CN116437892A - Sun protection emulsion comprising silicone emulsifier blend - Google Patents

Abstract

A water-in-oil sunscreen emulsion composition is provided comprising an aqueous phase emulsified in an external fatty phase. The external fatty phase comprises at least one silicone fatty compound and at least about 10% by weight of an organic UV filter relative to the total sunscreen composition. The composition comprises an emulsified silicone elastomer and a non-elastomeric silicone surfactant. The composition further comprises a swellable clay and a pigment.

Description

Sun protection emulsion comprising silicone emulsifier blend

Cross Reference to Related Applications

The present application claims priority from U.S. patent application Ser. No. 17/387,575 filed on 7/28 of 2021. The present application also claims priority from french patent application number 2108923 filed on 8.26 of 2021.

Technical Field

The present invention relates to cosmetic compositions, and in particular to sunscreen emulsions comprising silicone emulsifier blends.

Discussion of the background

Cosmetic compositions having pigments to provide hiding power and color, such as those suitable for facial make-up, are known. Cosmetic compositions comprising various emulsifiers are also known. However, compositions having both pigments and high levels of organic UV filters are difficult to formulate. The inventors have recognized that one problem with formulating such compositions is that the incorporation of relatively high levels of pigment and high levels of organic UV filter (levels of pigment and organic UV filter required to provide various benefits to the user) results in instability of the composition.

Thus, certain aspects of the present invention relate to stable and aesthetically pleasing compositions that can provide sun protection and can also provide color (hue), hiding power, and/or other benefits.

Disclosure of Invention

According to one aspect of the present invention, the present invention relates to a water-in-oil sunscreen emulsion composition comprising an aqueous phase emulsified in an external fatty phase. The external fatty phase comprises at least about 10% by weight of organic UV filter relative to the total composition. The external fatty phase further comprises at least one silicone fatty substance. The composition further comprises an emulsifying silicone elastomer and a non-elastomeric silicone surfactant. The composition further comprises a swellable clay and a pigment.

According to another aspect of the invention, the invention relates to a method of treating skin. The method comprises applying to the skin a water-in-oil sunscreen emulsion composition comprising an aqueous phase emulsified in an external fatty phase. The external fatty phase comprises at least about 10% by weight of organic UV filter relative to the total composition. The external fatty phase further comprises at least one silicone fatty substance. The composition further comprises an emulsifying silicone elastomer and a non-elastomeric silicone surfactant. The composition further comprises a swellable clay and a pigment.

In some embodiments, it is desirable for one or more organic UV filters selected from, comprising or consisting of: homosalate, ethylhexyl salicylate, and octocrylene.

In other embodiments, the composition is substantially free of one or more or all of avobenzone, oxybenzone, octylmethoxy cinnamate, inorganic sunscreens, and volatile silicone oils.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Detailed description of the invention

As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

Except in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term "about", meaning between 10 and 15% of the indicated number.

As used herein, "active-based" means that only a particular component of an ingredient (e.g., in a composition) is considered and other chemically unrelated components, which may also be present in the same raw material source as the particular component, are ignored. As used herein, "solids-based" means that only components that are solid at room temperature (e.g., in the composition) are considered and the liquid portion of the composition, such as water and volatile solvents, are ignored.

As used herein, "film former" or "film former" refers to any substance, such as a polymer or resin, that leaves a film on the substrate to which it is applied.

As used herein, "polymer" refers to a compound composed of at least two monomers.

"keratinous materials" include keratinous materials such as hair, skin, eyebrows, lips, and nails.

"substituted" as used herein is meant to include at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen and nitrogen atoms, and functional groups, such as hydroxyl, ether, alkoxy, acyloxyalkyl, oxyalkylene, polyoxyalkylene, carboxylic acid, amine, acylamino (acylamino), amide, halogen, ester, thiol, sulfonate, thiosulfate, siloxane, hydroxyl, and polysiloxane groups. One or more substituents may be further substituted.

As used herein, "volatile" means having a flash point of less than about 100 ℃.

As used herein, "non-volatile" means having a flash point greater than about 100 ℃.

As used herein, all ranges provided are intended to include each specific range within the given range as well as combinations of sub-ranges between the given ranges. Further, it is noted that the range description "about 1%, 2% or 3% to about 5%, 10% or 15%" includes at least 1% to 5%, 1% to 10%, 1% to 15%, 2% to 5%, 2% to 10%, 2% to 15%, 3% to 5%, 3% to 10% and 3% to 15%.

All percentages of ingredients herein are listed on an active basis and on a weight basis, unless specifically stated otherwise.

As used herein, the term "substantially free" or "substantially free" means that less than about 2 weight percent of the particular substance added to the composition is present, based on the total weight of the composition, and may comprise less than about 1 weight percent, less than about 0.5 weight percent, less than about 0.1 weight percent, or no particular substance. By "anhydrous" is meant substantially free of water.

The compositions of the present invention may have a variety of consistencies, including, for example, fluids, pastes, semisolids, and the like.

The compositions and methods of the present invention can comprise, consist of, or consist essentially of: the essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components or limitations described herein or otherwise available in personal care.

Aqueous phase

The composition of the present invention comprises an aqueous phase. The aqueous phase comprises water and optionally other ingredients dissolved dispersed or suspended therein. Sufficient water may be present in the aqueous phase such that the concentration of water in the composition as a whole is, for example, less than about 40% by weight, such as from about 5% or 10% or 15% to about 30% or 35% or 40%. The aqueous phase may contain preservatives, electrolytes such as sodium salts, various polyols, water-soluble UV filters, chelating agents, and various active ingredients, vitamins, extracts, and the like.

According to certain embodiments, the aqueous phase comprises a polyol, such as glycerol, propylene glycol, hexylene glycol, butylene glycol, and the like. The concentration of these polyols may be from about 5 wt%, 7 wt%, 10 wt% to about 12 wt%, 15 wt% or 20 wt%.

According to certain embodiments, the aqueous phase comprises a skin lightening agent such as niacinamide. The concentration of such skin lightening agent in the composition may be from about 0.25 wt%, 0.5 wt% or 1 wt% to about 1 wt% or 2 wt% or 5 wt%.

According to certain embodiments, the composition (e.g., aqueous phase thereof) is substantially free of water-soluble UV filters, such as various salts of terephthal-ylene-di-camphorsulfonic acid, phenylbenzimidazole sulfonic acid, benzophenone-4, aminobenzoic acid (PABA), 4-bis (polyethoxy) -polyethoxyethyl p-aminobenzoate (PEG-25 PABA), camphorbenzalkonium methylsulfate, methylenebis-benzotriazole-tetramethylbutylphenol (aobenzotriazole), disodium phenylbisbenzimidazole tetrasulfonate (Bisdisulizole disodium), and tris-biphenyltriazine, and water-soluble derivatives thereof; their derivatives and the corresponding salts; naphthalimide derivatives and cinnamamide cationic quaternary salts (cinnamido amine cationic quaternary salts).

The aqueous phase is emulsified within the external fatty phase.

In certain notable embodiments, the composition is a water-in-oil (W/O) emulsion, wherein "O" represents a fatty phase comprising an organic UV filter and at least one silicone fatty substance. In certain other embodiments, the composition is a double emulsion (O/W/O emulsion). Those skilled in the art will readily recognize that "emulsified" and "emulsions" refer to fine dispersions of droplets, in this case discontinuous aqueous phases in a continuous oil phase. The emulsion is stabilized using an emulsifier.

Although the relative proportions of the aqueous phase and the fatty phase may vary, according to certain embodiments of the present invention, the fatty phase is present at a concentration greater than the total weight of the aqueous phase emulsified therein.

External fatty phase

The external fatty phase comprises one or more fatty substances, such as those compounds having a hydrophobic moiety, and in certain notable embodiments is not amphiphilic, and thus in this embodiment does not comprise hydrophilic moieties, such as anionic, cationic, zwitterionic or nonionic groups, which are polar and include sulfate, sulfonate, carboxylate, phosphate, phosphonate, ammonium, including mono-, di-and trialkylammonium, pyridine

Imidazolines

Amidine->

(amidium), poly (ethyleneimine->

) (poly (ethyleneiminium)), ammonium alkylsulfonate, ammonium alkylcarboxylate, amphoacetate/groups, and poly (oxyethylene) sulfonyl moieties. In certain embodiments, the fatty material does not comprise a hydroxyl moiety.

The external fatty phase comprises one or more organic UV filters and at least one silicone fatty substance, and may optionally further comprise other ingredients dissolved dispersed or suspended therein.

Organic UV filters

Organic UV (ultraviolet) filters are organic compounds that reduce UV radiation, such as by absorbing ultraviolet radiation primarily. According to certain embodiments, the at least one UV filter comprises at least one salicylate compound and at least one β, β -diphenylacrylate compound.

As examples of one or more organic UV-filters, the following ones, expressed by their INCI names, and mixtures thereof, may be mentioned.

Examples of particularly suitable salicylic acid compounds include homosalate (monomethyl salicylate), such as sold under the trademark "EusolexHMS" by Rona/EM Industries; and ethylhexyl salicylate, such as sold under the trademark "Neo Heliopan OS" by Haarmann and Reimer; ethylene glycol salicylate. Other examples of salicylate compounds include phenyl salicylate; dipropylene glycol salicylate, such as that sold under the trademark "dipal" by Scher; and salicylic acid TEA salts, such as sold under the trademark "Neo Heliopan TS" by Haarmann and Reimer.

Examples of particularly suitable beta, beta-diphenylacrylate compounds include octocrylene, such as sold by BASF under the trademark "Uvinul N539", in particular; and etoricline, for example sold by BASF under the trademark "Uvinul N35", among others.

Although according to certain embodiments, the one or more UV filters comprise only at least one salicylate compound and at least one β, β -diphenylacrylate compound, according to certain other embodiments, other UV filters are included. Other such examples include anthranilic acid-based compounds, dibenzoylmethane-based compounds, cinnamic acid-based compounds, camphor-based compounds, benzophenone-based compounds, triazine-based compounds, benzotriazole-based compounds, benzalmalonate (Benzalmalonate) compounds, imidazoline-based compounds, para-aminobenzoic acid-based compounds, methylenebis- (hydroxyphenyl-benzotriazole) -based compounds, and benzoxazoles-based compounds.

Anthranilic acid compounds include menthyl anthranilates, such as sold under the trademark "NeoHeliopan MA" by Haarmann and Reimer.

Dibenzoylmethanes include butylmethoxydibenzoylmethane, for example sold by Hoffmann-La Roche under the trademark "Parsol 1789", in particular; and isopropyl dibenzoylmethane.

Cinnamic acid compounds include ethylhexyl methoxycinnamate, such as sold by Hoffmann-La Roche under the trademark "Parsol MCX", in particular; isopropyl methoxycinnamate; isopropoxy methoxy cinnamic acid ester; isoamyl methoxycinnamate, for example sold under the trademark "Neo Heliopan E1000" by Haarmann and Reimer; cinnolsha ester (2-ethoxyethyl-4-methoxycinnamate); methoxy cinnamic acid DEA; diisopropyl methyl cinnamate; and glyceryl ethylhexanoate dimethoxy cinnamate.

The camphor compounds include benzylidene camphor derivatives: 3-benzylidene camphor, such as manufactured by Chimex under the trademark "Mexoryl SD"; 4-methylbenzylidene camphor, such as that sold under the trade name "Eusolex 6300" by Merck; benzylidene camphorsulfonic acid, such as manufactured by Chimex under the trademark "Mexoryl SL"; camphorbenzalkonium methosulfate, such as manufactured by Chimex under the trademark "Mexoryl SO"; terephthalylene dicarbamate sulfonic acid, such as manufactured by Chimex under the trademark "Mexoryl SX"; and polyacrylamide methyl benzylidene camphor, such as manufactured by Chimex under the trademark "Mexoryl SW".

Benzophenone-type compounds include benzophenone-1 (2, 4-dihydroxybenzophenone), such as are sold under the trademark "Uvinul 400" by BASF; benzophenone-2 (tetrahydroxybenzophenone), such as is sold by BASF under the trademark "Uvinul D50"; benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone, such as sold by BASF under the trademark "Uvinul M40"; benzophenone-4 (hydroxymethoxybenzophenone sulfonic acid), such as sold by BASF under the trademark "Uvinul MS 40"; benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxy benzophenone), such as is sold under the trademark "heliorb 11" by norquaty; benzophenone-8, such as sold under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (disodium dihydroxydimethoxy benzophenone disulfonate), such as sold by BASF under the trademark "Uvinul DS-49"; and n-hexyl benzophenone-12 and 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (e.g., UVINIUL A+ from BASF).

Triazines include diethylhexylbutyrylaminotriazinone, such as sold under the trademark "Uvasorb HEB" by Sigma 3V, 2,4, 6-tris (4-aminobenzylidene-malonic acid dipivalyl) -S-triazine, bis-ethylhexyloxyphenol methoxyphenyl triazine, such as sold under the trademark "TINOSORB S" by CIBA GEIGY, and ethylhexyl triazinone, such as sold under the trademark "UVTNUL T150" by BASF.

Benzotriazole compounds include phenylbenzotriazole derivatives: 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, branched and straight chain; and those described in USP 5240975.

Benzylidene malonate compounds include 4' -methoxybenzylidene malonic acid dipivaloyl ester, and polyorganosiloxanes containing benzylidene malonate functionality, such as silicone-15, as sold under the trademark "Parsol SLX" by Hoffmann-LaRoche. Benzimidazole compounds, in particular phenylbenzimidazole derivatives: phenylbenzimidazole sulfonic acids, such as are sold, inter alia, by Merck under the trademark "Eusolex 232", and disodium phenylbisbenzimidazole tetrasulfonate, such as are sold by Haarmann and Reimer under the trademark "Neo Heliopan AP".

The imidazoline compounds include ethylhexyl dimethoxy benzylidene dioxoimidazoline propionate. Bisbenzoxazolyl compounds: derivatives are described in EP-669,323 and U.S. Pat. No. 2,463,264.

Para-aminobenzoic acid compounds include PABA (para-aminobenzoic acid), ethyl PABA, ethyl dihydroxypropyl PABA, amyl dimethyl PABA, ethylhexyl dimethyl PABA, such as sold in particular by ISP under the trademark "Escalol 507", glycerol PABA and PEG-25PABA, such as sold by BASF under the trademark "Uvinul P25".

Methylenebis- (hydroxyphenyl benzotriazol) type compounds, including 2,2' -methylenebis [6- (2H-benzotriazol-2-yl) -4-methyl-phenol ], such as sold under the trademark "Mixxim BB/200" by Fairmount Chemical, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ], such as sold under the trademark "Tinosorb M" by BASF Or under the trademark "Mixxim BB/100" by Fairmount Chemical, in micronized form in aqueous dispersion, and derivatives, such as described in U.S. Pat. Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197,26,184 and EP-893,119, and cresol trazotrisiloxane, such as sold under the trademark "Silazotri" by Rhodia Chimie Or "Mexoryl XL" by L ' Oral.

Benzoxazole compounds include 2, 4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino ] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, such as sold under the trademark uvosorb K2A by Sigma 3V. Masking polymer and masking silicone: silicones are described in WO 93/04665. Dimers derived from alpha-alkylstyrene: dimers described in DE-19855649. 4, 4-diaryl butadiene compound: 1, 1-dicarboxy (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene.

In some embodiments, it is desirable that the one or more organic UV filters are selected from, include, or consist of: homosalate, ethylhexyl salicylate, and octocrylene.

In other embodiments, the composition is substantially free of one or more or all of avobenzone, oxybenzone, octylmethoxy cinnamate, and optionally is also free of inorganic sunscreens, such as sunscreen-grade titanium dioxide and zinc oxide, such as those having a primary particle size of less than about 75 nm.

The at least one organic UV filter is present in an amount such that the weight concentration is at least about 10 wt%, such as at least about 15 wt%, such as from about 10 wt%, 12 wt%, 14 wt%, 15 wt% to about 20 wt%, 22 wt%, 15 wt%, 30 wt%, or 40 wt%, relative to the entire composition.

Silicone fatty substances

The composition of the invention comprises at least one silicone fatty substance, and in particular at least one silicone oil, in the external fatty phase. As will be readily appreciated by those skilled in the art, "silicone" or "silicone fatty material" means a fatty material having at least one silicon atom directly bonded to (1) at least one oxygen atom and further directly bonded to (2) at least one carbon atom, such as carbon included in a methyl group or as part of a chain of carbon atoms (alkyl, aryl, etc.). Such organic compounds of silicon are commonly referred to as organosiloxanes. The silicone may comprise two or more organosiloxane units.

As used herein, "silicone oil" refers to a silicone fatty substance having a melting point below about 30 ℃ and which is generally insoluble in water, and may comprise two or more alkylsiloxy groups. The silicone oil may be volatile or non-volatile. Suitable examples of silicone oils include volatile silicone oils such as those having flash points of from about 40 ℃ to about 100 ℃. The volatile silicone oils may be linear or cyclic, have a viscosity at room temperature of less than or equal to 6cSt, and have 2 to 7 silicon atoms, optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Examples of suitable volatile silicone oils include octyl trimethicone, hexyl trimethicone, cyclopentasiloxane, cyclohexasiloxane, polydimethylsiloxane. Although in certain embodiments the compositions of the present invention comprise volatile silicone oils, in other embodiments the compositions are substantially free of these materials.

Non-volatile silicone oils include Polymethylsiloxanes (PDMS) with linear or cyclic silicone chains, which are liquids or pastes at room temperature, especially octyl polymethylsiloxane, cyclomethicones (cyclomethicones) such as phenyl trimethicone, cyclohexyl siloxane; polydimethylsiloxanes (CTFA name "polydimethylsiloxanes") comprising alkyl or alkoxy groups pendant or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; polydiethylsiloxane; and a polydimethylsiloxane fluid having a viscosity of about 300cPs at 25 ℃ to about 1500cPs at 25 ℃. Particularly useful polydimethyl siloxane fluids have a viscosity of about 350cps at 25 ℃ to about 1000cps at 25 ℃. According to certain embodiments, the composition is substantially free of volatile silicone oils.

According to certain embodiments, the concentration of the at least one silicone fatty substance in the composition as a whole is from about 1 wt%, 2 wt% or 3 wt% or 5 wt% or to about 5 wt%, 8 wt%, 10 wt% or 20 wt%, including all ranges and subranges therebetween.

Other fatty substances that may be present in the fatty phase include fatty substances that are not organic UV filters or silicone fatty substances. Such as those having a carbon chain of at least six carbons, wherein none of the six carbons is a carbonyl carbon or has a hydrophilic moiety directly bonded thereto or has two or more sequential oxypropylene groups. The hydrophobic moiety may include linear, cyclic, aromatic, saturated or unsaturated groups.

Suitable examples of such compounds include oils, such as vegetable oils (glycerides, triglycerides of fatty acids) and fatty acid esters. Specific non-limiting examples include esters such as isopropyl palmitate, hexyl laurate, isohexadecane, isopropyl myristate, isononyl isononanoate, C benzoate ₁₂ -C ₁₅ Alkyl esters, caprylic/capric triglycerides, pentaerythritol tetracaprylate, mineral oil, and the like.

According to certain other embodiments, the fatty phase may comprise one or more waxes. Wax refers to a lipophilic fatty compound that is solid at room temperature (about 25 ℃) and atmospheric pressure (760 mmHg, i.e., 105 Pa), which undergoes a reversible solid/liquid state change, and which has a melting point of greater than 30 ℃, and in some embodiments, greater than about 55 ℃ to about 120 ℃ or even as high as about 200 ℃. The term wax may include waxes of animal origin, waxes of vegetable origin, waxes of mineral origin and waxes of synthetic origin. Examples of waxes of animal origin include beeswax, lanolin wax and chinese insect wax. Examples of waxes of vegetable origin include rice bran wax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax (bark fiber wax), sugar cane wax (sugar cane wax), japan wax, lacquer wax (sumach wax) and cotton wax. Examples of waxes of mineral origin include paraffin wax, microcrystalline wax, montan wax, and ceresin wax. Examples of waxes of synthetic origin include polyolefin waxes, such as polyethylene waxes, waxes obtained by Fischer-Tropsch synthesis, waxy copolymers and esters thereof, and silicone and fluorinated waxes. Silicone waxes may also be included.

The term wax may also comprise hydrogenated oils of high melting point animal or vegetable origin. Examples include hydrogenated jojoba waxes and hydrogenated oils, which are produced from C by catalytic hydrogenation ₈ -C ₃₂ Fats consisting of straight or non-straight fatty chains are obtained, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin and hydrogenated palm oil.

According to certain embodiments, the external fatty phase is characterized by a majority of non-silicone fatty substances (also referred to herein as "non-silicones") comprising organic UV filters that do not contain silicone moieties, and hydrocarbons, fatty acid esters, or other fatty substances or compounds that do not contain any silicone moieties; and a small portion of silicone fatty material. By "major portion of the non-silicone" or "minor portion of the silicone fatty material" is meant that the total weight percent of the non-silicone fatty material is greater than the weight percent of the one or more non-silicone fatty materials in the sunscreen composition or in the external fatty phase.

Silicone resin

According to certain embodiments, other silicones that may be included in the fat phase include silicone resins, such as those selected from the group consisting of siloxysilicate resins, silsesquioxane resins, and silicone elastomers such as polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymers.

In one embodiment, the silicone resin includes those selected from the group consisting of siloxysilicate resins, silsesquioxane resins, and combinations thereof. One non-limiting example of a siloxysilicate according to the present invention is trimethylsiloxysilicate, which may be represented by the formula:

[(CH3)3SiO]x(SiO4/2)y

Wherein x and y may be, for example, 50-80. Such siloxysilicates are available from General Electric, dow Corning, wacker, milliken, siltech, grant Industries, momentive and Shin-Etsu Silicones under the trade name Resin

Commercially available.

According to another embodiment of the present invention, the composition may contain a silsesquioxane resin comprising at least one polypropylsilsesquioxane film forming resin.

Silsesquioxane resins are a specific form of silicone resin. Silicone resin nomenclature is referred to in the art as "MDTQ" nomenclature, wherein the silicone resin is described in terms of the various monomeric siloxane units that make up the polymer. Each letter of "MDTQ" represents a different type of unit. When the film-forming resin consists essentially of trifunctional units (or T units), it is commonly referred to as a silsesquioxane resin, as described, for example, in US 2006/0292096, which is incorporated herein by reference.

Examples of silsesquioxane resins useful in the present invention are alkyl silsesquioxane resins that are silsesquioxane homopolymers and/or copolymers having an average siloxane unit of the formula R1 nSiO (4-n)/2 wherein each R1 is a propyl group wherein greater than 80 mole% of R1 represents a C3-C10 alkyl group, n is a value of 1.0 to 1.4, and greater than 60 mole% of the copolymer comprises R1SiO3/2 units. Since each R1 is a propyl group, these polymers are known as poly propyl silsesquioxane resins or "tertiary propyl" silsesquioxane resins. These resins and methods of making them are described, for example, in US 8,586,013, 2012/0301415, 2007/0093619 and 2006/0292096, all of which are incorporated herein by reference.

Non-limiting examples of suitable polypropylene silsesquioxane resins for use in the present invention are available from Dow Corning as either Dow Corning 670 fluid or Dow Corning 680 fluid. These Dow Corning resins have the general formula RnSiO (4-n)/2, wherein R is independently selected from hydrogen atoms and monovalent hydrocarbon groups containing 3 carbon atoms, wherein more than 80 mole% of R is propyl, n is a value of 1.0-1.4, more than 60 mole% of the copolymer contains RSiO3/2 units, and has a hydroxyl or alkoxy content of 0.2-10 wt%, for example 1-4 wt%, preferably 5-10 wt%, and more preferably 6-8 wt%. Preferably, the polypropylsilsesquioxane resin has a molecular weight of about 5000 to about 30,000 and a Tg of about-5 ℃ to about 5 ℃.

According to certain embodiments, the concentration of the at least one silicone resin in the composition as a whole is from about 0.1 wt%, 0.25 wt% or 0.5 wt% to about 0.5 wt%, 1 wt%, 2 wt% or 5 wt%, including all ranges and subranges therebetween.

Pigment

The compositions of the present invention comprise pigments for providing color and/or opacity or hiding power. Suitable "colored pigments" for providing cosmetic color are those having a color component other than white, such as, for example, iron oxide particles, which may or may not have a surface treatment. The iron oxide particles provide a masking powder to help mask skin imperfections while imparting some additional visible color. Any of a variety of cosmetic grade iron oxide particles are suitable for use in the compositions of the present invention. In certain embodiments, the iron oxide particles have an average particle size of about 0.1 microns to about 10 microns, for example about 0.15 microns to about 1 micron. Iron oxides of interest include red, black and brown iron oxides having a primary particle size of less than one micron and surface treated with an organosilane such as triethoxyoctylsilane. Suitable examples include those available from Sun Chemical of Parsippany, new Jersey

Ironoxides. Other colored pigments, such as any of a variety of other inorganic oxides that impart color, such as chromium oxide, may also be included. Other suitable colored pigments include various inorganic lake pigments. According to other embodiments, the pigment may not be a colored pigment, but rather an opacifying pigment, such as a pigment grade titanium dioxide, such as a titanium dioxide having an average primary particle size of greater than about 75 nanometers, such as greater than about 200 nanometers, such as from about 200 to about 300 nanometers. According to other embodiments, an opacifying pigment such as mica, talc or fluorophlogopite is included.

The concentration of pigment in the composition may be from about 2%, 3%, 4%, 5% or 7% to about 7%, 8%, 10% or 15% by weight, including all ranges and subranges therebetween. In certain embodiments, the pigment concentration is at least about 5% by weight.

Silicone emulsifiers

The composition also contains two different classes (i.e. "blends") of silicone emulsifiers (surfactants) to improve the stability of the high loading organic UV filters as well as the silicone oils and/or to provide wetting or dispersion of the particulate fraction.

The first type of emulsifier included is an emulsified silicone elastomer. The term "emulsified silicone elastomer" is intended to mean a silicone elastomer comprising at least one hydrophilic chain.

The emulsifying silicone elastomer may be selected from polyoxyalkylenated silicone elastomers and polyglycerolated silicone elastomers, and mixtures thereof.

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

Preferably, the polyoxyalkylenated crosslinked organopolysiloxane is obtained by the crosslinking addition reaction of (A1) a diorganopolysiloxane containing at least two hydrogens each bonded to silicon with (B1) a polyoxyalkylene containing at least two ethylenically unsaturated groups, particularly in the presence of (C1) a platinum catalyst, as described, for example, in U.S. patent No. 5,236,986 and U.S. patent No. 5,412,004.

In particular, the organopolysiloxane can be obtained by reaction of a polyoxyalkylene (in particular polyoxyethylene and/or polyoxypropylene) containing dimethylvinylsiloxy end groups with a methylhydro-polysiloxane containing trimethylsiloxy end groups in the presence of a platinum catalyst.

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

Thus, the compound (A1) may be selected from the group consisting of methylhydrogen polysiloxane containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogen siloxane copolymer containing trimethylsiloxy end groups, cyclic dimethylsiloxane-methylhydrogen siloxane copolymer, and dimethylsiloxane-methylhydrogen siloxane-lauryl methyl siloxane copolymer containing trimethylsiloxy end groups.

The compounds (C1) are crosslinking catalysts and are, in particular, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and supported platinum.

Advantageously, the polyoxyalkylenated silicone elastomer can be formed by reacting a divinyl compound, in particular a polyoxyalkylene having at least two vinyl groups, with Si-H bonds of a polysiloxane.

The polyoxyalkylenated silicone elastomer according to the invention is preferably mixed with at least one hydrocarbon-based oil and/or one silicone oil to form a gel. In these gels, the polyoxyalkylenated elastomer may be in the form of non-spherical particles.

Polyoxyalkylenated elastomers are described in particular in U.S. patent No. 5,236,986, U.S. patent No. 5,412,004, U.S. patent No. 5,837,793, and U.S. patent No. 5,811,487.

Polyoxyalkylenated silicone elastomers that may be used include those sold under the names KSG-21, KSG-20, KSG-30, KSG-31, KSG-32, KSG-33, KSG-210, KSG-310, KSG-320, KSG-330, KSG-340, and X-226146,Dow Corning by Shin-Etsu corporation under the names DC9010 and DC9011, with KSG-210 being particularly notable.

In another embodiment, the emulsified silicone elastomer may also be selected from polyglycerolated silicone elastomers.

The polyglycerolated silicone elastomer is a crosslinked elastomeric organopolysiloxane that can be obtained by a crosslinking addition reaction of a diorganopolysiloxane containing at least one hydrogen bonded to silicon and a polyglycerolated compound having an ethylenically unsaturated group, in particular in the presence of a platinum catalyst.

Preferably, the crosslinked elastomeric organopolysiloxane is obtained by the crosslinking addition reaction of (a) a diorganopolysiloxane containing at least two hydrogens each bonded to silicon with (B) a glycerinated compound having at least two ethylenically unsaturated groups, in particular in the presence of (C) a platinum catalyst.

In particular, the organopolysiloxane can be obtained by the reaction of a polyglycerolated compound containing a dimethylvinylsiloxy end group and a methylhydrogen polysiloxane containing a trimethylsiloxy end group in the presence of a platinum catalyst.

The organic group bonded to the silicon atom of the compound (A) may be an alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl (or lauryl), myristyl, cetyl or stearyl; substituted alkyl groups such as 2-phenethyl, 2-phenylpropyl or 3, 3-trifluoropropyl; aryl groups such as phenyl, tolyl, or xylyl; substituted aryl groups such as phenethyl; and groups based on substituted monovalent hydrocarbons, such as epoxy groups, carboxylate groups, or mercapto groups. Preferably, the organic group is selected from methyl, phenyl and lauryl.

Thus, the compound (a) may be selected from methyl hydrogen polysiloxane containing trimethylsiloxy end groups, dimethylsiloxane-methyl-hydrogen siloxane copolymer containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogen siloxane cyclic copolymer, and dimethylsiloxane-methyl-hydrogen siloxane-lauryl methyl siloxane copolymer containing trimethylsiloxy end groups.

The compound (B) may be a polyglycerolated compound corresponding to the following formula (B'):

CmH2m-1-O-[Gly]n-CmH2m-1 (B′)

wherein m is an integer from 2 to 6, n is an integer of: 2 to 200, preferably 2 to 100, preferably 2 to 50, preferably n is 2 to 20, preferably 2 to 10, and preferably 2 to 5, and in particular equal to 3; gly represents:

-CH2-CH (OH) -CH 2-O-or-CH 2-CH (CH 2 OH) -O-)

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

The compound (C) is a crosslinking reaction catalyst, and in particular chloroplatinic acid, a chloroplatinic acid-olefin complex, a chloroplatinic acid-alkenylsiloxane complex, a chloroplatinic acid-diketone complex, platinum black or platinum on a carrier.

The polyglycerolated silicone elastomer according to the invention is typically mixed with at least one hydrocarbon-based oil and/or one silicone oil to form a gel. In these gels, the polyglycerolated elastomer is typically in the form of non-spherical particles.

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

As polyglycerolated silicone elastomers, mention may be made of those sold under the names KSG-710, KSG-810, KSG-820, KSG-830 and KSG-840 by Shin-Etsu corporation.

The second type of emulsifier included in the compositions of the present invention is a non-elastomeric (e.g., non-crosslinked) silicone surfactant.

The non-elastomeric silicone surfactant may be any silicone surfactant that is not an emulsified silicone elastomer, as described above. Examples of non-elastomeric silicone surfactants include alkoxylated silicone surfactants. Examples include an organosilicone compound with an alkoxylated allyl group of any number of different repeating units of ethylene oxide or propylene oxide. The alkoxylated groups may be in terminal and/or non-terminal positions of the molecule.

According to one embodiment, the non-elastomeric silicone surfactant includes a non-terminal hydrophobic group. One suitable example is a copolymer of an alkoxylated polydimethylsiloxane and an alkyl polydimethylsiloxane, such as cetyl dimethicone copolyol, such as INCI: cetyl PEG/PPG-10/polydimethylsiloxane were purchased from Evonik as ABIL EM-90 or ABIL EM-180.

The total concentration of emulsifier and/or surfactant in the composition can be from about 1%, 2%, or 3% to about 4%, 5%, 6%, or 10% by weight relative to the total weight of the composition, including all combinations of such ranges.

According to certain embodiments, the weight concentration of the emulsified silicone elastomer is no greater than the weight concentration of the non-elastomeric silicone surfactant. The concentration of the emulsified silicone elastomer independently can be from about 0.2%, 0.4%, or 0.75% to about 0.75%, 1%, or 3%. The concentration of the non-elastomeric silicone surfactant independently can be from about 0.5%, 1%, or 2% to about 2%, 3%, 5%, or 10%. The weight concentration ratio of non-elastomeric silicone surfactant to emulsified silicone elastomer can be from about 0.5:1, 0.75:1, or 1:11.5:1, or 2:1 to about 2:1, 3:1, or 5:1.

Rheology modifier

The compositions of the present invention comprise rheology modifiers, and in particular swellable clays. "swellable clay" refers to a clay material capable of swelling in water. An example of a swellable clay is a smectite clay. The crystal structure of the smectite family is an octahedral aluminum oxide sheet between two tetrahedral silica sheets. In one notable embodiment, the swellable clay is bentonite. Bentonite is a rock formed from highly colloidal and plastic clays, which consist primarily of montmorillonite (a clay mineral of the smectite family), and is produced by in situ devitrification of pozzolans. In addition to montmorillonite, bentonite may contain feldspar, cristobalite and crystalline quartz. Bentonite has the ability to form thixotropic gels with water, absorbing large amounts of water. The variation of interstitial water and exchangeable cations in the interlayer space affects the properties of bentonite and thus the commercial use of different types of bentonite.

A well-known swellable clay suitable for use in the composition is BENTONE 38VCG, commercially available from Elementis Specialties, east Windsor, new Jersey. BENTONE GEL GTCC V is an organic (distearammonium) modified hectorite.

The swellable clay may be present in the compositions of the present invention in an amount from about 0.1%, 0.25% or 0.5% to about 0.5%, 0.75%, 1% or 3% by weight, based on the total weight of the composition, including all ranges and subranges therein. Propylene carbonate, if present, may be present in an amount such that the weight ratio of swellable clay to propylene carbonate is about 2:1 to about 5:1 is present in the composition of the invention.

The compositions of the present invention include other rheology modifiers, such as hydrophobically modified silica, e.g., silica aerogel.

Silica aerogel is a porous material obtained by replacing (by drying) the liquid component of silica gel with air. They are usually synthesized by sol-gel processes in a liquid medium and then dried, usually by extraction with supercritical fluids, the most common one being supercritical C0 ₂ . This type of drying makes it possible to avoid shrinkage of the pores and the material. Sol-Gel process and various drying methods are described in Brinker cj., and Scherer g.w., sol-Gel Science: new York: academic Press, 1990. Silica aerogel is generally disclosed in U.S. patent No. 9,320,689, the entire contents of which are incorporated herein by reference.

As the hydrophobic silica aerogel usable in the present invention, there may be mentioned, for example, an aerogel sold by Dow Corning under the name VM-2260 (INCI name: silica silylate), whose average particle size is about 1000 μm, and whose specific surface area per unit mass is 600 to 800m ² /g。

Mention may also be made of the labels AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, by Cabot corporation,

AEROGEL MT 1100, ENOVA AEROGEL MT 1200.

More particularly, an aerogel sold under the name VM-2270 (INCI name: silica silylate) by Dow Corning company will be used, having an average particle size of 5-15 microns and a specific surface area per unit mass of 600-800m ² /g。

If silica aerogel particles are used, they can be used in the compositions of the present invention in an amount of from 0.1 wt% to about 8 wt%, preferably from about 0.05 wt%, 0.1 wt% or 0.15 wt% to about 0.2 wt%, 0.5 wt%, 1 wt% or 2 wt%, all based on the weight of the composition as a whole.

Other ingredients

The compositions of the present invention may optionally contain other functional ingredients, such as those that can be readily dissolved, dispersed or suspended in the composition. These may include other particulate materials (organic, silicone-based); polymers, for example for thickening/rheology modification or film formation; a preservative; solvents for organic UV filters, such as butyl octyl salicylate, dyes, fragrances; an antioxidant; a vitamin; wetting agents, and the like. The person skilled in the art will take care to select the optional additional additives and/or the amounts thereof such that the advantageous properties of the composition according to the invention are not or substantially not adversely affected by the envisaged addition.

According to certain embodiments, the composition is substantially free of various ingredients. As noted above, the composition may be substantially free of one, more or all of the following: organic UV filters other than salicylates and beta, beta-diphenylacrylate compounds (e.g., avobenzone, oxybenzone, octylmethoxy cinnamate), inorganic sunscreens, volatile silicone oils, non-silicone surfactants, and/or water-soluble UV filters.

By "water-soluble organic sunscreen ingredient" is meant any organic compound used to mask UV radiation, which may be completely dissolved or miscible in the liquid aqueous phase in molecular form, or which may be dissolved in the liquid aqueous phase in colloidal form (e.g. in micellar form).

Non-limiting examples of water-soluble organic sunscreen ingredients useful in the present invention include, for example, terephthal-ylene-di-camphorsulfonic acid, phenylbenzimidazole sulfonic acid, benzophenone-4, aminobenzoic acid (PABA), 4-bis (polyethoxy) -polyethoxyethyl para-aminobenzoate (PEG-25 PABA), camphorbenzammonium methyl sulfate, methylenebis-benzotriazole-tetramethylbutylphenol (aobenzotriazole), disodium phenylbisbenzimidazole tetrasulfonate, and various salts of tris-biphenyltriazine and water-soluble derivatives thereof; their derivatives and the corresponding salts; naphthalimide derivatives, such as those described in European patent application EP 1990372 A2, the entire contents of which are incorporated herein by reference; and cinnamamide cationic quaternary salts and derivatives, such as those described in U.S. patent 5,601,811, the entire contents of which are incorporated herein by reference, and mixtures thereof.

These materials can be variously selected by those skilled in the art to prepare compositions having desired properties such as consistency or texture.

The other ingredients may be present in the composition at a concentration up to about 20%, for example from about 0%, 2% or 5% to about 10%, 15% or 20% (including all ranges and subranges therebetween).

According to certain specific embodiments of the present invention, the water-in-oil sunscreen emulsion composition comprises an aqueous phase emulsified in an external fatty phase. The external fat phase comprises: (1) At least about 10% by weight of an organic UV filter relative to the total composition; (2) At least one silicone having a weight concentration less than the total weight concentration of the UV filter; (3) emulsifying the silicone elastomer; (4) A non-elastomeric silicone surfactant in a weight concentration greater than the weight concentration of the emulsified silicone elastomer; (5) swellable clay; (6) silica aerogel; and (7) from about 5% to about 15% of a colored pigment. The water-in-oil sunscreen emulsion composition is substantially free of titanium dioxide sunscreens (titanium dioxide having an average primary particle size of less than about 75 nanometers), zinc oxide, and oxybenzone. The water-in-oil sunscreen emulsion composition may also be substantially free of one, more or all of the following: salicylates and beta, beta-diphenylacrylate compounds (e.g., avobenzone, oxybenzone, octylmethoxy cinnamate), organic UV filters, volatile silicone oils, non-silicone surfactants, and/or water-soluble UV filters.

According to a preferred embodiment of the present invention, there is provided a method for protecting, caring for and/or making up keratinous materials by applying to the keratinous materials a composition according to the present invention in an amount sufficient to protect, treat, care and/or make up the keratinous materials. According to other preferred embodiments, there is provided a method of improving the appearance of keratinous materials by applying to the keratinous materials a composition of the present invention in an amount sufficient to improve the appearance of the keratinous materials.

The composition may be applied to the desired area as desired, preferably once per day, and then preferably dried before being subjected to contact with, for example, clothing or other objects.

The compositions of the present invention may be prepared using methods known in the art, such as adding silicone fatty materials, organic UV filters, silicone emulsifiers, swellable clays, pigments, optional silicone film formers, and silica aerogels to a main vessel and homogenizing to form an oil phase formulation. Separately, aqueous formulations are prepared by combining water, optional ingredients such as polyols, actives, chelating agents, preservatives, and the like. The aqueous phase may be heated and cooled to room temperature, if desired. The aqueous phase preparation is added to the oil phase preparation and emulsified under shear.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The following examples are intended to illustrate the invention, but are not to be construed as limiting the scope thereof. The percentages are given on a weight basis.

EXAMPLE A composition according to the invention

Compositions consistent with the ingredients and approximate weight concentrations in table 1 below were prepared and evaluated for phase stability. Inventive example 1 was consistent with the embodiments of the invention described herein. Comparative example 1 is comparative. For simplicity, the concentrations are rounded in some cases.

TABLE 1

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Inventive example 1 and comparative example 1 were almost identical in composition except that inventive example 1 had more non-elastomeric silicone emulsifier than the emulsified silicone elastomer. Embodiments of the present invention also include swellable clay and silicone resin. When the phase stability was evaluated, it was observed that inventive example 1 was phase stable. Comparative example 1 immediately shows the phase.

The foregoing description illustrates and describes the present disclosure. In addition, the disclosure shows and describes only the preferred embodiments, but as noted above, it is to be understood that it is capable of use in various other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. The embodiments described hereinabove are further intended to explain best modes known of the applicant and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with the various modifications required by the particular applications or uses thereof. Accordingly, the description is not intended to limit the invention to the form disclosed herein. Moreover, it is intended that the appended claims be construed to include alternative embodiments.

Claims (16)

1. A water-in-oil sunscreen emulsion composition comprising:

an aqueous phase emulsified in an external fatty phase, wherein the external fatty phase comprises at least one silicone fatty compound, and wherein the external fatty phase further comprises a sufficient amount of an organic UV filter such that the organic UV filter is present at a concentration of at least about 10 wt% relative to the entire sunscreen composition;

Emulsifying the silicone elastomer;

a non-elastomeric silicone surfactant;

swellable clay; and

and (3) pigment.

2. The water-in-oil sunscreen emulsion composition of claim 1, wherein the water-in-oil sunscreen emulsion composition is substantially free of titanium dioxide sunscreens, zinc oxide, and oxybenzone.

3. The water-in-oil sunscreen emulsion composition of claim 1, wherein the oil phase is characterized by having a small portion of silicone.

4. The water-in-oil sunscreen emulsion composition of claim 1, wherein the emulsified silicone elastomer and the non-elastomeric silicone surfactant are each present in the composition at a respective weight concentration, and wherein the weight concentration of the emulsified silicone elastomer is no greater than the weight concentration of the non-elastomeric silicone surfactant.

5. The water-in-oil sunscreen emulsion composition of claim 1, wherein the emulsified silicone elastomer and the non-elastomeric silicone surfactant are each present in the composition at a weight concentration such that the ratio of the weight concentration of non-elastomeric silicone surfactant to the weight concentration of emulsified silicone elastomer is from about 1:1 to about 3:1.

6. The water-in-oil sunscreen emulsion composition of claim 1, wherein the water-in-oil sunscreen emulsion composition is substantially free of avobenzone.

7. The water-in-oil sunscreen emulsion composition of claim 1, wherein the composition is substantially free of volatile silicones.

8. The water-in-oil sunscreen emulsion composition of claim 1 wherein the composition comprises at least about 15% organic UV filter.

9. The water-in-oil sunscreen emulsion composition of claim 1 wherein the composition comprises at least about 5% colored pigment.

10. The water-in-oil sunscreen emulsion composition of claim 1, wherein the composition further comprises a silicone resin.

11. The water-in-oil sunscreen emulsion composition of claim 1, wherein the composition further comprises a silica aerogel.

12. The water-in-oil sunscreen emulsion composition of claim 1, wherein the composition further comprises niacinamide.

13. The water-in-oil sunscreen emulsion composition of claim 1, wherein the composition further comprises a polyol.

14. The water-in-oil sunscreen emulsion composition of claim 1 wherein the composition comprises less than about 40% by weight water.

15. The water-in-oil sunscreen emulsion composition of claim 4 wherein the emulsified silicone elastomer is present in the composition at a weight concentration of from 0.2% to about 3% relative to the total sunscreen composition, wherein the non-elastomeric silicone surfactant is present in the composition at a weight concentration of from about 2% to about 10%, wherein the swellable clay is present in the composition at a weight concentration of from about 0.1% to about 1%, and wherein

The pigment is present in the composition at a concentration of about 2% to about 10% by weight.

16. A method of treating skin comprising applying the composition of claim 1 to the skin.