EA045485B1 - COMPOSITIONS WITH INCREASED COLOR FASTENANCE - Google Patents

Description

Cross reference to related applications

This application claims priority to U.S. Patent Application No. 16/439472, filed June 12, 2019, which claims priority to U.S. Patent Application No. 62/683954, filed June 12, 2018, each of which is incorporated herein by reference throughout its completeness.

Field of technology to which the invention relates

The present invention generally relates to methods and compositions for topical application to the external surface of the human body, including the skin and lips. More specifically, the present invention relates to compositions with improved color fastness, methods of using these compositions and methods for their preparation.

Prerequisites for creating an invention

Pigmented topical products are often formulated using either emulsions or anhydrous systems. Typically include materials such as iron oxide pigments in aqueous systems to create a variety of skin tones. Typically, waterless systems consist primarily of oils and waxes and are used to formulate eye shadows and lipsticks. These anhydrous systems often contain a chemical class of dyes called azo dyes, providing compositions in a wide range of color palettes. When these azo dyes are deposited as salts onto a substrate, they become brightly colored paint pigments that are defined by the D&C and FD&C classes of dyes.

Typically, D&C and FD&C paint pigments cannot be incorporated into aqueous systems due to hydrolysis at multiple sites in these large molecules. It is well known that processing of paint pigments can delay hydrolysis in aqueous systems to some extent. For example, ITT treatment of organic pigments is often used to improve the color fastness of compositions containing azo dyes. However, factors such as heat during the manufacturing and filling processes can neutralize pigment processing and cause hydrolysis of azo-based colorants despite surface treatment. Such hydrolysis will change the final color of the compositions during manufacture, thereby resulting in a less desirable product. Instead of organic pigments, iron oxides are often used in combination with titanium dioxide to create a discreet palette of shades.

Cosmetic products also often use titanium dioxide (TiO ₂ ), which is mined as a combination of crystalline forms; rutile and anatase. Anatase is the predominantly used form of TiO ₂ in decorative cosmetics. Titanium dioxide is combined with organic pigment materials to produce the more vibrant colors seen in lipsticks, blushes and eye shadows by providing increased refraction of the pigment colors (TiO2 is typically a white solid). However, the electrons donated by titanium dioxide into the system often worsen the color change of compositions, in particular in aqueous compositions with organic pigments. Consequently, long-lasting emulsion lipsticks do not exist in a palette of rich shades of vibrant colors, since the colors obtained through various combinations of organic pigments are not achieved in these lipsticks.

It is therefore an object of the present invention to provide pigmented compositions having reduced color change over time.

Short description

According to the above and other purposes, this present invention provides compositions with reduced color change. Reduced color change can be observed after heating compositions for extended periods of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8 hours, etc.) at elevated temperatures (e.g., greater than 60°C, etc. .d.). Without being limited by any theory, it is believed that certain TiO2-based components are capable of preventing hydrolysis of organic components while imparting color stability. By stabilizing the organic pigments, the compositions of the present invention can be formulated in a wider range of shades than previously available. In certain embodiments, reduced color change is achieved by using a crystalline form of rutile TiO2 in combination with organic pigments. In certain embodiments, color fastness is most pronounced in aqueous systems that are heated and held at higher temperatures (e.g., greater than 60°C, greater than 70°C, greater than 80°C, greater than 85°C, etc.) for longer periods of time (e.g. 8 hours, etc.) since the onset of organic pigment instability is exothermic. In particular, these higher temperatures are above the melting temperature of the base composition (ie the composition without pigment grinding), where a complete phase transition from solid to liquid occurs.

Accordingly, pigmented compositions are provided containing (a) titanium dioxide (eg, pigmented TiO ₂ , a combination of pigmented TiO ₂ and radiation attenuation grade TiO ₂ , etc.) consisting of or predominantly consisting of rutile phase titanium dioxide; And

- 1 045485 (b) organic pigments optionally with a treated surface.

In certain embodiments, the organic pigments are surface treated with isopropyl triisostearyl titanate (ITT) and/or ITT/dimethicone. In most embodiments, the pigmented compositions are aqueous or contain an aqueous phase. In certain embodiments, the pigmented compositions further comprise radiation attenuation grade TiO2 (eg, radiation attenuation grade rutile TiO2, radiation attenuation grade anatase TiO2, etc.).

Typically the compositions are in the form of an emulsion. The emulsion may be, for example, 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-silicon. 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.

In certain embodiments, the pigmented composition may be provided as a glycerin-in-oil emulsion containing (a) from 0.1 to 10% rutile pigment TiO2 by weight of the composition;

(b) from 1 to 10% organic pigments (eg, red 7, red 6, red 27, red 33, blue 1, yellow 5, etc.) by weight of the composition;

(c) from 20 to 50% silicone by weight of the composition; and (d) from 1 to 40% (eg, 1-10%, 20-30%, 30-40%, etc.) glycerin, by weight of the composition.

Also presented is a method for coloring the outer cover of the human body, which includes applying to the outer cover of the human body a composition containing (a) titanium dioxide (for example, pigmented TiO2, a combination of pigmented TiO2 and TiO2 qualified for radiation attenuation, etc.), consisting of or predominantly consisting of rutile phase titanium dioxide; and (b) organic pigments, optionally surface treated.

In some embodiments, the outer covering of the human body is a keratinized surface. The keratinized surface may be hair (eg, eyebrows, eyelashes, etc.), skin, lips, or nails (eg, toes, fingernails, supraungual plates, etc.). In some embodiments, the compositions are applied to the lips.

Brief description of graphic materials

In fig. 1 shows the measured color change (AE) after 8 hours of heating of anhydrous and glycerin-in-oil emulsions with various pigment components.

Fig. 2-4 are scatter plots of the measured change in color hue measured over 8 hours for formulations 1, 2 and 3, respectively. The solid line with black circles represents data measured when each formulation was formulated with untreated anatase TiO2. The solid line with white circles represents data measured when each formulation was formulated with ITT-treated anatase TiO ₂ . The dotted line with open circles shows the composition formulated with ITT-treated rutile TiO ₂ .

In fig. 5 compares the values of the measured color change (AE) after 8 hours of heating for compositions 1-3 with different grinding compositions. The black column represents the untreated anatase TiO ₂ formulation, the white column represents the ITT-treated anatase TiO ₂ formulation, and the column shaded with parallel diagonal lines represents the ITT-treated rutile TiO ₂ formulation. The dashed horizontal line illustrates AE=2.3, the approximate limit for the minimum color change noticeable to the human eye.

In fig. 6 shows the measured color change (AE) for Formulation 4 after 8 hours of heating using TiO ₂ as raw anatase, raw rutile, ITT-treated anatase and ITT-treated rutile.

In fig. 7 shows the measured color change (AE) for formulation 5 after 8 hours of heating using TiO ₂ as raw anatase, raw rutile, ITT-treated anatase and ITT-treated rutile.

In fig. 8A illustrates color change values for various emulsion compositions formulated with and without radiation attenuation grade TiO ₂ .

In fig. 8B compares the color change values for each emulsion after 8 hours of heating at 90°C. The dotted horizontal line represents the AE approximation for a noticeable change in color.

Detailed Description of the Invention

Detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative

- 2 045485 for the present invention, which can be embodied in various forms. In addition, each of the examples given in relation to various embodiments of the invention are intended to be illustrative and not limiting.

All terms used herein are intended to have their common meaning in the art unless otherwise noted. All concentrations are expressed as a percentage by weight of the indicated component relative to the total weight of the topical composition unless otherwise indicated.

As used herein, the singular forms also include the plural. Singular forms used in conjunction with the word containing in this document also include the plural. As used herein, the term other means at least second or more.

As used herein, the expression predominantly consisting of relative to the rutile content of TiO2 means that the TiO2 is predominantly composed of rutile TiO2. For example, compositions with TiO2 consisting predominantly of rutile TiO2 would mean that the TiO2 present in the composition is greater than 60%, greater than 70%, greater than 80%, or greater than 90% rutile TiO2 by weight of the total TiO2 present in the composition (i.e. TiO2-based component). In one embodiment, the TiO2 present in the composition constitutes more than 80% by weight of the TiO2-based component. In a further embodiment, the TiO2 present in the composition is greater than 90% (eg, greater than 95%, greater than 99%, etc.) by weight of the _TiO2- based component.

All numeric value ranges used in this document include the endpoints and all possible values expanded between the expanded values. The exact values of all half-integer numeric values are also considered to be specifically disclosed and as limits for all subsets of the disclosed range. For example, the range from 0.1 to 3% specifically discloses the percentages of 0.1, 1, 1.5, 2.0, 2.5 and 3%. Additionally, the 0.1 to 3% range includes subsets of the original range, including 0.5 to 2.5%, 1 to 3%, 0.1 to 2.5%, etc. It should be understood that the sum of all weight % of the individual components will not exceed 100%.

The term oil as used herein is intended to include silicone oils unless otherwise noted. The term oil is intended to include volatile and/or non-volatile oils. The terms internal and dispersed phase are synonymous, as are the terms external and continuous phase. The terms glycerin and glycerol are synonymous and are used interchangeably. It should be understood that the oil phases of the compositions may contain one or more silicone oils as a major or non-primary component of the oil phase. It should also be understood that the aqueous phases of the compositions may contain one or more polyols (e.g., glycerin, etc.) as a minor component, and the polyol (e.g., glycerin, etc.) phases of the compositions may contain water as a minor component .

The compositions of the present invention are used for application to the human external integumentary system, including skin, lips, nails, hair and other keratinized surfaces. As used herein, the term keratinized surface means the keratin-containing portions of the human integumentary system, which includes, but is not limited to, the skin, lips, hair (including eyebrows and eyelashes), and nails (e.g., toenails, fingernails, supracungual plates, and etc.) mammals, preferably humans. Keratin fiber includes scalp hair, eyelashes, eyebrows, facial hair, and body hair such as arm hair, leg hair, etc.

The pigmented composition may contain (a) titanium dioxide consisting of or predominantly consisting of rutile phase titanium dioxide; and (b) organic pigments, optionally surface treated (eg, isopropyl triisostearyl titanate, ITT/dimethicone, etc.).

In some embodiments, the composition is aqueous or contains an aqueous phase.

Organic pigments may include, without limitation, at least one of carbon black, carmine, phthalocyanine blue and green pigments, diarylide yellow and orange pigments, and red and yellow azo 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 a salt of the organic pigment with Al ⁺ , Ba ⁺ , Ca ⁺ , etc.

The compositions may contain, for example, one or more dyes, toners or varnishes. Varnishes generally refer to a colorant derived from a water-soluble organic dye (e.g., D&C or FD&C, etc.) that has been deposited onto an insoluble reactive or adsorbent substrate or diluent. In some embodiments, the organic pigments may be based on an azo dye or contain one or more azo moieties. Typically, azo pigments are organic compounds containing an -N=N- bond. The term D&C refers to drug and cosmetic colorants that are approved by the FDA for use in drugs and cosmetics. The term FD&C refers to food, drug and cosmetic colorants that are approved by the FDA for use in food, drug and cosmetic products. D&C and FD&C certified colorants are listed in 21 C.F.R. § 74.101 et seq. and includes FD&C Blue 1, Blue 2, Green 3, Orange B, Citrus Red 2, Red 3, Red 4, Red 40, Yellow 5, Yellow 6, Blue 1, Blue 2; orange B, citrus red 2 and D&C blue 4, blue 9, green 5, green 6, green 8, orange 4, orange 5, orange 10, orange 11, red 6, red 7, red 17, red 21, red 22 , red 27, red 28, red 30, red 31, red 33, red 34, red 36, red 39, purple 2, yellow 7, yellow 8, yellow 10, yellow 11, blue 4, blue 6, green 5, green 6, green 8, orange 4, orange 5, orange 10, orange 11, etc. For example, the pigmented composition may contain D&C red 19 (for example, CI 45170, CI 73360 or Ci 45430); D&C red 9 (CI 15585); D&C red 21 (CI 45380); D&C orange 4 (CI 15510); D&C orange 5 (CI 45370); D&C red 27 (CI 45410); D&C red 13 (Cl 15630); D&C red 7 (CI 15850:1); D&C red 6 (CI 15850:2); D&C yellow 5 (CI 19140); D&C red 36 (CI 12085); D&C orange 10 (CI 45475); D&C yellow 19 (CI 15985); FD&C Red 40 (CI 16035); FD&C Blue 1 (CI 42090); FD&C Yellow 5 (CI 19140) or any combination thereof. In certain embodiments, the composition may contain one or more organic azo pigments. For example, the pigmented composition may contain red 7, and/or red 6, and/or red 27, and/or blue 1, and/or yellow 5, and/or red 33. The compositions may contain red 7. In certain embodiments, the composition may contain Red 7 and Red 6. In certain embodiments, the compositions may contain Red 7 and Blue 1. In various embodiments, the composition may contain Red 7, Red 27, and Blue 1.

Substrates suitable for forming varnishes include, but are not limited to, mica, bismuth oxychloride, sericite, alumina, aluminum, copper, bronze, silver, calcium, zirconium, barium and strontium, titanium mica, fumed silica, spherical silica, polymethyl methacrylate (PMMA) ), micronized TEFLON, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenyl succinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, silica, kaolin, magnesium aluminum silicate, magnesium trisilicate , maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silicon dioxide, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc resinate, aluminum oxide, attapulgite, calcium carbonate, calcium silicate, dextran, nylon, silicon dioxide silylate, powder silk, sericite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder and mixtures thereof.

Suitable varnishes include, but are not limited to, red dye varnishes from the monoazo, diazo, fluorane, xanthene, or indigoid dye families, such as Red 4, 6, 7, 17, 21, 22, 27, 28, 30, 31, 33, 34, 36 and red 40; varnishes of yellow pyrazole, monoazo dyes, fluorane, xanthene, quinoline dyes or salts thereof, such as yellow 5, 6, 7, 8, 10 and 11; varnishes made from violet dyes, including dyes from the anthraquinone family, such as violet 2; and varnishes from orange dyes, including orange 4, 5, 10, 11, etc.

Organic pigments can be processed onto the surface. In certain embodiments, the organic pigments are surface treated. In certain embodiments, more than 1% of the surface of the organic pigment is surface treated. For example, an organic pigment may be characterized by treating 1 to 50% (eg, 1 to 20%, 1 to 10%, etc.) of its surface.

It has been found that combining these organic pigments with a TiO ₂ -based pigment mill component, which is predominantly composed of rutile TiO ₂ , retards the color change typically associated with organic dyes. Thus, the compositions contain a TiO ₂ -based pigment mill component (i.e., all TiO ₂ present in the composition) that is greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% rutile TiO ₂ by weight of the TiO ₂ -based component. In some embodiments, the TiO ₂ -based component consists of rutile TiO ₂ . In some embodiments, TiO ₂ may be present in an amount greater than 0.01% by weight of the composition (eg, 0.1 to 10% by weight of the composition, 0.05 to 10% by weight of the composition, etc.). In some embodiments, the TiO ₂ in the pigment grind has a particle size greater than 200 nm. As used herein, particle size measurements can be performed using dynamic light scattering.

The ratio of rutile TiO2 to organic pigment can be varied to improve color fastness in compositions depending on the exact composition of the mixture and the weight percentage of the pigment component (eg organic pigments, pigment TiO2 and inorganic pigments). In some embodiments, the weight ratio of organic pigments (e.g., red 7, red 6, red 27, red 33, blue 1, yellow 5, red 7 varnish, red 6 varnish, red 27 varnish, blue 1 varnish, yellow 5 varnish, etc. .d.) to pigment rutile TiO ₂ is from 20:1 to 1:20 by weight. In certain embodiments, the weight ratio of organic pigments to rutile

- 4 045485

TiO2 can be from 20:1 to 1:1 by weight (for example, from 20:1 to 10:1, from 10:1 to 1:1, from 8:1 to 2:1, from 9:1 to 1: 1, from 8:1 to 1:1, from 7:1 to 1:1, from 6:1 to 1:1, from 5:1 to 1:1, from 4:1 to 1:1, from 3: 1 to 1:1, from 2:1 to 1:1, etc.). In other embodiments, the weight ratio of organic pigments to rutile TiO ₂ may be from 1:1 to 1:20 by weight (e.g., 1:1 to 1:10, 1:10 to 1:20, 1:5 to 1:15, from 1:8 to 1:2, from 1:9 to 1:1, from 1:8 to 1:1, from 1:7 to 1:1, from 1:6 to 1:1, from 1:5 to 1:1, from 1:4 to 1:1, from 1:3 to 1:1, from 1:2 to 1:1, etc.).

Non-pigmented TiO ₂ such as radiation attenuation grade TiO ₂ may also be included in the composition. Typically, TiO ₂ pigment grade is included to optimize visible light scattering, and most particles need to be approximately half the wavelength of the light to be scattered. For the visible part of the light spectrum, most grades of pigment TiO ₂ are characterized by a particle size of more than 200 nm (for example, from 200 to 400 nm, etc.). Non-pigment grades of TiO ₂ , such as Radiation Attenuation Grade TiO ₂ , are transparent to visible light because they do not scatter light in the visible portion of the spectrum. It has also been discovered that certain grades of non-pigmented TiO ₂ (eg, anatase, rutile, etc.) can be used to further maintain color fastness in pigmented compositions. For example, radiation attenuation grade TiO ₂ is able to further maintain the color stability of compositions containing organic pigments, with the greatest change in color shade. In most embodiments, radiation attenuation grade TiO ₂ has a particle size of less than 200 nm (eg, as measured by dynamic light scattering, etc.). In some embodiments, the radiation attenuation grade TiO ₂ is rutile radiation attenuation grade TiO ₂ , radiation attenuation grade anatase TiO ₂ , or combinations thereof. Suitable TiO ₂ radiation attenuation grades are available from KOBO Products (NJ, USA), such as TTB7 products. Pigmented compositions may contain 0.1 to 20% (eg, 0.1 to 10%, etc.) radiation attenuation grade TiO ₂ by weight of the composition. In specific embodiments, the composition may contain from 1 to 10% radiation attenuation grade TiO ₂ by weight of the composition. In some embodiments, the weight ratio of pigment TiO ₂ to radiation attenuation grade TiO ₂ is 10:1 to 1:10 (e.g., 10:1 to 1:1, 5:1 to 1:1, 2:1 to 1:1, from 1:10 to 1:1, from 1:5 to 1:1, from 1:2 to 1:1). In some embodiments, the composition may exhibit reduced color change after 8 hours of heating from 80 to 100° C. relative to an otherwise identical composition not containing radiation attenuation qualified TiO ₂ . For example, the compositions may contain such an amount of radiation attenuation grade TiO ₂ that the composition may have an AE of less than 5 after 8 hours of heating at greater than 80°C (eg, 80 to 100°C, etc.).

The compositions may contain additional pigments or particulate materials for absorbing or scattering ultraviolet light, such as zinc oxide particles, or for other aesthetic characteristics such as a pearlescent effect (eg, mica, bismuth oxychloride, etc.). Exemplary inorganic pigments include, but are not limited to, inorganic oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxides, alumina, aluminum hydroxide, iron oxides (a-Fe ₂ O ₃ , y-Fe ₃ O ₄ , Fe ₃ O ₄ , FeO) and iron hydroxides, including red iron oxide, yellow iron oxide and black iron oxide, lower titanium oxides, zirconium oxides, chromium oxides, chromium hydroxides, manganese oxides, manganese hydroxides, cobalt oxides, cobalt hydroxides, oxides cerium, cerium hydroxides, nickel oxides, nickel hydroxides, zinc oxides and zinc hydroxides, as well as complex oxides and complex 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 of 5 nm to 500 microns, or 5 nm to 250 microns, or 10 nm to 100 microns. In some embodiments, the particle size (median) will be less than about 5 microns or less than 1 micron. In some embodiments, the composition contains less than 5% inorganic pigments (other than TiO2) by weight of the composition. In some embodiments, the composition contains less than 1% inorganic pigments (other than TiO2) by weight of the composition. In some embodiments, the composition contains less than 0.5% inorganic pigments (other than TiO2) by weight of the composition. In some embodiments, the composition contains less than 5% iron oxide by weight of the composition. In some embodiments, the composition contains less than 1% iron oxide by weight of the composition. In some embodiments, the composition contains less than 0.5% iron oxide by weight of the composition

The total pigment content of the compositions (e.g., organic pigments, TiO ₂ (e.g., pigmented rutile TiO ₂ , inorganic pigments, etc.) is typically less than 30% by weight of the composition (e.g., less than 20% by weight of the composition, less than 15% by weight of the composition, less than 12% by weight of the composition, etc.) In some embodiments, the total pigment content is from 5 to 15% by weight of the composition. In some embodiments, the organic pigment content

- 5 045485 ment is from 1 to 10% by weight of the composition

The pigmented composition typically contains a mixture of individual pigments to produce specific shades of color in the composition. This pigment component may have reduced sensitivity to color change. For example, in some embodiments, the composition does not have a color characteristic value (L*, a*, b*) with the reflective component included (SCI) (L*=40±10, a*=54±20, b*=18±20) Those skilled in the art can measure L*a*b* values, for example, by the measurement procedure detailed in Example 1 In some embodiments, the composition exhibits a color change of less than 10 (e.g., less than 3, less than 2.5, etc.) after 8 hours of heating at greater than 80°C (e.g., 80 to 100°C, 85 to 95 °C, etc.) The difference between color space points can be calculated (or approximated) using standard Euclidean color space geometry. For example, color contrast can be calculated using equation (1)

-^+ and - +<h - h)’ with

Pigments, and in particular organic pigments, may be surface treated. In some embodiments, TiO ₂ is surface treated. In some embodiments, both TiO ₂ and organic pigments are independently surface treated. In certain embodiments, TiO ₂ (eg, TiO ₂ grade for radiation attenuation, rutile TiO ₂ , etc.) and organic pigment (for example, red 7, red 6, red 27, red 33, blue 1, yellow 5, red 7 lac, red 6 lac, red 27 lac, blue 1 varnish, yellow 5 varnish, etc. are independently surface treated. In various embodiments, the TiO ₂ , organic pigment, and inorganic pigment are independently surface treated. In certain embodiments, TiO ₂ (eg, radiation attenuation grade TiO ₂ , rutile TiO ₂ , etc.) and organic pigment (eg, red 7, red 6, red 27, red 33, blue 1, yellow 5, red 7 varnish, red 6 varnish, red 27 varnish, blue 1 varnish, yellow 5 varnish, etc.) are characterized by the same surface treatment. In various embodiments, the TiO ₂ , organic pigment, and inorganic pigment are independently surface treated. In some embodiments, the TiO ₂ , organic pigment, and inorganic pigment each have the same surface finish.

The surface treatment may be any such treatment that changes the surface of the modifying agent and/or the first coloring agent. For example, the surface treatment may make the pigments more hydrophobic or more dispersible in the carrier medium or may increase the adhesion of the pigments to the modifying agent. The surface of the pigments may, for example, be covalently or ionicly bonded to or adsorbed to an organic or silicone-based molecule, or a layer of material may be physically applied to the pigments. The surface treatment compound may be attached to the pigment via any suitable coupling agent, linker group, or functional group (eg, silane, ester, ether, etc.). The compound may contain a hydrophobic moiety, which may be selected from, for example, alkyl, aryl, allyl, vinyl, alkyl-aryl, aryl-alkyl, organosilicon material, di-silicon material, dimethicones, methicones, polyurethanes, silicone polyurethanes and fluoro- or perfluoro derivatives. Other hydrophobic modifiers include lauroyl lysine, isopropyl titanium triisostearate (ITT), cross-linked polymers of ITT and dimethicone (ITT/dimethicone), ITT and amino acids, cross-linked polymer of ITT/triethoxycaprylylsilane, waxes (eg, carnauba), fatty acids (eg, stearates, etc. .), HDI/trimethylolhexylactone cross-linked polymer, PEG-8 methyl ether triethoxysilane, aloe extract, jojoba ester, lecithin, perfluoroalcohol phosphate and magnesium myristate (MM), to name a few. In some embodiments, organic pigments and/or TiO ₂ (eg, pigmented TiO ₂ , radiation attenuation grade TiO ₂ , pigmented TiO ₂ and radiation attenuation grade TiO ₂ , etc.) are surface treated. In specific embodiments, the organic pigments are ITT-treated. In certain embodiments, the TiO ₂ is treated with ITT/dimethicone. In various embodiments, the organic pigments and TiO ₂ are ITT/dimethicone treated. In specific embodiments, the organic pigments are treated with ITT/dimethicone. In certain embodiments, the TiO ₂ is treated with ITT/dimethicone. In various embodiments, the organic pigments and TiO ₂ are ITT-treated. Specific surface treated organic pigments that may be used include (INCI names) blue 1 lacquer, (and) isopropyl titanium triisostearate, (and) triethoxysilylethyl polydimethylsiloxyethyl dimethicone;

red 6 varnish, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

red 7 varnish, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

red 30 varnish, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxy- 6 045485 ethyl dimethicone;

yellow 5 varnish, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

yellow 6 varnish, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone, as well as combinations thereof.

Specific surface treated TiO2 that can be used includes (INCI names) titanium dioxide (eg, radiation attenuation grade TiO2, rutile TiO2, etc.), (and) isopropyl titanium triisostearate, (and) triethoxysilylethyl polydimethylsiloxyethyl dimethicone;

titanium dioxide (eg, radiation attenuation grade TiO2, rutile TiO2, etc.), (and) isopropyl titanium triisostearate, (and) aluminum oxide, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

titanium dioxide (e.g. radiation attenuation grade TiO2, rutile TiO2, etc.), (and) cyclopentasiloxane, (and) PEG/PPG-18/18 dimethicone, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone, (and) ) disteardimonium hectorite, (and) tocopheryl acetate, as well as combinations thereof.

Specific surface treated inorganic pigments that can be used include (INCI names) iron oxides (CI 77491), (and) isopropyl titanium triisostearate, (and) triethoxysilylethyl polydimethylsiloxyethyl dimethicone;

iron oxides (CI 77492), (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

iron oxides (CI 77499), (and) isopropyltitanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

chrome green, (and) isopropyl titanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

ferric ammonium ferrocyanide, (and) isopropyltitanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone;

iron oxides (CI 77491), (and) cyclopentasiloxane, (and) PEG/PPG-18/18 dimethicone, (and) isopropyltitanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone, (and) disteardimonium hectorite, (and) tocopheryl acetate;

iron oxides (CI 77492), (and) cyclopentasiloxane, (and) PEG/PPG-18/18 dimethicone, (and) isopropyltitanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone, (and) disteardimonium hectorite, (and) tocopheryl acetate;

iron oxides (CI 77499), (and) cyclopentasiloxane, (and) PEG/PPG-18/18 dimethicone, (and) isopropyltitanium triisostearate, (and) triethoxysilylethylpolydimethylsiloxyethyl dimethicone, (and) disteardimonium hectorite, (and) tocopheryl acetate, and combinations thereof .

Surface treated components are available from KOBO Products (New Jersey, USA), for example, listed as TTB or ITT products.

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

The compositions may be in the form of an emulsion. Typically, emulsions may contain water and/or glycerin. Emulsions may be water-in-oil, oil-in-water, silicone-in, 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. In preferred embodiments, the emulsion is a water-in-oil, oil-in-water, silicone-in-water, or water-in-silicone emulsion. Emulsions may contain an anhydrous external phase (eg, an oil phase, a silicone phase, etc.). In some embodiments, the emulsions may contain an aqueous, polyol, or glycerol dispersed phase. In some embodiments, the composition may contain 1-40% (e.g., 1 to 10%, 20 to 30%, 30 to 40%, etc.) of a dispersed phase (e.g., glycerin, etc.)

In some embodiments, the outer (continuous) phase is an oil phase with an emollient. For example, the continuous oil phase may contain any suitable oils for emulsions, including, without limitation, vegetable oils; fatty acid esters; fatty alcohols; isoparaffins such as isododecane and isoeicosane; hydrocarbon oils such

- 7 045485 as mineral oil, petrolatum and polyisobutene; polyolefins and their hydrogenated analogues (for example, hydrogenated polyisobutene); natural or synthetic waxes; silicone oils such as dimethicones, cyclic silicones and polysiloxanes, and the like. In certain embodiments, the composition contains in the outer carrier phase from 20 to 50% emollient (eg, silicone such as diphenyl dimethicone, ester oil such as ethylhexyl palmitate, etc.) by weight of the composition.

Suitable ester oils include fatty acid esters. Specific reference may be made to such esters commonly used as emollients in cosmetic formulations. Such esters will typically be the esterification of an acid as R4(COOH) ₁₂ with an alcohol as _R5 (OH) ₁₃ , wherein R4 and _R5 are each independently a straight-chain, branched-chain or cyclic hydrocarbon group, optionally containing unsaturated bonds (for example, 1-6, or 1-3, or 1) and containing from 1 to 30 (for example, 630, or 8-30, or 12-30, or 16-30) carbon atoms, optionally replaced by one or more functional groups, including hydroxyl, oxa-, oxo- and the like groups. Preferably at least one of R ₄ and R ₅ contains at least 8, or at least 10, or at least 12, or at least 16, or at least 18 carbon atoms, such that the ester contains at least one fatty acid chain. The esters defined above will include, without limitation, esters of monoacids and monohydric alcohols, monoacid acids and diols and triols, diacid acids and monohydric alcohols, and tribasic acids and monohydric alcohols.

Suitable fatty acid esters include, but are not limited to, butyl acetate, butyl isostearate, butyl oleate, butyl octyl oleate, cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetyl stearate, diisostearyl fumarate, diisostearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, di-C _{12_13 -} alkyl malate, dicetearyl dimer dilinoleate, dicetyl adipate , diisocetyl adipate, diisononyl adipate, diisopropyl dimerate, triisostearyl trilinoleate, octodecyl stearoyl stearate, hexyl laurate, hexadecylisostearate, hexadecyl laurate, hexyldecyl octanoate, hexyldecyl oleate, hexyldecyl palmitate, hexyldecyl stearate, isononyl isononanoate , 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 hepta noate, stearyl stearate, tetratriacontanyl stearate, triarachidine, tributyl citrate, triisostearyl citrate, tri-C ₁₂ _ ₁₃ -alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyl dodecyl citrate, tridecyl cocoate, tridecyl isononanoate, glyceryl monoricinoleate, 2-octyl decyl palmitate, 2-octyl dodecyl myristate or lactate, di(2-ethylhexyl) succinate, tocopheryl acetate and the like.

Other suitable esters include esters in which R ₅ is a polyglycol of the form H-(O-CHR*-CHR*) _n -, where R* is independently selected from hydrogen or C1_ ₁₂ straight chain alkyl, including methyl and ethyl, an example of which is polyethylene glycol monolaurate.

The oil may also include volatile or non-volatile silicone oil. Suitable silicone oils include straight or cyclic silicones such as polyalkyl or polyaryl siloxanes, optionally containing alkyl or alkoxy groups, which contain from 1 to 10 carbon atoms. Exemplary silicone oils include, for example, caprylylmethicone, cyclomethicone, cyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, diphenyl dimethicone, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, methicone, methyl-phenylpolysiloxane, octamethylcyclotetrasiloxane, octamethyltrisiloxane, perfluorononyl dimethicone, polydimethylsiloxanes and combinations thereof. The silicone oil will have a viscosity, typically, but not necessarily, between 5 and 3000 centistokes (cSt), preferably between 50 and 1000 cSt, measured at 25°C.

In one embodiment, the silicone oil contains phenyl groups, as in the case of silicone oil, such as methylphenylpolysilocean (INCI name - diphenyl dimethicone), commercially available from Shin Etsu Chemical Co under the names including F-5W, KF-54 and KF-56 . Diphenyl dimethicones have good organic compatibility and can impart film-forming characteristics to the product. In addition, the presence of phenyl groups increases the refractive index of the silicone oil and thus can contribute to a high gloss product if desired. In one embodiment, the silicone oil will have a refractive index of at least 1.3, preferably at least 1.4, more preferably at least 1.45, and even more preferably at least 1.5 when measured at 25°C. Another suitable phenyl-functionalized silicone oil has the INCI name phenyl trimethicone and is sold under the trade name DC 556 from Dow Coining. DC 556 has a refractive index of 1.46. In one embodiment, the silicone oil is a fluorinated silicone, such as

- 8 045485 for example, perfluorinated silicone (i.e. fluorosilicones). Fluorosilicones are predominantly both hydrophobic and oleophobic, and due to this, they provide the product with the required sliding properties and tactile characteristics. Fluorosilicones also impart properties that promote long-lasting durability of the lip product. If necessary, fluorosilicones can be thickened using behenyl behenate. 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 contain 5 to 75% emollient (e.g., silicone oil, ester oil, etc.) by weight of the composition (e.g., 10 to 60% by weight of the composition, 20 to 50% by weight of the composition, 25 up to 45% by weight of the composition, etc.).

The compositions may also contain hydrocarbon oils. Exemplary hydrocarbon oils are straight or branched chain paraffinic hydrocarbons containing from 5 to 80 carbon atoms, typically from 8 to 40 carbon atoms and more typically from 10 to 16 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 C8-9 isoparaffins, _C9 isoparaffins, _C12 isoparaffins, C20-40 isoparaffins and the like. Particular mention should be made of isoparaffins having INCI names such as isohexadecane, isoeicosane and isododecane (IDD).

Also suitable as hydrocarbon oils are poly-a-olefins typically containing more than ₂₀ carbon atoms, including (optionally hydrogenated) C24-28 olefins, _{C30_45} olefins, polyisobutene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, hydrogenated polycyclopentane, mineral oil, pentahydrosqualene, squalene, squalane and the like. The hydrocarbon oil may also include higher fatty alcohols such as oleyl alcohol, octyldodecanol and the like.

Other suitable oils include, but are not limited to, castor oil, C ₁₀ - ₁₈ triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil, bassia nut oil, canola oil, soybean oil, sunflower oil, walnut oil, avocado oil, camellia oil, macadamia 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 of the above ester oils, silicone oils and hydrocarbon oils are considered suitable in the compositions described herein. Therefore, in one embodiment, the compositions contain at least one oil selected from the ester oils, silicone oils and hydrocarbon oils described above. In another embodiment, the compositions contain two or more oils selected from the ester oils, silicone oils and hydrocarbon oils described above. In yet another embodiment, the compositions will contain at least one ester oil, 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 preferred that the compositions contain at least one ester oil, and they may optionally contain at least one additional oil selected from hydrocarbon oils, silicone oils, and combinations thereof .

Although not required, the compositions typically contain an aqueous phase. In most embodiments, the aqueous phase is the dispersed phase of emulsions (eg, water-in-oil, glycerin-in-oil, etc.). Since hydrolysis of organic pigments can cause color changes, these compositions are most susceptible to the improved color fastness provided by the compositions of the present invention. In some embodiments, aqueous phase solvents are present in an amount of 1 to 50% (eg, 1 to 20%, 5 to 15%, 1 to 10%, etc.) by weight of the composition. In other embodiments, the compositions are anhydrous.

Waxes and/or fillers may also optionally be added (particularly in those embodiments where the composition is a stable solid at room temperature) in an amount ranging from 1 to 20%, inclusive, by weight of the composition, or in the range from 1 up to 10% inclusive by weight of the composition. Examples of fillers may include, without limitation, 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, uricuri wax, rice bran wax, castor wax, building wax, stearone, Acrawax, waxwort wax, castor wax, sumac fruit wax, ozokerite, beeswax , candelilla wax, liquid paraffin, ceresin wax, cocoa butter, bassia nut butter, esparto wax, shellac wax, diesters or triesters of ethylene glycol and C ₁₈ -C ₃₆ fatty acids, cetyl palmitate, tallow,

- 9 045485 paraffin wax, lanolin, lanolin alcohol, cetyl alcohol, glyceryl monostearate, sugar cane wax, jojoba wax, stearyl alcohol, silicone waxes and combinations thereof.

In some embodiments, the oil phase may include one or more waxes. Wax can give consistency to an emulsion so that the emulsion has the physical form of a semi-solid or solid. As used herein, the term solid is intended to mean a composition that retains its shape and is suitable for molding into a shape-retaining rod (eg, a lipstick). In some embodiments, the waxes are present in an amount sufficient to give the emulsion the form of a solid emulsion. For example, the solid emulsion may have a hardness of at least 30 g. The composition typically has a hardness of at least 40 g at room temperature. In one embodiment, the composition may have a significantly higher hardness, from 100 to 300 g. The hardness of the emulsion can be measured using a Model QTS-25 Texture Analyzer equipped with a 4 mm stainless steel probe (TA-24), as described in US Pat. No. 8580283 issued to Avon, the disclosure of which is incorporated herein by reference.

Waxes can be natural, mineral and/or synthetic. Natural waxes include waxes of animal origin (for example, beeswax, spermaceti, lanolin and shellac wax) and waxes of plant origin (for example, carnauba, candelilla, wax, and sugar cane wax). Mineral waxes include, but are not limited to, ozokerite, ceresin, montane wax, paraffin, microcrystalline, petroleum waxes and liquid paraffin. Synthetic waxes include, for example, polyethylene glycols such as PEG-18, PEG-20, PEG-32, PEG-75, PEG-90, PEG-100 and PEG-180, commercially available under the trade name CARBOWAX® (The Dow Chemical Company). Mention should be made of the polyethylene glycol wax CARBOWAX 1000, which has a molecular weight ranging from 950 to 1050 and a melting point of 38°C, CARBOWAX 1450, which has a molecular weight ranging from 1305 to 1595 and a melting point of 56°C, CARBOWAX 3350, which has a molecular weight ranging from 3015 to 3685 and a melting point of 56°C, and CARBOWAX 8000 which has a molecular weight ranging from 7000 to 9000 and a melting point of 61°C.

Synthetic waxes also include Fischer-Tropsch (FT) waxes and polyolefin waxes such as ethylene homopolymers, ethylene-propylene copolymers and ethylene-hexene copolymers. Exemplary ethylene homopolymer waxes are commercially available under the trade name POLYWAX® Polyethylene (Baker Hughes Incorporated) having melting points ranging from 80 to 132°C. Commercially available ethylene-a-olefin copolymer waxes include those commercially available under the trade name PETROLITE® Copolymers (Baker Hughes Incorporated) having melting points ranging from 95 to 115°C.

In one embodiment, the oil phase of the emulsion includes at least one wax selected from Acrawax (N,N'-ethylene-bis-steαparamideα), microcrystalline wax, linear polyethylene wax, stearone (18-pentatriacontanone), castor wax, montane wax, lignite wax, uricuri wax, carnauba wax, rice bran wax, shellac wax, esparto wax, ozokerite wax, jojoba wax, candelilla wax, ceresin wax, beeswax, castor wax, sugar cane wax, stearyl alcohol, tallow, cetyl alcohol, liquid paraffin, glyceryl monostearate, sumac wax, silicone wax, paraffin wax, lanolin wax, lanolin alcohol, wax, cetyl palmitate, bassia nut oil, cocoa butter and di- or triesters of ethylene glycol and C ₁₈ - ₃₆ fatty acids .

The amount of wax, if present, may be less than 2% (eg, 0.1-2%) 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 10% (eg, 10-20%) by weight of the composition if the composition is semi-solid or solid, or if clarity is not the goal. In some embodiments, the emulsion may contain wax in an amount of from 1 to 25% (or 1-20%, or 1-5%, or 1-10%) by weight of the composition, particularly in embodiments formulated as lipsticks.

In one embodiment, the oil phase of the composition includes 0.1-2%, or 2-5%, or 5-10%, or 10-15%, or 15-20% by weight of at least one wax (for example, microcrystalline wax , ozokerite wax, polyethylene wax, solid paraffin, liquid paraffin, etc.). In one embodiment, the oil phase of the composition includes microcrystalline wax within the above amounts. In one embodiment, the oil phase of the composition includes ozokerite wax within the above amounts. In one embodiment, the oil phase of the composition includes a polyethylene-based wax within the above amounts. In one embodiment, the oil phase of the composition includes liquid paraffin within the above amounts. In one embodiment, the oil phase of the composition includes paraffin wax within the above amounts.

- 10 045485

Typically, the emulsions of the present invention additionally contain one or more emulsifiers. For example, one or more emulsifiers may be present in a general range of from 0.01 to 10.0% by weight of the emulsion. In some embodiments, the total amount of emulsifier ranges from 0.1 to 6.0% by weight or from 0.5 to 4.0% by weight of the emulsions. Examples of emulsifiers include polyglyceryl compounds such as polyglyceryl 6-polyricinoleate, polyglyceryl pentaoleate, polyglyceryl isostearate and polyglyceryl 2-diisostearate; glycerol esters such as glycerol monostearate or glycerol monooleate; phospholipids and phosphate esters such as lecithin and trilaureth-4-phosphate (available under the trade name HOSTAPHAT®KL-340-D); sorbitan-containing esters (including SPAN® esters), such as sorbitan laurate, sorbitan oleate, sorbitan stearate or sorbitan sesquioleate; polyoxyethylenephenols such as polyoxyethyleneoctylphenol; polyoxyethylene ethers such as polyoxyethylene cetyl ether and polyoxyethylene stearyl ether; polyethylene glycol emulsifiers such as PEG-30 polyhydroxystearate or alkyl polyethylene glycols; polypropylene glycol based emulsifiers such as PPG-6-laureth-3; dimethicone polyols and emulsifiers based on polysiloxane, etc. Combinations of emulsifiers are provided, such as a combination of lecithin and sorbitan. Additional emulsifiers are listed in the INCI Ingredient Dictionary and Handbook, 12th edition (2008), the disclosure of which is incorporated herein by reference.

As is customary in the cosmetics field, additional components can be included in the composition for various functional purposes, in particular in the internal phase of emulsions, in the external phase of emulsions or as a dispersed phase. However, while additional ingredients suitable for formulating the above cosmetic compositions may be included, the inclusion of additional ingredients is limited to amounts of such ingredients that do not affect the formation or stability of the compositions (eg, emulsions, etc.).

Such components may be selected from the group consisting of film formers, pigments, waxes, emollients, humectants, preservatives, flavoring agents, antioxidants, botanicals, and mixtures thereof. Special mention should be made of highly purified plant extracts or synthetic agents that may have wound-healing, anti-inflammatory or other beneficial effects for treating skin or lips. Additional embodiments may include antioxidants such as tocopherol and/or α-hydroxy acids such as glycolic acid, lactic acid, etc. The compositions may include one or more film formers to increase the affinity of the product.

Film formers, including film-forming polymers, can also be used. The term film-forming polymer can be understood as a term denoting a polymer that is capable, alone or in the presence of at least one adjuvant film-forming agent, to form a continuous film that adheres to a surface and functions as a binder for the particulate material. Polymeric film-forming agents include, but are not limited to, acrylic polymers or copolymers, (meth)acrylates, alkyl(meth)acrylates, polyolefins, polyvinyls, polyacrylates, polyurethanes, silicones, polyamides, polyethers, polyesters, fluoropolymers, polyethers, polyacetates, polycarbonates, polyamides , polyimides, rubbers, epoxy resins, formaldehyde resins, organosiloxanes, dimethicones, amodimethicones, dimethiconols, methicones, silicone acrylates, copolymers of polyurethane and silicones, cellulose polymers, polysaccharides, polyquaterniums, etc. Suitable film-forming agents include those listed in the Cosmetic Ingredient Dictionary (INCI and Handbook, 12th edition (2008)), the disclosure of which is incorporated herein by reference.

The composition may contain one or more of preservatives or antimicrobial agents such as methyl, ethyl or propyl paraben, etc., in amounts ranging from 0.0001 to 5 wt.% by weight of the entire composition. The compositions may contain other ingredients such as one or more anesthetics, antiallergenic, antifungal, anti-inflammatory, antimicrobial, antiseptic, chelating agents, emollients, emulsifiers, fragrances, humectants, lubricants, masking agents, medicinal agents, humectants, pH adjusters, preservatives , protectants, soothing agents, stabilizers, sunscreens, surfactants, thickeners, viscosity enhancers, vitamins or any combination thereof.

In one embodiment, the emulsions of the present invention are provided as products for application to the lips. Such lip products may include lip cream, lip balm, lip gloss, lip treatment, lip moisturizer, lip cosmetic, lip sunscreen and lip fragrance. In one embodiment, the lip product is a creamy, pourable lip product. In certain embodiments, the products of the present 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, emulsions according to the present invention can

- 11 045485 package in a resealable container. Such containers may comprise a body or chamber into which the emulsion formulated as a cosmetic composition is loaded, and a lid removably attached to the container or rotatably configured on the container. In one embodiment, the cap may be attached to a collapsible body (eg, formed from a soft plastic material) such that the cap can be removed from the opening of the collapsible body and replaced when dispensing of the composition is completed. The lid may be attached to the collapsible body body (eg, by screw threads, snap-locking, or the like) to facilitate resealing the collapsible housing for storage between uses. In one embodiment, the lid is pivotally attached to the container to seal the contents when in the closed position and to dispense the contents of the container when in the open position. Various containers are contemplated, including, but not limited to, pens, barrel dispensers, pumps, airless pumps, aerosol containers, hand squeeze containers, cosmetic applicators, and the like.

In other embodiments, the emulsions may be in the form of emulsions for skin care (e.g., lotions, creams, gels, etc.), decorative cosmetics, mascara and eyebrow varieties, eye shadow, lipstick, contour pencil, lips, foundation, concealer, makeup remover, sunscreen, deodorant, just to name a few.

A sunscreen to protect the skin that protects against damage from ultraviolet rays may also be included in the claimed compositions. In one embodiment, sunscreens may include, but are not limited to, broad spectrum UVB and UVA protection agents such as octocrylene, avobenzone, octytyl methoxycinnamate, octyl salicylate, oxybenzone, homosylate, benzophenone, camphor derivatives, zinc oxide, triazine complexes (e.g., Tinsorb, Univul, and etc.) and titanium oxide. If present, the sunscreen may be present in an amount ranging from 0.01 to 70%, inclusive, by weight of the composition.

Suitable exfoliants may include, for example, α-hydroxy acids, β-hydroxy acids, oxacids, oxadic acids and derivatives thereof such as esters, anhydrides and salts. Suitable hydroxy acids include, for example, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, 2-hydroxyalkanoic acid, mandelic acid, salicylic acid and derivatives thereof. In some embodiments, the exfoliant is lactic acid. If present, the exfoliating agent may be present in an amount ranging from 0.1 to 80%, inclusive, by weight of the composition.

The claimed compositions described herein may also contain one or more cosmetic powders or particulate materials, for example, calcium aluminum borosilicate, PMMA, polyethylene, polystyrene, cross-linked methyl methacrylate polymer, nylon-12, ethylene/acrylic acid copolymer, nitride boron, Teflon, silicon dioxide and the like. Typically, especially in the case of makeup compositions, the compositions described herein may further include colorants or pigments to impart the desired color or effect. Non-limiting examples may include inorganic pigments, organic pigments and varnishes. 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, alumina, aluminum hydroxide, iron oxides (a-Fe ₂ O ₃ , y-Fe ₂ O ₃ , Fe ₃ O ₄ , FeO), red iron oxide, yellow iron oxide, black iron oxide, iron hydroxides, titanium dioxide, lower titanium oxides, zirconium oxides, chromium oxides, chromium hydroxides, manganese oxides, cobalt oxides, cerium oxides, diatomaceous earth , nickel oxides, zinc oxides, complex oxides and complex hydroxides such as iron titanate, cobalt titanate and cobalt aluminate. Non-metal oxides are also considered suitable, including aluminum oxide and silica, ultramarine blue, Prussian blue, dark violet dye, bismuth oxychloride, talc, mica, sericite, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminosilicate, silicate, titanium mica, iron oxide titanium-containing mica, bismuth oxychloride and the like. Organic pigments may include, without limitation, at least one of carbon black, carmine, phthalocyanine blue and green pigments, diarylide yellow and orange pigments, and red and yellow azo pigments such as toluidine red, litho red, naphthol red and brown pigments, and combinations thereof .

In some embodiments, the compositions contain a polysaccharide thickener. In some embodiments, the compositions contain an anionic polysaccharide (eg, xanthan gum, etc.). In other embodiments, the compositions do not contain a polysaccharide thickener, or the composition contains less than 5%, less than 1%, or less than 0.1% polysaccharide thickener by weight of the composition.

In one embodiment, topical compositions (or an aqueous phase thereof including an internal glycerol phase) may have a pH in the range of 1 to 7, but typically have a pH in the range of 3 to 6. In some embodiments, the internal phase has a pH of 3 up to 5, or

- 12 045485 from 3.5 to 4.5, or from 3.7 to 3.9. Suitable pH adjusters, such as, but not limited to, sodium hydroxide, citric acid and triethanolamine, can be included in the described composition to maintain the pH in the desired range.

Exemplary ranges of composition ingredients are presented in table. 1 (percentages are stated as percentages by weight of the composition) for a cosmetic composition such as lipstick. Please note that some components are optional. In addition, the pigment component may include organic pigments, rutile TiO2 and additional inorganic pigments (optional) in certain quantities. It will be clear that for the weight percent values shown in table. 1, crystalline forms of TiO2 other than rutile (such as anatase) can be considered as inorganic pigments. In some embodiments, the compositions contain an emulsifier, fragrance oil, powder, preservative, sweetener, sunscreen, or combinations thereof.

Table 1

Component Weight percentage(%) Emollient 1-60% Emulsifier 0.1-10% Glycerin (humectant) 1-40% Additional Ingredients 0-0.1-20% Wax 2-30% Water 1-10% Pigment component 1-30% - organic pigments 0.5-20% - rutile pigment TiO ₂ 0.5-20% - inorganic pigments 0.01-10% TiO ₂ qualifications for radiation attenuation 0.1%-10%

The compositions can be formulated by producing pigment grinds, wherein inorganic pigments, organic pigments and pigment TiO2 can be dispersed in a suitable carrier by providing shear force. The pressure and/or shear force (eg, abrasion, scraping, carding, etc.) applied to the pigment grinding may be provided by any suitable means to disperse the pigment in the carrier, for example, through the use of a three-roll mill. In some embodiments, each of the pigments is surface treated. Suitable carriers include ester oils such as ethylhexyl palmitate and silicones such as diphenyl dimethicone. In certain embodiments, a pigment grind formulated as an emulsion can then be used.

Examples

The following examples illustrate specific aspects of this description. The examples should not be construed as limiting, as the example only provides a specific understanding and practical application of the embodiments and their various aspects.

Example 1. Lack of color fastness of compositions with organic pigments without rutile TiO2.

Eight color formulations were prepared both as an anhydrous formulation and as a glycerin-in-oil emulsion. For each color composition, identical pigment grinds were placed in an anhydrous emulsion and a glycerin-in-oil emulsion at a level of 10% by weight of the composition. The pigments in each composition to provide a shade of color are shown in the table. 2. In addition, the L*a*b* (±5) color space values with reflective component included (SCI) for each composition to provide color tint are shown in Table. 2.

- 13 045485

table 2

Composition for providing color tint 1 2 3 4 5 6 7 8 Titanium dioxide (anatase) 1.91 11.42 7 18.48 37.06 0.5 13.96 22.41 Red 7 varnish/ITT 9.02 15.91 8.4 27.13 3.04 31.9 32.97 0 Cosmetic brown 24.14 0 0 0 3.82 4.88 0 0 Red iron oxide 8.58 0 0 0 0 0 0 0 Cosmetic red oxide 6.35 13.04 0 0 0 4.67 0.55 0 Fd&C blue No. 1 aluminum varnish-ITT 0 9.63 0 0.48 0 0 2.52 0 D&C red No. 6 barium varnish-ITT 0 0 34.53 0 0 0 0 8.02 Black iron oxide 0 0 0.07 0 0 0.95 0 0 D&C red No. 27 aluminum varnish-ITT 0 0 0 3.91 0 0 0 18.87 Red iron oxide 34 0 0 0 0 5.47 0 0 0 Yellow iron oxide 0 0 0 0 0.61 0 0 0.7 Yellow 5 varnish-ITT 0 0 0 0 0 7.1 0 0 Original L* 19 17 33 25 37 18 22 40 Initial a* 26 16 53 38 19 32 25 54 Original b* 26 16 53 38 19 32 25 54

The compositions were heated at 87°C. This temperature was selected as the optimal retention temperature by assessing the melting temperature of the wax phase of the lipstick base through differential scanning calorimetry (DSC) and determining the range where complete phase transition from solid to liquid of the wax phase of the test formulations occurred. At hourly intervals, starting when the emulsions reached 87°C (t=0), the change in color shade of each composition from the initial heating time was measured (ΔΕ). To measure color at each time point, the volume was poured onto a Lanetta card with a constant thickness of 3 mm. The measurements were carried out on the white part of the Lanetta map. Spectroscopic measurements were carried out in the L*a*b* color space using a Konica Minolta CM-2600D spectrophotometer. This process was developed to reflect the manufacturing stresses to which the compositions are subjected, thereby demonstrating the durability of the color shade and consistency of the composition during mass production. Color does not usually change when cooled, since the forces that accelerate color instability are sources of energy (eg heat, light, etc.). In table Figure 2 shows the corresponding space coordinates L*a*b* of the original color shade for each composition at the moment t=0.

The change in color shade was monitored at hourly intervals. In fig. 1 illustrates color shade measurements for each composition after 8 hours of heating at 87°C. As you can see, the durability of the color shade in anhydrous formulations is much greater than in glycerin-oil emulsions. This durability has been demonstrated for a combination of pigment grinds that provide formulations with shades of color in the L*a*b* coordinate system, in addition to color shade 8 (L*=40, a*=54, b*=18). Therefore, color shades that exist in other regions of the color space (eg, colors 1-7) cannot be formulated in glycerin-in-oil emulsions because they would not retain their color when mass produced. These non-inventive compositions contain only anatase TiO ₂ and exhibit increased instability of organic pigments in an aqueous environment.

Although anhydrous formulations have increased color shade stability compared to their glycerin-in-oil counterparts, it can be seen that some of these formulations are also subject to variations in color shade (i.e., instability is also observed in anhydrous formulations). As shown below, these experiments performed with compositions with increased levels of rutile TiO2 will exhibit less color change due to the increased persistence of organic pigments in environments containing rutile TiO2.

Example 2. Leveling out color changes in formulations containing only ITT-treated rutile TiO ₂ .

Three different compositions of pigment grinds were tested to illustrate the effect of ITT-treated rutile TiO ₂ on the color change of pigmented compositions. In table Figure 3 shows the tested compositions of pigment grinds. Each of grind compositions 1, 2 and 3 was used to produce three different pigment grinds: A) with untreated TiO ₂ (U-TiO ₂ ) as anatase; B) with ITT-treated TiO ₂ (ITT-TiO ₂ ) in the form of anatase and rutile; and C) with ITT-treated TiO ₂ in the form of rutile.

Table 3

Component Weight percentage in pigment grinding Composition of 1 grind TiO ₂ (raw or ITT treated) 7.00% Red 7 (ITT-processed) 8.40% Red 6 (ITT-processed) 34.53% Black Iron Oxide (ITT-Treated) 0.07% Diphenyl dimethicone 50% Composition 2 grinds TiO ₂ (raw or ITT treated) 18.48% Red 7 (ITT-processed) 27.13% Blue 1 (ITT-processed) 0.48% Red 27 (ITT-treated) 3.91% Diphenyl dimethicone 50% Composition 3 grinds TiO ₂ (raw or ITT treated) 13.96% Red 7 (ITT-processed) 32.97% Red Iron Oxide (ITT-Treated) 0.55% Blue 1 (ITT-processed) 2.52% Diphenyl dimethicone 50%

Each pigment grind was then used to create an emulsion with an internal glycerol phase. The emulsions contained 10% of each prepared pigment grind. The final compositions are shown in table. 4. It will be clear that the weight percentages in pigment grinding indicated in the table. 4, include 50% diphenyl dimethicone. Therefore, the compositions contained 55.11% emollients by weight of the composition.

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Table 4

Component Weight percentage (%) a-hydroxy acid 2.00 The basis 0.35 Emollient 50.11 Emulsifier 3.75 Fragrant oil 0.13 Glycerin (humectant) 10.00 Powder 5.63 Preservative 0.50 Sunscreen 7.50 Sweetener 0.28 Wax 2.92 Demineralized water 1.00 Pigment grinding 10.00

The emulsions were heated to 87°C. At hourly intervals, starting when the emulsions reached 87°C (t=0), the color change (ΔΕ) of each emulsion from the initial heating time was measured, as in example 1. Color measurements with the reflective component included (SCI) for each of the compositions 1 , 2 and 3 pigment grinding are shown in table. 5, 6 and 7 respectively.

Table 5

U-TiO ₂ (anatase) ITT-TiO ₂ (anatase) ITT-TiO ₂ (rutile) Grinding 1(A) Grinding 1(B) Grinding 1(C) 0 0.00 0.00 0.00 1 1.52 1.69 0.72 2 2.00 2.41 1.19 3 2.60 0.59 1.37 4 8.20 0.61 1.83 5 15.43 1.06 2.47 6 20.46 1.32 1.68 7 23.31 1.79 2.29 8 21.20 2.81 1.09

Table 6

U-TiO ₂ (anatase) ITT-TiO ₂ (anatase) ITT-TiO ₂ (rutile) Grinding 2(A) Grinding 2(B) Grinding 2(C) 0 0.00 0.00 0.00 1 3.09 3.92 1.78 2 3.70 4.16 2.95 β 5.73 5.85 2.59 4 4.77 6.89 2.54 5 5.88 8.88 3.75 6 5.31 7.75 3.65 7 6.27 8.98 3.23 8 8.08 9.49 2.54

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Table 7

U-TiO ₂ (anatase) ITT-TiO ₂ (anatase) ITT-TiO ₂ (rutile) Grinding 3(A) Grinding 3(B) Grinding 3(C) 0 0.00 0.00 0.00 1 0.93 2.32 0.69 2 1.67 2.54 0.95 3 2.30 3.38 1.28 4 4.76 3.26 1.92 5 4.75 1.71 2.24 6 13.44 2.30 2.83 7 14.44 3.25 2.68 8 12.71 3.51 2.98

In fig. 2-4 show the values characterizing the difference in color change for compositions 1-3 of pigment grinds, respectively. In fig. 5 is a bar graph comparing the color change for each of the pigment grinds after 8 hours of heating above the melting point of the wax component for each formulation (87°C). The black bar represents the color change when using untreated anatase TiO ₂ , the white bar shows the color change when using ITT-treated anatase TiO ₂ , and the bar shaded with diagonal parallel lines represents the color change when using ITT-treated rutile TiO ₂ . The dotted horizontal line represents the Δε approximation for noticeable color change, as disclosed in Mahy M., Color Research and Application, 19:105-21 (1994), incorporated by reference herein in its entirety. In each emulsion, rutile ITT-TiO ₂ exhibited reduced color migration compared to its untreated and ITT-treated anatase counterparts. The use of rutile TiO ₂ in these compositions provides increased pigment stability.

As can be seen, the use of rutile TiO ₂ instead of anatase TiO ₂ provides increased color stability. This effect was shown for each of the compositions measured after 8 hours of heating. Without being limited by any theory, it is believed that rutile TiO ₂ minimizes the hydrolysis of organic pigments, thereby providing reduced color changes. Rutile TiO ₂ can provide stabilization of organic pigments that anatase TiO ₂ does not provide. Fluctuations in color change in formulations 1, 2 and 3 may occur due to different concentrations of azo dye, instability due to interactions between combinations of azo dyes associated with the type of dye, dye concentration, if and which dye cation is used (e.g. Al ⁺ , Ba ⁺ , Ca ^{+ ,} etc.) in salt form, the support to which the dyes are bound, and the strength of binding to the support (eg, the amount of dye released into the medium). In addition, the pH and electrolyte content of the aqueous phases can also have an impact on the durability of the color shade. In formulations 1-3, the pH of the glycerol phase ranged from 3.7 to 3.9. However, these multiple stability problems can be mitigated by including rutile TiO ₂ rather than anatase TiO ₂ .

Example 3: Reversal of discoloration using only rutile TiO ₂ (untreated and ITT-treated).

Grind formulations 4 and 5 were created to illustrate the increase in color fastness provided by using untreated rutile TiO ₂ and ITT-treated rutile TiO ₂ compared to their anatase counterparts from Example 1 (formulations 4 and 5, respectively, to provide color tint). The pigment components of each grinding composition, providing the initial values of the color characteristic L*a*b* at t=0, are shown in table. 8.

Table 8

Composition for providing color tint 4 5 Original L* 19 17 Initial a* 26 16 Original b* 26 16

The color tint fastness of each color tint composition was tested as in Examples 1 and 2. FIG. 6 shows the color change for the composition to provide color shade 4, and FIG. 7 shows the color change for the composition to provide color shade 5 after 8 hours of heating at 87°C.

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As can be seen, exclusively untreated rutile TiO2 is able to neutralize the color instability observed with these organic azo pigment formulations (eg glycerin-in-oil emulsions). Variations in increased durability depend on the specific pigments used.

However, rutile TiO2 (treated or untreated) stabilized the pigments and color shade of these formulations for every shade of color measured.

Example 4: Increased color fastness using Radiation Attenuation Qualified TiO2.

Grind compositions were tested in various emulsions to demonstrate the effect of radiation attenuation grade TiO2 on color hue variation and stability of pigmented compositions. The grinding compositions were created as shown in table. 9, and measured the original values of the L*a*b* color space. ITT-treated and ITT/dimethicone-treated (DTV) compounds were purchased from KOBO Products (NJ, USA).

Table 9

Component Weight percentage in pigment grinding Composition 4 grinds Rutile TiO ₂ (ITT-treated) 32.50% Cosmetic red oxide (ITT-processed) 8.20% Yellow 5 varnish (ITT-treated) 4.00% Red Iron Oxide (ITT-Treated) 5.30% Ethylhexyl palmitate 50% Composition 5 grinding Rutile TiO ₂ (TTV-treated) 32.50% Cosmetic red oxide (TTV-processed) 12.20% Yellow 5 varnish (TTV-treated) 4.00% Black Iron Oxide (TTB-treated) 1.30% Ethylhexyl palmitate 50% Composition 6 grinding Rutile TiO ₂ (TTV-treated) 35.00% Red 7 (TTV-processed) 10.00% Yellow Iron Oxide (TTV-Treated) 5.00% Ethylhexyl palmitate 50%

Pigment grinds were made in a glycerin-in-oil emulsion. Each pigment grind was formulated into three different batches. Batch A was a glycerin-in-oil emulsion with 10% pigment milling. Batch B was a glycerin-in-oil emulsion with an acidic internal phase (pH 3.7 to 3.9) and 10% pigment grind. Batch C was a glycerin-in-oil emulsion with an acidic internal phase (pH 3.7 to 3.9) with 5% pigment ground, 5% surface treated radiation attenuation grade TiO2 (TTO-TTV7, available from KOBO Products). Initial L*a*b* color space (SCI) values were measured as described above for several batches of emulsions. Batch C with grinding composition 5 had L*a*b* values of 42.12, 22.97 and 12.71, respectively. Measurements could not be taken for batch B because the pigment had precipitated from the emulsion, resulting in an uneven color tone. The results are shown in table. 10.

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Table 10

Composition 4 grinds Batch A Party C L* 42.95 42.00 A* 24.42 25.49 b* 19.95 18.89

As can be seen, there is minimal difference in color between Batch A and Batch C even though Batch C contains half the amount of pigment grind as Batch A. The initial difference in color shade between Batch A and Batch C for pigment grind 4 is

ΔΕ = V(42.95-42.00) ² +(24.42-25.49) ² +(19.95-18.89) ² - 1.78

Similar measurements were carried out for milling composition 6 and the color shade values L*a*b* were measured with the reflective component included. The grinding composition 6 was made into two emulsions, and the color space values of the resulting emulsion are shown in table. eleven.

Table 11

Component Control, weight percentage (%) Emulsion with TiO ₂ qualification for radiation attenuation, weight percentage (%) Composition of the internal phase of the emulsion 29.89 29.89 Emollient 50.11 55.11 Pigment grinding 6 20.00 10.00 Rutile TiO ₂ qualified for radiation attenuation (TTO-TTV) 0.00 5.00 Original L* 46.47 41.31 Initial a* 34.08 34.12 Original b* 6.18 4.19

In these experiments, the weight percentage of emollients is not included in the emollients added with the pigment grind. Therefore, each emulsion contains 60.11% emollients by weight of the composition. In these experiments, the radiation attenuation qualification component was dispersed in the continuous phase rather than in the pigment grind due to its high level of dispersibility. As can be seen, these emulsions have similar initial color characteristic values (ΔΕ=5.53).

These emulsions were heated to 90°C. At hourly intervals, starting when the emulsions reached 90°C (t=0), the change in color shade (ΔΕ) for each emulsion from t=0 was measured as in example 1. The ΔΕ values at each time point are shown in table. 12 and shown in FIG. 8A and 8B.

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Table 12

Time (hours) Control (ΔΕ) Emulsion with qualification component for radiation attenuation (ΔΕ) 0 0.00 0.00 1 11.01 0.72 2 12.78 2.44 3 20.85 2.94 4 24.10 1.88 5 29.01 3.97 6 29.83 3.97 7 31.32 2.78 8 31.56 3.18

As can be seen, the emulsion with rutile TiO ₂ radiation attenuation grade significantly reduces the color change compared to the emulsion without radiation attenuation grade TiO ₂ . Radiation attenuation grade TiO ₂ can also help reduce color change and promote pigment stability achieved by incorporating rutile pigment TiO ₂ into the pigment grind. This reduction in color change (and increase in pigment stability) ensures minimal change in the emulsion's original color shade compared to its higher percentage pigment mill counterpart.

Specific Embodiments

Specific embodiments of the present invention are numbered below.

Specific Embodiment 1. A pigmented composition comprising (a) a pigmented titanium dioxide consisting of or predominantly consisting of rutile phase titanium dioxide; and (b) organic pigments, optionally treated with isopropyl triisostearyl titanate (ITT) and/or ITT/dimethicone.

Specific Embodiment 2: The pigmented composition according to Specific Embodiment 1, further comprising water and/or glycerin.

Specific Embodiment 3: The pigmented composition according to Specific Embodiment 1 or 2, wherein the composition is in the form of an emulsion.

Specific Embodiment 4. The pigmented composition according to Specific Embodiment 3, wherein the emulsion is a water-in-oil, oil-in, glycerin-in-oil, silicone-in-water, or water-in-silicone emulsion.

Specific Embodiment 5. The pigmented composition according to any one of Specific Embodiments 1 to 4, wherein said emulsion contains an aqueous phase, and said aqueous phase constitutes from 1% to 20% by weight of said composition.

Specific Embodiment 6. The pigmented composition according to any one of Specific Embodiments 1 to 5, wherein said titanium dioxide is treated with isopropyl triisostearyl titanate (ITT) or ITT/dimethicone.

Specific embodiment 7. The pigmented composition according to any of specific embodiments 1-6, wherein said organic pigments include red 7 and/or red 6 and/or red 27 and/or blue 1 and/or yellow 5 and /or red 33.

Specific Embodiment 8. The pigmented composition according to any one of specific embodiments 1-7, wherein said organic pigments contain from 5 to 40% red 7 by weight of the composition.

Specific Embodiment 9. The pigmented composition according to any one of specific embodiments 1-8, wherein said composition does not have a color characteristic value (L*, a*, b*) (L*=40±10, a*=54±20, b*=18±20).

Specific embodiment 10. The pigmented composition according to any one of specific embodiments 1-9, wherein said composition further comprises a wax.

Specific embodiment 11. The pigmented composition according to specific embodiment 10, wherein said wax comprises paraffin wax, microcrystalline petroleum wax, or combinations thereof.

Specific Embodiment 12. The pigmented composition according to any one of specific embodiments 1 to 11, wherein said composition further comprises an emulsifier, a fragrance oil, a powder, a preservative, a sweetener, a sunscreen, or combinations thereof.

Specific embodiment 13. The pigmented composition according to any one of specific embodiments 1-12, wherein the composition is in the form of a solid rod, liquid, cream, lotion or powder.

Specific Embodiment 14. The pigmented composition according to any one of Specific Embodiments 1 to 13, wherein said composition is in the form of a lipstick, lipstick stick, mascara, eyeliner, blush, tanning product, powder, eye shadow, nail polish, foundation, lotion or concealer.

Specific embodiment 15. The pigmented composition according to any one of specific embodiments 1-14, wherein the composition contains less than 1% iron oxide by weight of the composition.

Specific embodiment 16. The pigmented composition according to any one of specific embodiments 1-15, wherein the composition contains (a) from 0.1 to 10% rutile pigment TiO ₂ by weight of the composition; and (b) from 1 to 10% organic pigments by weight of the composition.

Specific Embodiment 17. The pigmented composition of Specific Embodiment 16, wherein said composition is in the form of a glycerin-in-oil emulsion and further contains (c) 20 to 50% emollient (e.g., silicone such as diphenyl dimethicone, ester oil such as ethylhexyl palmitate, etc.) by weight of the composition; and (d) 1 to 40% (eg, 1 to 10%, 20 to 30%, 30 to 40%, etc.) glycerol, by weight of the composition.

Specific embodiment 18. A pigmented glycerin-in-oil emulsion composition comprising:

(a) from 0.1 to 10% rutile pigment TiO ₂ by weight of the composition and (b) from 1 to 10% organic pigments (for example, red 7, red 6, red 27, red 33, blue 1, yellow 5, etc. .d.) by weight of the composition;

(c) from 20 to 50% silicone by weight of the composition; and (d) from 1 to 40% (eg, 1-10, 20-30, 30-40%, etc.) glycerol, by weight of the composition.

Specific embodiment 19. The pigmented composition according to any one of specific embodiments 1-18, wherein the weight ratio of said organic pigments to said rutile pigment TiO ₂ is from 20:1 to 1:20 (for example, from 20:1 to 10:1, from 10:1 to 1:1, from 8:1 to 2:1, from 9:1 to 1:1, from 8:1 to 1:1, from 7:1 to 1:1, from 6:1 to 1:1, from 5:1 to 1:1, from 4:1 to 1:1, from 3:1 to 1:1, from 2:1 to 1:1, from 1:1 to 1:10, from 1:10 to 1:20, 1:5 to 1:15, 1:8 to 1:2, 1:9 to 1:1, 1:8 to 1:1, 1:7 to 1 :1, from 1:6 to 1:1, from 1:5 to 1:1, from 1:4 to 1:1, from 1:3 to 1:1, from 1:2 to 1:1, etc. d.).

Specific embodiment 20. The pigmented composition according to any of specific embodiments 1-19, further comprising TiO ₂ qualified for radiation attenuation.

Specific embodiment 21. The pigmented composition according to specific embodiment 20, wherein said radiation attenuation grade TiO ₂ is rutile TiO 2 , anatase TiO 2 , or combinations thereof.

Specific embodiment 22. The pigmented composition according to specific embodiment 20 or 21, wherein the weight ratio of pigmented TiO ₂ to radiation attenuation grade TiO ₂ is from 10:1 to 1:10 (for example, from 10:1 to 1:1, from 5:1 to 1:1, from 2:1 to 1:1, from 1:10 to 1:1, from 1:5 to 1:1, from 1:2 to 1:1).

Specific embodiment 23. The pigmented composition according to any one of specific embodiments 20-22, wherein said radiation attenuation grade TiO ₂ is surface treated with isopropyl triisostearyl titanate (ITT) or ITT/dimethicone.

Specific Embodiment 24: A method for coloring the outer covering of a human body, comprising applying to said outer covering of the human body a composition according to any of Specific Embodiments 1-23.

Specific embodiment 25. The method according to specific embodiment 24, wherein said outer covering of the human body is a keratinized surface.

Specific embodiment 26. The method according to specific embodiment 24, wherein said outer covering of the human body is hair, skin, lips or nails.

Specific embodiment 28. The method according to any one of specific embodiments 24-26, wherein said application step forms a film of said composition on said outer covering of the human body.

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Claims (19)

Since various modifications may be made to the foregoing subject matter without departing from the scope and spirit of the present invention, it is intended that all subject matter contained in the foregoing description or as defined in the appended claims are to be interpreted as descriptive and illustrative of the present invention. In light of the above provisions, the present invention is subject to many modifications and variations. Accordingly, the present description is intended to cover all such alternatives, modifications and variations that come within the scope of the appended claims. CLAIM 1. A pigmented composition for application to the outer cover of the human body, containing (a) pigmented titanium dioxide containing more than 60% by weight of rutile phase titanium dioxide; and (b) organic pigments that are based on azo dyes or contain one or more azo moieties, wherein said pigment titanium dioxide and organic pigments are treated with isopropyl triisostearyl titanate (ITT) or ITT/dimethicone. 2. Pigmented composition according to claim 1, additionally containing water and/or glycerin. 3. Pigmented composition according to claim 1 or 2, where the specified composition is presented in the form of an emulsion. 4. The pigmented composition according to claim 3, wherein said emulsion is a water-in-oil, oil-in-water, glycerin-in-oil, silicone-in-water or water-in-silicone emulsion. 5. A pigmented composition according to claim 3 or 4, wherein said emulsion contains an aqueous phase and said aqueous phase constitutes from 1 to 20% by weight of said composition. 6. Pigmented composition according to any one of claims 1 to 5, where said organic pigments include red 7, and/or red 6, and/or red 27, and/or blue 1, and/or yellow 5, and/or red 33 . 7. Pigmented composition according to any one of claims 1 to 6, wherein said organic pigments contain from 5 to 40% red 7 by weight of the composition. 8. A pigmented composition according to any one of claims 1 to 7, wherein said composition further contains wax. 9. The pigmented composition of claim 8, wherein said wax comprises paraffin wax, microcrystalline petroleum wax, or combinations thereof. 10. A pigmented composition according to any one of claims 1 to 9, wherein said composition is presented in the form of a solid rod, liquid, cream, lotion or powder. 11. A pigmented composition according to any one of claims 1 to 10, where the said composition is presented in the form of lipstick, lipstick pencil, mascara for eyelashes and eyebrows, eyeliner pencil, blush, tanning cosmetic, powder, eye shadow, nail polish, foundation, lotion or concealer. 12. Pigmented composition according to any one of claims 1 to 11, where the weight ratio of said organic pigments to said rutile pigment TiO ₂ is from 20:1 to 1:20. 13. A pigmented composition for application to the outer cover of the human body in the form of a glycerin-in-oil emulsion containing (a) from 0.1 to 10% rutile pigment TiO2 by weight of the composition; (b) from 1 to 10% organic pigments by weight of the composition, where the organic pigments are based on azo dyes or contain one or more azo fragments; (c) from 20 to 50% silicone by weight of the composition; and (d) from 1 to 40% glycerol by weight of the composition, wherein said pigment TiO ₂ and organic pigments are treated with isopropyl triisostearyl titanate (ITT) or ITT/dimethicone. 14. The pigmented composition according to claim 13, where the weight ratio of said organic pigments to said rutile pigment TiO ₂ is from 20:1 to 1:20. 15. Pigmented composition according to any one of claims 1 to 14, additionally containing TiO ₂ qualified for attenuating radiation. 16. The pigmented composition according to claim 15, wherein said TiO ₂ of radiation attenuation qualification is rutile TiO2, anatase TiO2 or combinations thereof. 17. The pigmented composition according to claim 15 or 16, wherein the weight ratio of pigmented TiO ₂ to radiation attenuation grade TiO ₂ is from 10:1 to 1:10. 18. The pigmented composition according to any one of claims 15 to 17, wherein said TiO ₂ is surface-treated with isopropyl triisostearyl titanate (ITT) or ITT/dimethicone for radiation attenuation. 19. A method for coloring the outer cover of the human body, including applying a composition according to any one of claims 1 to 18 to said outer cover of the human body. -