Patent Description:
Pigmented topical products are often created using either emulsions or anhydrous systems. It is common to include materials such as iron oxide pigments in hydrous systems to create varying colors of skin-tone. Usually, anhydrous systems consist predominantly of oils and waxes and are used for formulating eyeshadows and lipsticks. These anhydrous systems often contain a chemical class of dyes called azo dyes allowing for the creation of compositions in a large range of the color palette. When these azo dyes are precipitated as salts onto a substrate they become brightly colored lake pigments which are identified by the D&C and FD&C colorant classes.

Cosmetic compositions are known, for example, from <CIT> which discloses cosmetic compositions comprising a gel formed from a cellulosic polymer and a polar oil, a non-polar film-forming agent, polyhydroxystearic acid, and one or more pigments. <CIT> discloses emulsion makeup compositions for keratinous surfaces which change color upon application and methods for treating keratinous surfaces with an emulsion cosmetic composition that changes color upon application. <CIT> discloses water-resistant lip-films formed from water-based compositions comprising water; an alkali-dispersible or alkali soluble, water-insoluble thermoplastic film forming resin; a volatile base; and a water-insoluble plasticizer.

Typically, D&C and FD&C lake pigments cannot be incorporated into hydrous systems due to hydrolysis at several sites within these large molecules. It is well known that treating the lake pigments can retard the hydrolysis in hydrous systems to some extent. For example, ITT-treatment of organic pigments is often used to increase the color stability of compositions comprising azo dyes. However, factors such as heat during the manufacturing and filling processes can counteract the pigment treatment and cause the azo dye based colorants to hydrolyze regardless of surface treatment. Such hydrolysis will alter the resultant color of compositions over the course of manufacture thus resulting in a less desired product. Instead of organic pigments, iron oxides are often used in conjunction with titanium dioxide to create a muted palette of shades.

Cosmetic products also often use titanium dioxide ("TiO<NUM>") which is mined as a combination of rutile and anatase crystalline forms. For example, <CIT> (which forms part of the state of the art only for the purposes of Article <NUM>(<NUM>) EPC) relates to compositions comprising organic pigments and rutile TiO<NUM> and <CIT> discloses a cosmetic containing rutile-type titanium dioxide. Anatase is the predominantly used form of TiO<NUM> in color cosmetics. The titanium dioxide is combined with organic pigment materials to yield brighter colors seen in lipsticks, blush, and eyeshadow by providing increased refraction of pigment colors (TiO<NUM> is typically a white solid). However, electrons donated from titanium dioxide to the system often exacerbate the color shade shift of compositions-in particular in aqueous compositions with organic pigments. Accordingly, true emulsion lipsticks do not exist in a full shade palette of bright colors since the colors accessed by various combinations of organic pigments are inaccessible in these lipsticks.

It is therefore an object of this invention to provide pigmented compositions comprising with reduced color shift over time.

In accordance with the foregoing objectives and others, this present disclosure provides compositions with reduced color shift and/or homogenous color distribution. The reduction in color shift and/or homogenous color distribution may be observed following heating of the compositions for prolonged periods of time (e.g., one hour, two hours, three hours, four hours, five hours, six hours, seven hours, eight hours) at elevated temperatures (e.g., above <NUM>). Without wishing to be bound by theory, it is believed that metal oxide components are able to prevent hydrolysis of organic components thereby conferring color stability. By stabilizing the organic pigments, the compositions of the present disclosure may be capable of being formulated in a wider shade palette than previously available. The reduced color shift is accomplished through the use of metal oxide components having a particle size of less than <NUM> or less than <NUM> or less than <NUM> or less than <NUM>. The particle size of these components may be measured by dynamic light scattering. In certain embodiments, color stability is most pronounced in aqueous systems which are heated and maintained at higher temperatures (e.g., above <NUM>, above <NUM>, above <NUM>, above <NUM>) for longer periods of time (e.g., eight hours) as the organic pigment instability reaction is exothermic. In particular, these higher temperatures are above the melting point of a composition base (i.e., the composition without the pigment grind) where the full phase transition from solid to liquid occurs.

Provided is a pigmented composition according to claim <NUM>. The pigmented composition may comprise:.

wherein the weight ratio of said pigmentary titanium dioxide and said organic pigments to said metal oxide particles in said composition is greater than <NUM>:<NUM> (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>), and wherein said metal oxide particles are selected from silica, alumina, zirconia, zinc oxide, indium tin oxide, ceria, and mixtures thereof, and/or wherein said metal oxide particles are fumed metal oxide particles.

Typically, the compositions are in the form of an emulsion. The emulsion may be, for example, a water-in-oil, oil-in-water, silicone-in-water, water-in-silicone, polyol-in-oil, oil-in-polyol, glycerin-in-oil, oil-in-glycerin, silicone-in-glycerin, glycerin-in-silicone, silicone-in-polyol, or polyol-in-silicone emulsion. In one embodiment, the emulsion is a water-in-oil, oil-in-water, glycerin-in-oil, silicone-in-water, or water-in-silicone emulsion. In further embodiments, the emulsion is a glycerin-in-oil, or water-in-oil emulsion. In certain embodiments, the emulsion is a glycerin-in-oil emulsion.

Also provided is a pigmented composition in the form of a glycerin-in-oil emulsion according to claim <NUM>. In certain implementations, the pigmented composition may be in the form of a glycerin-in-oil emulsion comprising:.

wherein the weight ratio of said pigmentary titanium dioxide and said organic pigments to said metal oxide particles in said composition is greater than <NUM>:<NUM>, and wherein the metal oxide particles have a particle size of less than <NUM>.

A method for coloring a human integument is also provided according to claim <NUM>. In embodiments, the method comprises applying to the human integument a composition comprising:.

wherein the weight ratio of said pigmentary titanium dioxide and said organic pigments to said metal oxide particles in said composition is greater than <NUM>:<NUM> (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>), and wherein said metal oxide particles are selected from silica, alumina, zirconia, zinc oxide, indium tin oxide, ceria, and mixtures thereof, and/or wherein said metal oxide particles are fumed metal oxide particles. In some embodiments, the human integument is a keratinous surface. The keratinous surface may be hair (e.g., eyebrows, eyelashes), skin, lips, or nails (e.g. toenails, fingernails, cuticles). In some implementations, the compositions are applied to the lips. In some embodiments, application to a human integument results in the formation of a film on the integument.

Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the invention that may be embodied in various forms. In addition, each of the examples given in connection with the various embodiments of the invention is intended to be illustrative, and not restrictive.

All terms used herein are intended to have their ordinary meaning in the art unless otherwise provided. All concentrations are in terms of percentage by weight of the specified component relative to the entire weight of the topical composition, unless otherwise defined.

As used herein, "a" or "an" shall mean one or more. As used herein when used in conjunction with the word "comprising," the words "a" or "an" mean one or more than one. As used herein "another" means at least a second or more.

As used herein, "consisting predominantly" with respect to the rutile content of TiO<NUM> means that the TiO<NUM> is predominantly composed of rutile-TiO<NUM>. For example, compositions with TiO<NUM> consisting predominantly of rutile TiO<NUM> shall mean that the TiO<NUM> present in the composition is above <NUM>%, <NUM>%, <NUM>%, or <NUM>%, rutile TiO<NUM> by weight of all the TiO<NUM> present in the composition (i.e., the TiO<NUM> component). In one embodiment, the TiO<NUM> present in the composition is above <NUM>% by weight of the TiO<NUM> component. In a further embodiment, the TiO<NUM> present in the composition is above <NUM>% (e.g., above <NUM>%, above <NUM>%) by weight of the TiO<NUM> component.

As used herein, all ranges of numeric values include the endpoints and all possible values disclosed between the disclosed values. The exact values of all half integral numeric values are also contemplated as specifically disclosed and as limits for all subsets of the disclosed range. For example, a range of from <NUM>% to <NUM>% specifically discloses a percentage of <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, and <NUM>%. Additionally, a range of <NUM> to <NUM>% includes subsets of the original range including from <NUM>% to <NUM>%, from <NUM>% to <NUM>%, from <NUM>% to <NUM>% It will be understood that the sum of all weight % of individual components will not exceed <NUM>%.

As used herein, the term "oil" is intended to include silicone oils, unless otherwise noted. The term "oil" is intended to encompass volatile and/or nonvolatile oils. The terms "internal" and "discontinuous" phase are synonymous, as are the terms "external" and "continuous" phase. The terms "glycerin" and "glycerol" are synonymous and used interchangeably. It will be understood that the oil phases of compositions may comprise one or more silicone oils as either the primary or non-primary component of the oil phase. It will also be understood that water phases of compositions may comprise one or more polyol (e.g., glycerin) as a non-primary component and polyol (e.g., glycerin) phases of compositions may comprise water as a non-primary component.

The compositions of the invention are useful for application to the human integumentary system, including, skin, lips, nails, hair, and other keratinous surfaces. As used herein, the term "keratinous surface" refers to keratin-containing portions of the human integumentary system, which includes, but is not limited to, skin, lips, hair (including eyebrows and eyelashes), and nails (e.g., toenails, fingernails, cuticles) of mammalians, preferably humans. A "keratin fiber" includes hair of the scalp, eyelashes, eyebrows, facial hair, and body hair such as hair of the arms, legs.

wherein the weight ratio of said pigmentary titanium dioxide and said organic pigments to said metal oxide particles in said composition is greater than <NUM>:<NUM> (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>). In certain implementations, the composition is aqueous or comprises an aqueous phase.

The organic pigments can include, but are not limited to, at least one of carbon black, carmine, phthalocyanine blue and green pigment, diarylide yellow and orange pigments, and azo-type red and yellow pigments such as toluidine red, litho red, naphthol red and brown pigments, and combinations thereof. The organic pigment may be in salt form, for example, the Al+, Ba+, Ca+ salt of the organic pigment.

The compositions may comprise, for example, one or more dyes, toners or lakes. Lakes generally refer to a colorant prepared from a water-soluble organic dye (e.g., D&C or FD&C) which has been precipitated onto an insoluble reactive or adsorptive substratum or diluent. In some embodiments, the organic pigments may be azo dye based or comprise one or more azo moieties. Typically, azo based pigments are organic compounds comprising the linkage -N=N-. The term "D&C" means drug and cosmetic colorants that are approved for use in drugs and cosmetics by the FDA. The term "FD&C" means food, drug, and cosmetic colorants which are approved for use in foods, drugs, and cosmetics by the FDA. Certified D&C and FD&C colorants are listed in <NUM> C. § <NUM> et seq. and include the FD&C colors Blue <NUM>, Blue <NUM>, Green <NUM>, Orange B, Citrus Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Yellow <NUM>, Yellow <NUM>, Blue <NUM>, Blue <NUM>; Orange B, Citrus Red <NUM>; and the D&C colors Blue <NUM>, Blue <NUM>, Green <NUM>, Green <NUM>, Green <NUM>, Orange <NUM>, Orange <NUM>, Orange <NUM>, Orange <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Violet <NUM>, Yellow <NUM>, Yellow <NUM>, Yellow <NUM>, Yellow <NUM>, Blue <NUM>, Blue <NUM>, Green <NUM>, Green <NUM>, Green <NUM>, Orange <NUM>, Orange <NUM>, Orange <NUM>, Orange <NUM>, and so on. For example, the pigmented composition may comprise D&C Red <NUM> (e.g., CI <NUM>, CI <NUM> or CI <NUM>); D&C Red <NUM> (CI <NUM>); D&C Red <NUM> (CI <NUM>); D&C Orange <NUM> (CI <NUM>); D&C Orange <NUM> (CI <NUM>); D&C Red <NUM> (CI <NUM>); D&C Red <NUM> (CI <NUM>); D&C Red <NUM> (CI <NUM>:<NUM>); D&C Red <NUM> (CI <NUM>:<NUM>); D&C Yellow <NUM> (CI <NUM>); D&C Red <NUM> (CI <NUM>); D&C Orange <NUM> (CI <NUM>); D&C Yellow <NUM> (CI <NUM>); FD&C Red <NUM> (CI <NUM>); FD&C Blue <NUM> (CI <NUM>); FD&C Yellow <NUM> (CI <NUM>); or any combinations thereof. In certain implementations, the composition may comprise one or more azo based organic pigments. For example, the pigmented composition may comprise Red <NUM> and/or Red <NUM> and/or Red <NUM> and/or Blue <NUM> and/or Yellow <NUM> and/or Red <NUM>. The compositions may comprise Red <NUM>. In certain embodiments the composition may comprise Red <NUM> and Red <NUM>. In certain embodiments, the compositions may comprise Red <NUM> and Blue <NUM>. In various implementations, the composition may comprise Red <NUM>, Red <NUM>, and Blue <NUM>.

Substrates suitable for forming lakes include, without limitation, mica, bismuth oxychloride, sericite, alumina, aluminum, copper, bronze, silver, calcium, zirconium, barium, and strontium, titanated mica, fumed silica, spherical silica, polymethylmethacrylate (PMMA), micronized TEFLON, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium aluminum silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate, calcium silicate, dextran, nylon, silica silylate, silk powder, sericite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder, and mixtures thereof.

Suitable lakes include, without limitation, those of red dyes from the monoazo, disazo, fluoran, xanthene, or indigoid families, such as Red <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and Red <NUM>; lakes of yellow pyrazole, monoazo, fluoran, xanthene, quinoline, dyes or salt thereof, such as Yellow <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>; lakes of violet dyes including those from the anthroquinone family, such as Violet <NUM> as well as lakes of orange dyes, including Orange <NUM>, <NUM>, <NUM>, <NUM>, and the like.

The organic pigments may be surface treated. In certain embodiments, the organic pigments are surface treated. In certain embodiments, more than <NUM>% of the surface of the organic pigment is surface treated. For example, the organic pigment may have between <NUM>% and <NUM>% (e.g., between <NUM>% and <NUM>%, between <NUM>% and <NUM>%) of its surface treated.

The compositions may comprise a TiO<NUM> pigment grind component (i.e. all of the TiO<NUM> present in the composition) that is more than <NUM>%, more than <NUM>%, more than <NUM>%, more than <NUM>%, more than <NUM>%, or more than <NUM>% rutile TiO<NUM> by weight of the TiO<NUM> component. In some embodiments, the TiO<NUM> component consists of rutile-TiO<NUM>. In some embodiments, TiO<NUM> may be present in an amount greater than <NUM>% by weight of the composition (e.g., <NUM>% to <NUM>% by weight of the composition, <NUM>% to <NUM>% by weight of the composition). In some embodiments, the TiO<NUM> in the pigment grind has a particle size greater than <NUM>. As used herein, particle size measurements may be performed with dynamic light scattering.

The ratio of TiO<NUM> and organic pigment may be altered to enhance the stability of the color in compositions dependent on the exact mixture and weight percentage of the pigment component (e.g., organic pigments, pigmentary TiO<NUM>, and inorganic pigments). In some embodiments, the weight ratio of organic pigments (e.g., Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Blue <NUM>, Yellow <NUM>, Red <NUM> lake, Red <NUM> lake, Red <NUM> lake, Blue <NUM> lake, Yellow <NUM> lake) to pigmentary rutile TiO<NUM> is between <NUM>:<NUM> and <NUM>:<NUM> by weight. In certain embodiments, the weight ratio of organic pigments to rutile TiO<NUM> may be between <NUM>:<NUM> and <NUM>:<NUM> by weight (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>). In other embodiments, the weight ratio of organic pigments to rutile TiO<NUM> may be between <NUM>:<NUM> and <NUM>:<NUM> by weight (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>).

Without wishing to be bound by theory, it is believed that the incorporation of metal oxide particles may enhance the color stability of the pigmented compositions. Furthermore, metal oxide particles with particle sizes of less than <NUM> or less than <NUM> or less than <NUM> or less than <NUM> or less than <NUM> or less than <NUM>µ or less than <NUM> result in compositions result in more homogenous color distributions in the bulk as compared to metal oxide particles with larger particles sizes. The metal oxide particles are selected from metal oxide particle is silica, alumina, zirconia, zinc oxide, indium tin oxide, ceria, and mixtures thereof, and/or wherein the said metal oxide particles are fumed metal oxide particles. In certain embodiments, the metal oxide component comprises less than <NUM>% or less than <NUM>% or less than <NUM>% or less than <NUM>% titanium oxide by weight of the metal oxide component. In some embodiments, the composition does not comprise titanium oxide. In some embodiments, the composition may be characterized as having a reduced color shift after <NUM> hours of heating between <NUM> and <NUM> as compared to an otherwise identical composition without the attenuation grade TiO<NUM>. For example, the compositions may comprise an amount of attenuation grade TiO<NUM> such that the composition may be characterized as having a ΔE of less than <NUM> after eight hours of heating at more than <NUM> (e.g., between <NUM> and <NUM>).

The compositions may comprise additional pigments or particulate materials for ultraviolet light absorption or scattering such as zinc oxide particulates, or for other aesthetic characteristics such as pearlescence (e.g., mica, bismuth oxychloride). Exemplary inorganic pigments include, but are not limited to, inorganic oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminum hydroxide, iron oxides (α-Fe<NUM>O<NUM>, γ-Fe<NUM>O<NUM>, Fe<NUM>O<NUM>, FeO) and iron hydroxides including red iron oxide, yellow iron oxide and black iron oxide, titanium lower oxides, zirconium oxides, chromium oxides, chromium hydroxides, manganese oxides, manganese hydroxides, cobalt oxides, cobalt hydroxides, cerium oxides, cerium hydroxides, nickel oxides, nickel hydroxides, zinc oxides and zinc hydroxides and composite oxides and composite hydroxides such as iron titanate, cobalt titanate and cobalt aluminate and the like. Preferably, the inorganic oxide particles may be selected from silica, alumina, zinc oxide, and iron oxide particles, and mixtures thereof. In one embodiment, the inorganic pigments have a particle size from <NUM> to <NUM> microns, or from <NUM> to <NUM> microns, or from <NUM> to <NUM> microns. In some embodiments, the particle size (median) will be less than bout <NUM> microns or less than <NUM> micron. In some embodiments, the composition comprises less than <NUM>% inorganic pigments (other than TiO<NUM>) by weight of the composition. In some embodiments, the composition comprises less than <NUM>% inorganic pigments (other than TiO<NUM>) by weight of the composition. In some embodiments, the composition comprises less than <NUM>% inorganic pigments (other than TiO<NUM>) by weight of the composition. In some embodiments, the composition comprises less than <NUM>% iron oxide by weight of the composition. In some embodiments, the composition comprises less than <NUM>% iron oxide by weight of the composition. In some embodiments, the composition comprises less than <NUM>% iron oxide by weight of the composition.

The total pigment content of the compositions (e.g., organic pigments, TiO<NUM> (e.g., pigmentary rutile TiO<NUM>, inorganic pigments)) is typically less than <NUM>% by weight of the composition (e.g., less than <NUM>% by weight of the composition, less than <NUM>% by weight of the composition, less than <NUM>% by weight of the composition). In some embodiments, the total pigment content is between <NUM>% and <NUM>% by weight of the composition.

The pigmented composition typically has a mix of individual pigments to result in certain color shades of the composition. This pigment component may have decreased susceptibility to color shift. For example, in some embodiments, the composition does not have a (L*,a*,b*) color value with the specular component included ("SCI") of (L*=<NUM>±<NUM>, a*=<NUM>±<NUM>, b*=<NUM>±<NUM>). Persons of ordinary skill in the art are able to measure L*a*b* values, for example by the measurement procedure detailed in Example <NUM>. In some embodiments, the composition has a change in color of less than <NUM> (e.g., less than <NUM>, less than <NUM>) after eight hours of heating at more than <NUM> (e.g., between <NUM> and <NUM>, between <NUM> and <NUM>). Differences between points in color space can be calculated (or approximated) using standard Euclidean geometry of the color space. For example, the color difference may be calculated with equation (<NUM>): <MAT>.

The pigments, and specifically the organic pigments, may be surface treated. In some embodiments, the TiO<NUM> is surface treated. In some embodiments, both the TiO<NUM> and the organic pigments are independently surface treated. In certain implementations, the TiO<NUM> (e.g., attenuation grade TiO<NUM>, rutile TiO<NUM>) and the organic pigment (e.g., Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Blue <NUM>, Yellow <NUM>, Red <NUM> lake, Red <NUM> lake, Red <NUM> lake, Blue <NUM> lake, Yellow <NUM> lake) are independently surface treated. In various embodiments, TiO<NUM>, the organic pigment, and the inorganic pigment are independently surface treated. In certain implementations, the TiO<NUM> (e.g., attenuation grade TiO<NUM>, rutile TiO<NUM>) and the organic pigment (e.g., Red <NUM>, Red <NUM>, Red <NUM>, Red <NUM>, Blue <NUM>, Yellow <NUM>, Red <NUM> lake, Red <NUM> lake, Red <NUM> lake, Blue <NUM> lake, Yellow <NUM> lake) have the same surface treatment. In various embodiments, TiO<NUM>, the organic pigment, and the inorganic pigment are independently surface treated. In some embodiments, TiO<NUM>, the organic pigment, and the inorganic pigment each have the same surface treatment.

The surface treatment may be any such treatment that modifies the surface of the modifying agent and/or the first colorant. For example, the surface treatment may make the pigments more hydrophobic or more dispersible in a vehicle or may increase the adhesion of the pigments to a modifying agent. The surface of the pigments may, for example, be covalently or ionically bound to an organic molecule or silicon-based molecule or may be adsorbed thereto, or the pigments may be physically coated with a layer of material. The surface treatment compound may be attached to the pigment through any suitable coupling agent, linker group, or functional group (e.g., silane, ester, ether). The compound may comprise a hydrophobic portion which may be selected from, for example, alkyl, aryl, allyl, vinyl, alkylaryl, aryl-alkyl, organosilicone, di-organosilicone, dimethicones, methicones, polyurethanes, silicone-polyurethanes, and fluoro- or perfluoro-derivatives thereof. Other hydrophobic modifiers include lauroyl lysine, Isopropyl Titanium Triisostearate (ITT), ITT and Dimethicone (ITT/Dimethicone) cross-polymers, ITT and Amino Acid, ITT/Triethoxycaprylylsilane Crosspolymer, waxes (e.g., carnauba), fatty acids (e.g., stearates), HDI/Trimethylol Hexylactone Crosspolymer, PEG-<NUM> Methyl Ether Triethoxysilane, aloe, jojoba ester, lecithin, Perfluoroalcohol Phosphate, and Magnesium Myristate (MM), to name a few. In some embodiments, the organic pigments and/or the TiO<NUM> (e.g., pigmentary TiO<NUM>, attenuation grade TiO<NUM>, pigmentary TiO<NUM> and attenuation grade TiO<NUM>) is surface treated. In specific embodiments, the organic pigments are ITT treated. In certain embodiments, the TiO<NUM> is ITT/Dimethicone treated. In various embodiments, the organic pigments and the TiO<NUM> are /Dimethicone treated. In specific embodiments, the organic pigments are /Dimethicone treated. In certain embodiments, the TiO<NUM> is ITT/Dimethicone treated. In various embodiments, the organic pigments and the TiO<NUM> are ITT treated. Specific surface treated organic pigments which may be used include (INCI names):.

The surface treatment may comprise, in some embodiments, a material selected from aluminum laurate, aluminum stearate, an amino acid, chitin, collagen, fluorochemical, lecithin, metal soap, natural wax, polyacrylate, polyethylene, silicone, silane, titanatate ester, urethane, dimethicone, perfluoropolymethylisopropyl ether, styrene acrylates copolymer, magnesium myristate, lauroyl lysine and a combination thereof. In other embodiments, the surface treatment comprises a material selected from methicone, triethoxycaprylylsilane, trimethoxycaprylylsilane, dimethicone copolyol and a combination thereof.

The compositions may be in the form of an emulsion. Typically, the emulsions may comprise water and/or glycerin. The emulsions may be a water-in-oil, oil-in-water, silicone-in-water, water-in-silicone, polyol-in-oil, oil-in-polyol, glycerin-in-oil, oil-in-glycerin, silicone-in-glycerin, glycerin-in-silicone, silicone-in-polyol, or polyol-in-silicone emulsion. In preferred embodiments, the emulsion is a water-in-oil, oil-in-water, silicone-in-water, or water-in-silicone emulsion. The emulsions may comprise a non-aqueous external phase (e.g., oil phase, silicone phase). In some embodiments, the emulsions may comprise an aqueous, a polyol, or a glycerin internal phase. In some embodiments the composition may comprise from <NUM>-<NUM>% (e.g., <NUM>% to <NUM>%, <NUM>% to <NUM>%, <NUM>% to <NUM>%) of the internal phase (e.g., glycerin).

In some embodiments, the external (continuous) phase is an emollient oil phase. For example, the continuous oil phase may comprise any suitable oils for emulsions, including, without limitation, vegetable oils; fatty acid esters; fatty alcohols; isoparaffins such as isododecane and isoeicosane; hydrocarbon oils such as mineral oil, petrolatum, and polyisobutene; polyolefins and hydrogenated analogs thereof (e.g., hydrogenate polyisobutene); natural or synthetic waxes; silicone oils such as dimethicones, cyclic silicones, and polysiloxanes; and the like. In certain implementations, the composition comprises from external phase carrier comprises from <NUM>% to <NUM>% emollient (e.g., silicone such as diphenyl dimethicone, ester oil such as ethylhexyl palmitate) by weight of the composition.

Suitable ester oils include fatty acid esters. Special mention may be made of those esters commonly used as emollients in cosmetic formulations. Such esters will typically be the etherification product of an acid of the form R<NUM>(COOH)<NUM>-<NUM> with an alcohol of the form R<NUM>(OH)<NUM>-<NUM> where R<NUM> and R<NUM> are each independently linear, branched, or cyclic hydrocarbon groups, optionally containing unsaturated bonds (e.g., from <NUM>-<NUM> or <NUM>-<NUM> or <NUM>), and having from <NUM> to <NUM> (e.g., <NUM>-<NUM> or <NUM>-<NUM>, or <NUM>-<NUM>, or <NUM>-<NUM>) carbon atoms, optionally substituted with one or more functionalities including hydroxyl, oxa, oxo, and the like. Preferably, at least one of R<NUM> and R<NUM> comprises at least <NUM>, or at least <NUM>, or at least <NUM>, or at least <NUM> or at least <NUM> carbon atoms, such that the ester comprises at least one fatty chain. The esters defined above will include, without limitation, the esters of mono-acids with mono-alcohols, mono-acids with diols and triols, diacids with mono-alcohols, and tri-acids with mono-alcohols.

Suitable fatty acid esters include, without limitation, butyl acetate, butyl isostearate, butyl oleate, butyl octyl oleate, cetyl palmitate, ceyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetyl stearate, diisostearyl fumarate, diisostearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, di-C<NUM>-<NUM> alkyl malate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisopropyl dimerate, triisostearyl trilinoleate, octodecyl stearoyl stearate, hexyl laurate, hexadecyl isostearate, hexydecyl laurate, hexyldecyl octanoate, hexyldecyl oleate, hexyldecyl palmitate, hexyldecyl stearate, isononyl isononanaote, isostearyl isononate, isohexyl neopentanoate, isohexadecyl stearate, isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, lauryl lactate, octacosanyl palmitate, propylene glycol monolaurate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, ethylhexyl palmitate, hexacosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, stearyl lactate, stearyl octanoate, stearyl heptanoate, stearyl stearate, tetratriacontanyl stearate, triarachidin, tributyl citrate, triisostearyl citrate, tri-C<NUM>-<NUM>-alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl cocoate, tridecyl isononanoate, glyceryl monoricinoleate, <NUM>-octyldecyl palmitate, <NUM>-octyldodecyl myristate or lactate, di(<NUM>-ethylhexyl)succinate, tocopheryl acetate, and the like.

Other suitable esters include those wherein R<NUM> comprises a polyglycol of the form H-(O-CHR*-CHR*)n- wherein R* is independently selected from hydrogen or straight chain C<NUM>-<NUM> alkyl, including methyl and ethyl, as exemplified by polyethylene glycol monolaurate.

The oil may also comprise a volatile or non-volatile silicone oil. Suitable silicone oils include linear or cyclic silicones such as polyalkyl- or polyarylsiloxanes, optionally comprising alkyl or alkoxy groups having from <NUM> to <NUM> carbon atoms. Representative silicone oils include, for example, caprylyl methicone, cyclomethicone, cyclopentasiloxane decamethylcyclopentasiloxane, decamethyltetrasiloxane, diphenyl dimethicone, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, methicone, methyl-phenyl polysiloxane, octamethylcyclotetrasiloxane, octamethyltrisiloxane, perfluorononyl dimethicone, polydimethylsiloxanes, and combinations thereof. The silicone oil will typically, but not necessarily, have a viscosity of between <NUM> and <NUM>,<NUM> centistokes (cSt), preferably between <NUM> and <NUM>,<NUM> cSt measured at <NUM>° C.

In one embodiment, the silicone oil comprises phenyl groups, as is the case for a silicone oil such as methylphenylpolysiloxane (INCI name diphenyl dimethicone), commercially available from Shin Etsu Chemical Co under the name including F-5W, KF-<NUM> and KF-<NUM>. Diphenyl dimethicones have good organic compatibility and may impart film-forming characteristics to the product. Further, the presence of phenyl groups increases the refractive index of the silicone oil and thus may contribute to high gloss of product if desired. In one embodiment, the silicone oil will have a refractive index of at least <NUM>, preferably at least <NUM>, more preferably at least <NUM>, and more preferred still at least <NUM>, when measured at <NUM>° C. Another suitable phenyl-functionalized silicone oil has the INCI name phenyltrimethicone and is sold under the trade name DC <NUM> by Dow Corning. DC <NUM> has a refractive index of <NUM>. In one embodiment, the silicone oil is a fluorinated silicone, such as a perfluorinated silicone (i.e., fluorosilicones). Fluorosilicones are advantageously both hydrophobic and oleophobic and thus contribute to a desirable slip and feel of the product. Fluorosilicones also impart long-wearing characteristics to a lip product. Fluorosilicones can be gelled with behenyl behenate if desired. One suitable fluorosilicone is a fluorinated organofunctional silicone fluid having the INCI name perfluorononyl dimethicone. Perfluorononyl dimethicone is commercially available from Pheonix Chemical under the trade name PECOSIL®. The compositions may comprise between <NUM>% and <NUM>% emollient (e.g., silicone oil, ester oil) by weight of the composition (e.g., between <NUM>% and <NUM>% by weight of the composition, between <NUM>% and <NUM>% by weight of the composition, between <NUM>% and <NUM>% by weight of the composition).

The compositions may also comprise hydrocarbon oils. Exemplary hydrocarbon oils are straight or branched chain paraffinic hydrocarbons having from <NUM> to <NUM> carbon atoms, typically from <NUM> to <NUM> carbon atoms, and more typically from <NUM> to <NUM> carbon atoms, including but not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, tridecane, and the like. Some useful hydrocarbon oils are highly branched aliphatic hydrocarbons, including C<NUM>-<NUM> isoparaffins, C<NUM>-<NUM> isoparaffins, C<NUM> isoparaffin, C<NUM>-<NUM> isoparaffins and the like. Special mention may be made of the isoparaffins having the INCI names isohexadecane, isoeicosane, and isododecane (IDD).

Also, suitable as hydrocarbon oils are poly-α-olefins, typically having greater than <NUM> carbon atoms, including (optionally hydrogenated) C<NUM>-<NUM> olefins, C<NUM>-<NUM> olefins, polyisobutene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, hydrogenated polycyclopentane, mineral oil, pentahydrosqualene, squalene, squalane, and the like. The hydrocarbon oil may also comprise higher fatty alcohols, such as oleyl alcohol, octyldodecanol, and the like.

Other suitable oils include without limitation castor oil, C<NUM>-<NUM> triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, walnut oil, avocado oil, camellia oil, macadamia nut oil, turtle oil, mink oil, soybean oil, grape seed oil, sesame oil, maize oil, rapeseed oil, sunflower oil, cottonseed oil, jojoba oil, peanut oil, olive oil, and combinations thereof.

Any one of the foregoing ester oils, silicone oils, and hydrocarbon oils are contemplated to be useful in the compositions described herein. Accordingly, in one embodiment, the compositions comprise at least one oil selected from the ester oils, silicone oils, and hydrocarbon oils described above. In another embodiment, the compositions comprise two or more oils selected from the ester oils, silicone oils, and hydrocarbon oils described above. In yet another embodiment, the compositions will comprise at least one ester, at least one silicone oil, and at least one hydrocarbon oil from the list above. Because the ester oils described herein function as emollients, it may be advantageous for the compositions comprise at least one ester oil, and may optionally comprise at least one additional oil selected from hydrocarbon oils, silicone oils, and combinations thereof.

Although not required, the compositions typically have an aqueous phase. In most embodiments, the aqueous phase is the discontinuous phase of emulsions (e.g., water-in-oil, glycerin-in-oil). As hydrolysis of the organic pigments may cause the color shift, these compositions are most affected by the increased color stability provided by the compositions of the invention. In some embodiments, the aqueous phase solvents are present from <NUM>% to <NUM>% (e.g., <NUM>% to <NUM>%, <NUM> to <NUM>%, <NUM> to <NUM>%) by weight of the composition. In other embodiments, the compositions are anhydrous.

Waxes and/or fillers may also be optionally added (particularly in those embodiments where the composition is a free standing solid at room temperature), in an amount ranging from at or <NUM>% to or including <NUM>% by weight of the composition or ranging from at or <NUM>% to or including <NUM>% by weight of the composition. Examples of fillers may include, but are not limited to silica, PMMA, nylon, alumina, barium sulfate, or any other filler used in such compositions. Examples of waxes may include, but are not limited to, linear polyethylene, microcrystalline petroleum wax, carnauba wax, lignite wax, ouricouri wax, rice bran wax, castor wax, mortar wax, stearone, acrawax, bayberry wax, castor wax, Japan wax, ozokerite, beeswax, candelilla wax, petrolatum, ceresin wax, cocoa buter, illipe butter, esparto wax, shellac wax, ethylene glycol diesters or triesters of C<NUM>-C<NUM> fatty acids, cetyl palmitate, hard tallow, paraffin wax, lanolin, lanolin alcohol, cetyl alcohol, glyceryl monostearate, sugarcane wax, jojoba wax, stearyl alcohol, silicone waxes, and combinations thereof.

In some embodiments, the oil phase can include one or more waxes. Waxes may impart body to the emulsion so that the emulsion has the physical form of a semi-solid or solid. As used herein, the term "solid" is intended to refer to a composition that is self-supporting and capable of being molded into a free-standing stick (e.g., a lip stick). In some embodiments, the waxes are present in an amount sufficient to make the emulsion a solid emulsion. For example, the solid emulsion can have a hardness of at least <NUM>. The composition typically has hardness at room temperature of at least <NUM>. In one embodiment, the composition may have a substantially greater hardness, between <NUM> and <NUM>. The hardness of an emulsion may be measured on a Texture Analyzer Model QTS-<NUM> equipped with a <NUM> stainless steel probe (TA-<NUM>), as described in Avon's <CIT>.

The waxes may be natural, mineral and/or synthetic waxes. Natural waxes include those of animal origin (e.g., beeswax, spermaceti, lanolin, and shellac wax) and those of vegetable origin (e.g., carnauba, candelilla, bayberry, and sugarcane wax). Mineral waxes include, without limitation ozokerite, ceresin, montan, paraffin, microcrystalline, petroleum, and petrolatum waxes. Synthetic waxes include, for example, polyethylene glycols such as PEG-<NUM>, PEG-<NUM>, PEG-<NUM>, PEG-<NUM>, PEG-<NUM>, PEG-<NUM>, and PEG-<NUM> which are sold under the tradename CARBOWAX® (The Dow Chemical Company). Mention may be made of the polyethylene glycol wax CARBOWAX <NUM> which has a molecular weight range of <NUM> to <NUM>,<NUM> and a melting point of <NUM>° C. , CARBOWAX <NUM> which has a molecular weight range of <NUM>,<NUM> to <NUM>,<NUM> and a melting point of <NUM>° C. , CARBOWAX <NUM> which has a molecular weight range of <NUM>,<NUM> to <NUM>,<NUM> and a melting point of <NUM>° C. , and CARBOWAX <NUM> which has a molecular weight range of <NUM>,<NUM> to <NUM>,<NUM> and a melting point of <NUM>° C.

Synthetic waxes also include Fischer Tropsch (FT) waxes and polyolefin waxes, such as ethylene homopolymers, ethylene-propylene copolymers, and ethylene-hexene copolymers. Representative ethylene homopolymer waxes are commercially available under the tradename POLYWAX® Polyethylene (Baker Hughes Incorporated) with melting points ranging from <NUM>° C. to <NUM>° C. Commercially available ethylene-α-olefin copolymer waxes include those sold under the tradename PETROLITE® Copolymers (Baker Hughes Incorporated) with melting points ranging from <NUM>° C. to <NUM>° C.

In one embodiment, the emulsion includes, in the oil phase, at least one wax selected from arcawax (N,N'-ethylenebisstearamide), microcrystalline wax, linear polyethylene wax, stearone (<NUM>-pentatriacontanone), castor wax, montan wax, lignite wax, ouricouri wax, carnauba wax, rice bran wax, shellac wax, esparto wax, ozokerite wax, jojoba wax, candelilla wax, ceresin wax, beeswax, castor wax, sugarcane wax, stearyl alcohol, hard tallow, cetyl alcohol, petrolatum, glyceryl monostearate, Japan wax, silicone wax, paraffin wax, lanolin wax, lanolin alcohol, bayberry wax, cetyl palmitate, illipe butter, cocoa butter, and ethylene glycol di- or tri-esters of C<NUM>-<NUM> fatty acids.

The amount of wax, if present, may be less than <NUM>% (e.g., <NUM>-<NUM>%) by weight of the composition if the composition is a liquid or if clarity is desired. The amount of wax, if present, will typically be greater than <NUM>% (e.g., <NUM>-<NUM>%) by weight of the composition if the composition is a semisolid or solid or if clarity is not a concern. In some embodiments, the emulsion may comprise wax from <NUM>% to <NUM>% (or <NUM>-<NUM>% or <NUM>-<NUM>% or <NUM>-<NUM>%) by weight of the composition, particularly in embodiments formulated as lip sticks.

In one embodiment, composition includes, in the oil phase, from <NUM>-<NUM>% or <NUM>-<NUM>% or <NUM>-<NUM>% or <NUM>-<NUM>% or <NUM>-<NUM>% by weight of at least one wax (e.g., microcrystalline wax, ozokerite wax, polyethylene wax, paraffin wax, petrolatum wax). In one embodiment, the composition includes, in the oil phase, microcrystalline wax within the foregoing amounts. In one embodiment, the composition includes, in the oil phase, ozokerite wax within the foregoing amounts. In one embodiment, the composition includes, in the oil phase, polyethylene wax within the foregoing amounts. In one embodiment, the composition includes, in the oil phase, petrolatum wax within the foregoing amounts. In one embodiment, the composition includes, in the oil phase, paraffin wax within the foregoing amounts.

Typically, emulsions according to the invention further comprise one or more emulsifiers. For example, the one or more emulsifiers may be present in a total range from <NUM>% to <NUM>% by weight of the emulsion. In some embodiments, the total amount of emulsifier ranges from <NUM>% to <NUM>% be weight, or from <NUM>% to <NUM>% by weight of the emulsions. Examples of emulsifiers include polyglyceryl compounds such as polyglyceryl-<NUM>-polyricinoleate, polyglyceryl pentaoleate, polyglyceryl-isostearate, and polyglyceryl-<NUM>-diisostearate; glycerol esters such as glycerol monostearate or glycerol monooleate; phospholipids and phosphate esters such as lecithin and trilaureth-<NUM>-phosphate (available under the tradename HOSTAPHAT®KL-<NUM>-D); sorbitan-containing esters (including SPAN® esters) such as sorbitan laurate, sorbitan oleate, sorbitan stearate, or sorbitan sesquioleate; polyoxyethylene phenols such as polyoxyethylene octyl phenol; polyoxyethylene ethers such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether; polyethylene glycol emulsifiers such as PEG-<NUM>-polyhydroxystearate or alkylpolyethylene glycols; polypropylene glycol emulsifiers such as PPG-<NUM>-laureth-<NUM>; dimethicone polyols and polysiloxane emulsifiers; and the like. Combinations of emulsifiers, such as the combination of lecithin and sorbitan, are envisioned. Additional emulsifiers are provided in the <NPL>.

Additional components may be incorporated for various functional purposes as is customary in the cosmetic arts into the composition, and specifically the internal phase of emulsions, the external phase of emulsions, or as a particulate phase. However, while additional components consistent to formulate the above cosmetic compositions may be included, the inclusion of additional ingredients is limited to those ingredients in amounts which do not interfere with the formation or stability of the compositions (e.g., emulsions).

Such components may be selected from the group consisting of film-formers, pigments, waxes, emollients, moisturizers, preservatives, flavorants, antioxidants, botanicals, and mixtures thereof. Particular mention may be made of highly purified botanical extracts or synthetic agents which may have wound-healing, anti-inflammatory, or other benefits useful for treating the skin or lips. Additional embodiments may include antioxidants such as tocopherol and/or α-hydroxy acids like glycolic acid, and lactic acid. The compositions may include one or more film-formers to increase the substantivity of the product.

Film formers, including film forming polymers, may also be employed. The term film-forming polymer may be understood to indicate a polymer which is capable, by itself or in the presence of at least one auxiliary film-forming agent, of forming a continuous film which adheres to a surface and functions as a binder for the particulate material. Polymeric film formers include, without limitation, acrylic polymers or co-polymers, (meth)acrylates, alkyl(meth)acrylates, polyolefins, polyvinyls, polacrylates, polyurethanes, silicones, polyamides, polyethers, polyesters, fluoropolymers, polyethers, polyacetates, polycarbonates, polyamides, polyimides, rubbers, epoxies, formaldehyde resins, organosiloxanes, dimethicones, amodimethicones, dimethiconols, methicones, silicone acrylates, polyurethane silicones copolymers, cellulosics, polysaccharides, polyquaterniums, and the like. Suitable film formers include those listed in the Cosmetic Ingredient Dictionary (<NPL>).

The composition may comprise one or more preservatives or antimicrobial agents, such as methyl, ethyl, or propyl paraben, and so on, in amounts ranging from <NUM>-<NUM> wt % by weight of the total composition. The compositions may have other ingredients such as one or more anesthetics, anti-allergenics, antifungals, anti-inflammatories, antimicrobials, antiseptics, chelating agents, emollients, emulsifiers, fragrances, humectants, lubricants, masking agents, medicaments, moisturizers, pH adjusters, preservatives, protectants, soothing agents, stabilizers, sunscreens, surfactants, thickeners, viscosifiers, vitamins, or any combinations thereof.

In one embodiment, the emulsions according to the invention are provided as products for application to the lips. Such lip products may include lip cream, lip balm, lip gloss, medicated lip treatment, lip moisturizer, lip cosmetic, lip sunscreen, and lip flavorant. In one embodiment, the lip product is a creamy, flowable lip product. In certain embodiments, products according to the invention may have the consistency of a semi-viscous liquid or paste. In other embodiments, the product is a lipstick.

When formulated as lip products, the emulsions according to the invention may be packaged in a re-closeable container. Such containers may include an enclosure or chamber charged with the emulsion formulated as a cosmetic composition and a cap removably attached to the container or reversibly configured on the container. In one embodiment, a cap may be attached to a squeezable enclosure (e.g., formed of a pliant plastic material) such that the cap can be removed from the orifice of the squeezable enclosure and replaced upon completion of dispensing of the composition. A cap may be attached to the body of a squeezable enclosure (e.g., by screw threads, a snap fit, or the like), to facilitate re-sealing the squeezable enclosure for storage between uses. In one embodiment, the cap is reversibly attached to the container for sealing the contents when in a closed position and for permitting the contents of the container to be dispensed when in an open position. Various containers are envisioned, including without limitation click pens, barrel dispensers, pumps, air-less pumps, pressurized packages, hand-squeezed containers, a cosmetic applicator, and the like.

In other embodiments, the emulsions may be in the form of skin care emulsions (e.g., lotions, creams, gels), color cosmetics, mascaras, eye shadows, lip color, lip liner, foundation, concealer, make up remover, sunscreen, deodorants, to name a few.

A sunscreen for protecting the skin from damaging ultra-violet rays may also be included in the embodied compositions. In one embodiment, sunscreens may include, without limitation, those with a broad range of UVB and UVA protection, such as octocrylene, avobenzone, octyl methoxycinnamate, octyl salicylate, oxybenzone, homosylate, benzophenone, camphor derivatives, zinc oxide, triazine complexes (e.g., Tinsorb, Univul), and titanium oxide. When present, the sunscreen may be in an amount ranging from at or <NUM>% to or including <NUM>% by weight of the composition.

Suitable exfoliating agents may include, for example α-hydroxy acids, β-hydroxy acids, oxaacids, oxadiacids, and their derivatives such as esters, anhydrides, and salts thereof. Suitable hydroxy acids include, for example, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, <NUM>-hydrocxyalkanoic acid, mandelic acid, salicylic acid, and derivatives thereof. In some embodiments, the exfoliating agent is lactic acid. When present, the exfoliating agent may be in an amount ranging from at or <NUM>% to or including <NUM>% by weight of the composition.

The embodied compositions described here may further comprise one or more cosmetic powders or particulates, for example, calcium aluminum borosilicate, PMMA, polyethylene, polystyrene, methyl methacrylate crosspolymer, nylon-<NUM>, ethylene/acrylic acid copolymer, boron nitride, Teflon, silica, and the like. Typically, especially for makeup compositions, the compositions described here may additionally include colorants or pigments to impart a desired color or effect. Non-limiting examples may include inorganic pigments, organic pigments, and lakes. Exemplary inorganic pigments may include, but are not limited to, metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminum hydroxide, iron oxides (α-Fe<NUM>O<NUM>, γ-Fe<NUM>O<NUM>, Fe<NUM>O<NUM>, FeO), red iron oxide, yellow iron oxide, black iron oxide, iron hydroxides, titanium dioxide, titanium lower oxides, zirconium oxides, chromium oxides, chromium hydroxides, manganese oxides, cobalt oxides, cerium oxides, diatomaceous earth, nickel oxides, zinc oxides, composite oxides, and composite hydroxides such as iron titanate, cobalt titanate, and cobalt aluminate. Non-metal oxides are also contemplated to be suitable including alumina and silica, ultramarine blue, Prussian blue, manganese violet, bismuth oxychloride, talc, mica, sericite, magnesium carbonate, calcium carbonate, magnesium silicate, aluminum magnesium silicate, silicate, titanated mica, iron oxide titanated mica, bismuth oxychloride, and the like. Organic pigments may include, but are not limited to, at least one of carbon black, carmine, phthalocyanine blue and green pigment, diarylide yellow and orange pigments, and azo-type red and yellow pigments such as toluidine red, litho red, naphthol red and brown pigments, and combinations thereof.

In some embodiments, the compositions comprise polysaccharide thickener. In some embodiments, the compositions comprise an anionic polysaccharide (e.g., xanthan gum). In other embodiments, the compositions do not comprise a polysaccharide thickener or the composition comprises less than <NUM>%, less than <NUM>%, or less than <NUM>% a polysaccharide thickener by weight of the composition.

In one embodiment, the topical compositions (or aqueous phase thereof including an internal glycerin phase) may have a pH ranging from <NUM> to <NUM>, but typically have a pH ranging from <NUM> to <NUM>. In some embodiments, the internal phase has a pH between <NUM> and <NUM> or between <NUM> and <NUM> or between <NUM> and <NUM>. Suitable pH adjusters such as, but not limited to, sodium hydroxide, citric acid and triethanolamine may be included in the described composition to bring the pH within the desired range.

Exemplary ranges of composition ingredients are provided in Table <NUM> (percentages are listed as weight percentage of the composition) for a cosmetic composition, such as a lipstick. It should be noted that some components are optional. Additionally, the Pigment Component may comprise organic pigments, TiO<NUM> (e.g., anatase TiO<NUM>, rutile TiO<NUM>, a TiO<NUM> component consisting predominantly of rutile TiO<NUM>) and additional inorganic pigments (optional) in the specified amounts. In some embodiments, the compositions comprise an emulsifier, a fragrance oil, a powder, a preservative, a sweetening agent, a sunscreen agent, or combinations thereof.

Compositions may be formulated by preparing a pigment grind, wherein inorganic pigments, organic pigments, and pigmentary TiO<NUM> may be dispersed in a suitable carrier via shear. The pressure and/or shear (e.g., rubbing, brushing, combing) that is applied to the pigment grind may be provided by any suitable means for dispersing the pigment in the carrier, for example, by a three-roll mill. In some embodiments, each of the pigments are surface treated. Suitable carriers include ester oils such as ethylhexyl palmitate and silicones such as diphenyl dimethicone. In certain embodiments, the pigment grind may then be used formulated as an emulsion.

Table <NUM> shows several Pigment Grind Formulations which may be incorporated into the pigmented compositions described herein.

Pigment grinds may also be used to construct an emulsion with a glycerin internal phase. In some embodiments, the emulsions may comprise from <NUM>%-<NUM>% pigment grind by weight of the composition. An exemplary formulation is shown in Table <NUM>. It will be understood that the pigment grind weight percentage indicated in Table <NUM> includes <NUM>% diphenyl dimethicone. Accordingly, the composition illustrated in Table <NUM> comprises <NUM>% emollients by weight of the composition.

The following examples illustrate specific aspects of the instant description. The examples should not be construed as limiting, as the example merely provides specific understanding and practice of the embodiments and its various aspects.

Eight color formulations were prepared in both an anhydrous formulation and a glycerin-in-oil emulsion. For each color formulation, identical pigment grinds were placed in the anhydrous and the glycerin-in-oil emulsion at <NUM>% by weight of the composition. The pigments in each Color Shade Formulation are shown in Table <NUM>. Additionally, the L*a*b* space values (± <NUM>) with the specular component include ("SCI") for each Color Shade Formulation are shown in Table <NUM>.

The formulations were heated to <NUM>. This temperature was chosen as an optimal hold temperature by evaluating the melt point of the lipstick base wax phase by Differential Scanning Calorimetry ("DSC") and determining a range where the full phase transition from solid to liquid of the wax phase of the tested formulations occurred. At hour intervals beginning when the emulsions reached <NUM> (t=<NUM>), the change in color shade of each formulation from the initial heating time was measured (ΔE). Table <NUM> shows the corresponding L*a*b* space coordinates of the initial color shade of each formulation at t=<NUM>.

To measure the color at each time point, the bulk is drawn over a Lanetta card with a consistent <NUM> mil thickness. Measurements were performed on the white portion of the Lanetta card. Spectrophotometric measurements were performed in the L*a*b* color space using a Konica Minolta CM-2600D spectrophotometer. This process was designed to reflect manufacturing stresses placed on the compositions thereby being indicative of the color shade stability and consistency of a formulation in mass production. Color does not typically shift upon cooling as the forces which accelerate shade instability are energy sources (e.g., heat, light). Table <NUM> shows the corresponding L*a*b* space coordinates of the initial color shade of each formulation at t=<NUM>.

The change in color shade was monitored at hour intervals after each hour. At hour intervals beginning when the emulsions reached <NUM> (t=<NUM>), the change in color shade of each formulation from the initial heating time was measured (ΔE). <FIG> illustrates the change in color shade measurement for each of the anhydrous and glycerin-in-oil emulsion version of each Color Shade Formulation after eight hours of heating at <NUM> (ΔE between t=<NUM> and t=<NUM> hours).

As can be seen in <FIG>, as between anhydrous and glycerin-in-oil emulsion versions of each Color Shade Formulation, the color shade stability in anhydrous formulations is generally much greater than in glycerin-in-oil emulsions across the L*a*b* coordinate system, with the exception of Color Shade <NUM> (L*=<NUM>, a*=<NUM>, b*=<NUM>).

As can also be seen in <FIG>, some Color Shade Formulations, whether the anhydrous and glycerin-in-oil emulsion version, also are more affected by shifts in color shade than others (i.e., the instability also exists in anhydrous formulations, albeit to a lesser degree).

Grind formulation <NUM> (shown in Table <NUM>) was tested in various emulsions in order to demonstrate the effect the color shade stability afforded by the use of metal oxide particles with particle sizes of less than <NUM> or less than <NUM>. ITT Treated and ITT/dimethicone (TTB) treated compounds were purchased from KOBO products (New Jersey, USA).

Pigment Grind formulation <NUM> was formulated into glycerin-in-oil emulsions illustrated in Table <NUM>.

Each emulsion was a glycerin-in-oil emulsion with an acidic internal phase (pH between <NUM> and <NUM>). The initial L*a*b* space color values (SCI) were measured as described above in each batch with the initial L*a*b* color values shown in Table <NUM>.

As can be seen, there is minimal color difference between the batches. The initial difference in color shade between control and the fumed alumina emulsion is, for example: <MAT>.

In these experiments, the emollients weight percent does not include the emollients added from the pigment grind (total emollients in each composition are indicated in Table <NUM>). In these experiments, the attenuation grade TiO<NUM> was dispersed in the continuous phase rather than the pigment grind due to its high level of dispersibility.

The emulsions were heated to <NUM>. At hour intervals beginning when the emulsions reached <NUM> (t=<NUM>), the change in color shade (ΔE) for each emulsion from t=<NUM> was measured as in Example <NUM>. The ΔE values at each time point are shown in Table <NUM> and illustrated in <FIG>.

Claim 1:
A pigmented composition comprising:
(a) pigmentary titanium dioxide;
(b) organic pigments; and
(c) metal oxide particles having an average particle size of less than <NUM> (e.g., as measured by dynamic light scattering);
wherein the weight ratio of said pigmentary titanium dioxide and said organic pigments to said metal oxide particles in said composition is greater than <NUM>:<NUM> (e.g., <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>);
wherein said metal oxide particles are selected from silica, alumina, zirconia, zinc oxide, indium tin oxide, ceria, and mixtures thereof, and/or wherein said metal oxide particles are fumed metal oxide particles.