12 0.12 0.12 0.12 D Disteardimonium hectorite (gelling agent) 1 1 1 1 1 1 1 1 1 E Water (aqueous phase) 29.6 29.59 28.6 26.6 30.1 30.5 30.53 29.6 25.4 E PEG-20 (silicone emulsifier) 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 E Ethylhexylglycerin (preservative) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E Magnesium sulfate (salt) 1 1 1 1 1 1 1 1 1 E Phenoxyethanol (preservative) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 F1 Silica silylate (hydrophobic silica aerogel) 1.5 1.5 1.5 1.5 1.5 1.5 0.57 1.5 1.5 F2 Talc (filler) 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 F3 Isododecane (volatile hydrocarbon oil) 10 10 10 10 10 10 10 10 10 F4 Alcohol denatured (solvent) 5 5 5 5 5 5 5 5 5 Total 100 100 100 100 100 100 100 100 100

EXAMPLE 2 Measurement and evaluation methods

Compositions C(1) to C(8) as prepared in Example 1 above were evaluated with respect to their stability characteristics, viscosity, durability, and sensory aspects.

Stability assessment

The stability of the compositions was evaluated by placing them at various temperatures within a range of 25°C to 45°C for a period of two months. Any cloudiness, discoloration, crystallization, or other changes in the appearance of the compositions were observed.

Long-term trial

Test Protocol: The post-application durability of the compositions was tested. Each composition was applied to a sample card and placed in an incubator at 37°C for 6 hours and 20 hours to dry the composition deposit. The weight of the cards with the applied composition was individually measured using a precision balance and recorded as the initial weight (W _{_initial}). The cards were then subjected to passes using thin paper over 5, 10, 20, 35, and 50 passes. The weight of the cards was measured after each set of passes and recorded as W_{_final.} The corresponding weight of the composition that transferred to the thin paper was obtained as W_{_transfer} = W _{_initial} - W _{_final} . Additionally, a grading score was provided on a scale of 1 to 5, where a score below 1 corresponded to a greater transfer of the composition from the cards and was therefore considered to indicate poor durability.

Sensory evaluation

Test Protocol: A sequential monadic protocol with 5 days of placement with each composition was tested (self-application trial). This protocol also involved three on-site visits by each volunteer to record their appreciation of the product through in-depth interviews and online interactions via mobile applications. Sixteen human volunteers aged 18 to 40 years who were regular users of liquid foundation products were included in the trial. The compositions as disclosed herein and the commercial product were evaluated for sensory aspects, such as oil control, long-lasting makeup appearance, buildable coverage, and sun protection.

RESULTS Long-term trial

Compositions C(1a), and C(2) to C(8) with the viscosity as listed in Table 2 were subjected to a long-term test to evaluate their attributes such as long-lasting and resistance to transfer.

Compositions C(1a), C(2) and C(3) prepared according to this disclosure exhibited the lowest transfer of the composition onto thin paper after being dried for 20 hours at 37 °C, after deposition onto a sample card (Table 2, FIG. 1 -1C). Compositions C(1a), C(2) and C(3) comprised an optimal weight percentage of hydrophobic film-forming polymer (1%), as well as an optimal combination of non-volatile hydrocarbon oil and hydrophobic silica aerogel resulting in transfer resistance and a lasting effect.

Compositions C(4), C(5), and C(8), containing 0.5%, 0.1%, and 5.2% by weight of the hydrophobic silicone film-forming polymer, respectively, exhibited the highest transfer of the compositions onto the thin paper after being dried for 20 hours at 37°C (Table 2, Figures 1D, 1E, and 1H). Composition C(8), with 5.2% by weight of the hydrophobic silicone film-forming polymer, resulted in the maximum transfer due to the formation of a rigid film, which eventually decomposed. Thus, it is clear that compositions containing hydrophobic silicone film-forming polymer outside the stated weight percentages resulted in a weak and lasting effect.

Composition C(6), comprising the essential components within the claimed weight range, still exhibited higher transfer due to the weight difference of the hydrophobic silica aerogel compared to the disclosed composition (Table 2, FIG. 1 ).

Composition C(7) comprised 9% by weight of phenyl trimethicone instead of the preferred combination of non-volatile hydrocarbon oil in this disclosure ( FIG. 1 ). Therefore, C(7), although it exhibits lower transfer due to its non-volatility, fails to provide UV protection in the absence of the preferred combination of non-volatile hydrocarbon oil of this disclosure.

Thus, it could be clearly observed that the compositions of the present disclosure prepared with the desired components in the disclosed weight ranges offered the desired lasting effect and associated skin benefits.

Composition Weight in g of the composition transferred after Grading after 50 runs 5 Passages 10 Passages 20 Passages 35 Passages 50 Passages C(1a) 0.001 0.003 0.009 0.016 0.025 4 C(2) 0.004 0.009 0.018 0.031 0.039 4 C(3) 0.003 0.008 0.013 0.018 0.024 5 C(4) 0.010 0.017 0.030 0.047 0.061 2 C(5) 0.010 0.014 0.024 0.042 0.056 2 C(6) 0.006 0.016 0.030 0.044 0.054 1 C(7) 0.002 0.008 0.014 0.023 0.033 2 C(8) 0.001 0.007 0.013 0.022 0.030 3

Sensory evaluation

Composition C(1b) of this disclosure has been evaluated with respect to various sensory aspects, such as sebum control, long-lasting makeup appearance, buildable coverage and sun protection, compared to a selected commercial product CP(1).

Results

During the 5 days of monadic testing, many volunteers (9-12/16) reported that composition C(1b) had a rich and creamy texture, compared to the commercial product CP(1).

The majority of volunteers (13-15/16) reported that composition C(1b) provided long-lasting, waterproof makeup indoors for up to 6 hours. Therefore, the volunteers did not need to touch up their makeup throughout the day.

The majority of volunteers (13-15/16) reported that composition C(1b) offered adjustable coverage.

The majority of volunteers (13-15/16) reported that composition C(1b) offered good sun protection compared to the commercial product CP(1) and the volunteers observed that there was no burning sensation of the skin and no redness around the facial area even after being exposed to the sun.

Thus, compositions C(1a), C(1b), C(2) and C(3) according to this disclosure comprising an optimal combination of volatile hydrocarbon oil, volatile silicone oil, hydrophobic silicone film-forming polymer, hydrophobic silica aerogel, silicone emulsifiers, non-volatile hydrocarbon oil and pigments in a water-in-oil emulsion provided a long-lasting makeup appearance with improved sun protection.

Consequently, it was observed that the use of specific ingredients in the desired weight ranges as disclosed in various embodiments herein facilitated the obtaining of a makeup composition with the desired sensory properties.

Benefits of this disclosure

This disclosure proposes a water-in-oil emulsion for coating keratinous material comprising: i) a continuous oil phase comprising: a) at least one volatile hydrocarbon oil; b) at least one volatile silicone oil; c) at least one non-volatile hydrocarbon oil; d) at least one hydrophobic silicone film-forming polymer; e) at least one hydrophobic silica aerogel; f) at least one silicone emulsifier; and g) at least one pigment; and ii) an aqueous phase. The composition, with an optimized ratio of film-forming polymer to silica aerogel in combination with volatile and non-volatile oils, offers the following perceived consumer benefits, as listed below.

The composition has a smooth, creamy liquid texture and is easy to spread and blend on the skin.

The formula offers a long-lasting made-up look for up to 6 hours, without touch-ups during the day.

The formula provides transfer-resistant and waterproof makeup.

The formula offers many other benefits for the skin, such as sebum control, a hydrated and matte appearance, a lightweight feel, and improved sun protection.

Claims (10)

Composition in the form of a water-in-oil emulsion, preferably in a physiologically acceptable medium, said composition comprising:
i) a continuous oily phase comprising:
a) at least one volatile hydrocarbon oil;
(b) at least one volatile silicone oil;
(c) at least one non-volatile hydrocarbon oil;
d) at least one hydrophobic silicone film-forming polymer in a weight range of 1% to 4.9% relative to the total weight of the composition;
e) at least one hydrophobic silica aerogel in a weight range of 1% to 5% relative to the total weight of the composition;
(f) at least one silicone emulsifier having a hydrophilic-lipophilic balance (HLB) of less than 8; and
(g) at least one pigment; and
ii) an aqueous phase,
in which at least one non-volatile hydrocarbon oil is selected from among non-UV-blocking synthetic ester oils, lipophilic liquid organic UV filters or mixtures thereof. Composition according to claim 1, wherein the volatile hydrocarbon oil is selected from hydrocarbon oils containing 8 to 16 carbon atoms, preferably from _C8 - _C16 isoalkanes, more preferably is isododecane. Composition according to claim 1, wherein the volatile silicone oil is selected from non-cyclic volatile silicone oils, preferably selected from dimethicones, trisiloxane, dodecamethylpentasiloxane, or mixtures thereof, more preferably selected from dimethicones. Composition according to claim 1, wherein the non-volatile hydrocarbon oil is selected from isononyl isononanoate, octocrylene or mixtures thereof. Composition according to claim 1, wherein the hydrophobic silicone film-forming polymer is selected from silicone resins, vinyl polymers comprising at least one carbosiloxane dendrimer-derived motif, silicone acrylate copolymers, silicone polyamide and hydrocarbon-based polyamide copolymers, or mixtures thereof, preferably selected from silicone resins, more preferably trimethylsiloxysilicate. Composition according to claim 1, wherein the hydrophobic silica aerogel is selected from amorphous hydrophobic silicas, hydrophobically treated sublimated silicas, or mixtures thereof, preferably hydrophobically treated sublimated silicas, more preferably silylated silica. Composition according to claim 1, wherein the silicone emulsifier is selected from polyether, polyglycerin-modified silicones, silicone elastomers, or mixtures thereof, preferably selected from cetyl polyethylene glycol (PEG)/polypropylene glycol (PPG)-10/1 dimethicone, polyglyceryl-4 isostearate, PEG-10 dimethicone, PEG-20, or mixtures thereof. Composition according to claim 1, wherein the pigment is selected from pigments coated with at least one compound selected from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl tristearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; silicone surfactants such as organopolysiloxanes, alkylalkoxysilanes such as triethoxycaprylylsilane; fluorinated surfactants such as perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups; Fluorosilicone surfactants such as perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialcoxysilanes; and mixtures thereof.
. Kit comprising (a) the composition according to claim 1; (b) a container; and (c) optionally, an applicator. Method for coating a keratinous material, preferably for makeup and/or care of a keratinous material, preferably skin, characterized in that said method comprises the application of said composition according to claim 1 on the keratinous material, preferably skin.