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Title:
COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES, USE OF A COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES AND PROCESSES FOR MANUFACTURING A COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES
Document Type and Number:
WIPO Patent Application WO/2022/160021
Kind Code:
A1
Abstract:
The present invention relates to a cosmetic composition for providing dark color shades, comprising (a) from 5.0 to 20.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of yellow, black and red iron oxides; (b) at least one UV filter; wherein the relative weight ratio between the iron oxides is from 52.0 to 65.0 % of yellow iron oxide, from 20.0 to 26.0 % of red iron oxide, and from 10.0 to 22.0 % of black iron oxide. The present invention is also directed to a use of a cosmetic composition for providing dark color shades, and to processes for manufacturing a cosmetic composition for providing dark color shades.

Inventors:
NEVES PITTA PAULA (BR)
BOISDRON MARIE (CN)
SAUCE SILVA RAFAEL (BR)
HANASHIRO TASSIA (BR)
NASCIMENTO ANA PAULA (BR)
Application Number:
PCT/BR2021/050046
Publication Date:
August 04, 2022
Filing Date:
January 29, 2021
Export Citation:
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Assignee:
OREAL (FR)
NEVES PITTA PAULA (BR)
International Classes:
A61Q17/04; A61K8/19; A61K8/29; A61K8/35; A61K8/37; A61K8/40; A61K8/49; A61Q1/02
Domestic Patent References:
WO2020000071A12020-01-02
WO2020000072A12020-01-02
WO2010019164A12010-02-18
WO1993004665A11993-03-18
WO2004006878A12004-01-22
WO2005058269A12005-06-30
WO2006032741A12006-03-30
WO2004085412A22004-10-07
WO2006035000A12006-04-06
WO2006034982A12006-04-06
WO2006034991A12006-04-06
WO2006035007A12006-04-06
WO2006034992A12006-04-06
WO2006034985A12006-04-06
Foreign References:
US20070248550A12007-10-25
US20160303020A12016-10-20
JPH05262617A1993-10-12
KR102058513B12019-12-23
US20020018791A12002-02-14
EP0696451A11996-02-14
US8541009B22013-09-24
US4578266A1986-03-25
US5624663A1997-04-29
EP0669323A11995-08-30
US2463264A1949-03-01
US5237071A1993-08-17
US5166355A1992-11-24
GB2303549A1997-02-26
DE19726184A11998-12-24
EP0893119A11999-01-27
EP0832642A21998-04-01
EP1027883A22000-08-16
EP1300137A22003-04-09
DE10162844A12003-07-03
DE19855649A12000-06-08
EP0967200A11999-12-29
DE19746654A11999-02-18
DE19755649A11999-06-17
EP1008586A12000-06-14
EP1133980A22001-09-19
EP1133981A22001-09-19
US6225467B12001-05-01
EP1990372A22008-11-12
US5601811A1997-02-11
Other References:
"Symmetrical Triazine Derivatives", IP.COM JOURNAL, 20 September 2004 (2004-09-20)
Attorney, Agent or Firm:
NAKATA, Carolina et al. (BR)
Download PDF:
Claims:
SET OF CLAIMS

1 . A cosmetic composition for providing dark color shades, comprising:

(a) from 5.0 to 20.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of yellow, black and red iron oxides,

(b) at least one UV filter, wherein the relative weight ratio between the iron oxides is

- from 52.0 to 65.0 % of yellow iron oxide,

- from 20.0 to 26.0 % of red iron oxide, and

- from 10.0 to 22.0 % of black iron oxide.

2. The composition, according to claim 1 , wherein the iron oxides are selected from coated or uncoated iron oxides.

3. The composition, according to claim 1 , comprising:

- from 50.0 to 55.0 % of uncoated yellow iron oxide,

- from 22.0 to 26.0 % of uncoated red iron oxide, and

- from 15.0 to 22.0 % of uncoated black iron oxide.

4. The composition, according to claim 1 , comprising:

- from 60.0 to 65.0 % of coated yellow iron oxide,

- from 20.0 to 25.0 % of coated red iron oxide, and

- from 10.0 to 15.0 % of coated black iron oxide.

5. The composition, according to claim 1 , wherein it is free of pigment titanium dioxide.

6. The composition, according to claim 1 , wherein the at least one UV filter is selected from octocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl salicylate, ethylhexyl triazone, butyl methoxydibenzoylmethane, UV-filter titanium dioxide, bis-ethylhexyloxyphenol methoxyphenyl triazine, homosalate and mixtures thereof.

7. The composition, according to claim 1 , wherein the amount of the at least one UV filter ranges from 15.0 to 25.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition.

8. The composition, according to claim 1 , further comprising from 1 .0 to 5.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of Copernicia cerifera (carnauba) wax.

9. The composition, according to claim 1 , further comprising from 55.0 to 80.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, cosmetically acceptable ingredients selected from additional pigments, active compounds, fatty compounds, fillers, perfume/fragrance, polymers, preserving agents, solvents, surfactants, vitamins, silicones and mixtures thereof.

10. The composition, according to claim 9, wherein the additional compounds is selected from the group of magnesium sulfate, caffeine, triethanolamine, Citrus limon (lemon) fruit extract and mixtures thereof.

11 . The composition, according to claim 9, wherein the fatty compound is selected from isononyl isononanoate, stearyl alcohol, and mixtures thereof.

12. The composition, according to claim 9, wherein the filler is selected from silica, silica silylate, disteardimonium hectorite, synthetic fluorphlogopite, and mixtures thereof.

13. The composition, according to claim 9, wherein the polymer is selected from ammonium acryloyldimethyltaurate/vp copolymer, aluminum starch octenylsuccinate, aery lates/C 10-30 alkyl acrylate crosspolymer, and mixtures thereof.

14. The composition, according to claim 9, wherein the preserving and/or chelating agent is selected from phenoxyethanol, chlorphenesin, disodium EDTA and mixtures thereof.

15. The composition, according to claim 9, wherein the solvent or emollient is selected from caprylyl glycol, water, glycerin, propanediol, alcohol, propylene glycol, and mixtures thereof.

16. The composition, according to claim 9, wherein the surfactant is selected from glyceryl stearate (and) PEG-100 stearate, potassium cetyl phosphate, sodium methyl stearoyl taurate, poloxamer 338, stearic acid, polyglyceryl-4 diisostearate/polyhydroxystearate/sebacate, PEG-30 dipolyhydroxystearate, and mixtures thereof.

17. The composition, according to claim 9, wherein the vitamin is selected from ascorbyl glucoside, tocopherol, niacinamide, and mixtures thereof.

18. The composition, according to claim 9, wherein the silicon is selected from dimethicone, vinyl dimethicone/methicone silsesquioxane crosspolymer, and mixtures thereof.

19. The composition, according to claim 1 , wherein the dark color shades offer color shades suitable for skin phototypes 5 and 6.

20. A use of a cosmetic composition for providing dark color shades, comprising:

(a) from 5.0 to 20.0 % by weight, based on the total weight of the composition, of yellow, black and red iron oxides,

(b) at least one UV filter, wherein the relative weight ratio between the iron oxides is

- from 52.0 to 65.0 % of yellow iron oxide,

- from 20.0 to 26.0 % of red iron oxide, and

- from 10.0 to 22.0 % of black iron oxide, wherein it is for the manufacture of a dark tinted sunscreen cosmetic composition, suitable for skin phototypes 5 and 6.

21. A process for manufacturing a cosmetic composition for providing dark color shades, comprising:

(a) from 5.0 to 20.0 % by weight, based on the total weight of the composition, of yellow, black and red iron oxides,

(b) at least one UV filter, wherein the relative weight ratio between the iron oxides is

- from 52.0 to 65.0 % of yellow iron oxide,

- from 20.0 to 26.0 % of red iron oxide, and

- from 10.0 to 22.0 % of black iron oxide; wherein the process comprises the steps of:

Step (A): Main Vessel - Hot oily phase comprising oil raw materials in a temperature ranging from 75 eC 80 eC;

Step (B): Side Vessel - room temperature or 75-80 eC aqueous phase comprising aqueous raw materials;

(C): the aqueous phase of step (B) is added to the oil phase of step (A), after which the emulsifier is subsequently added, followed by mixing the mixture;

(D): the polymers are added to the mixture obtained in step (C), subsequently followed by a neutralization;

(E): the fillers are gradually added to the mixture obtained in step (D) and mixed until homogeneity, at a temperature of below 30eC.

22. A process for manufacturing a cosmetic composition for providing dark color shades, comprising:

(a) from 5.0 to 20.0 % by weight, based on the total weight of the composition, of yellow, black and red iron oxides,

(b) at least one UV filter, wherein the relative weight ratio between the iron oxides is - from 52.0 to 65.0 % of yellow iron oxide,

- from 20.0 to 26.0 % of red iron oxide, and

- from 10.0 to 22.0 % of black iron oxide; wherein the process comprises the steps of:

(A) mixing the aqueous phase ingredients with each other in a main vessel, therefore forming an aqueous phase, and

(B) adding the oily ingredients to the aqueous phase, individually, therefore forming an emulsion, and

(C) adding the pigments.

Description:
COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES, USE OF A COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES AND PROCESSES FOR MANUFACTURING A COSMETIC COMPOSITION FOR PROVIDING DARK COLOR SHADES FIELD OF THE INVENTION

The present invention relates to a cosmetic composition for providing dark color shades, comprising (a) from 5.0 to 20.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition, of yellow, black and red iron oxides; (b) at least one UV filter; wherein the relative weight ratio between the iron oxides is from 52.0 to 65.0 % of yellow iron oxide, from 20.0 to 26.0 % of red iron oxide, and from 10.0 to 22.0 % of black iron oxide. The present invention is also directed to a use of a cosmetic composition for providing dark color shades, and to processes for manufacturing a cosmetic composition for providing dark color shades. The composition for providing dark color shades of the present invention is suitable for skin phototypes 5 and 6.

BACKGROUND OF THE INVENTION

Widely used to protect skin from damages caused by the sun, untinted cosmetic compositions with UV filters, particularly cosmetic sunscreen compositions, are a big part of market. Due to the big demand for multibenefits products, bringing different benefits in the same product, the consumers are always looking for products that provide high UV protection with a makeup effect and medium to high coverage and fit with diverse skin tones and subtones.

Among the scales to access the skintype of subjects, one example is the Fitzpatrick scale. In particular, a phototype 1 of said scale is associated with very light skin, red or blonde hair, blue or green eyes, and a skin that always burns and/or never tans in the sun, wherein phototype 5 is commonly associated with dark brown skin, dark brown or black hair, brown eyes and tan easily and a skin that rarely burns when exposed to the sun, and phototype 6 is commonly associated with black skin, black hair, dark brown eyes and a skin that does not burn when exposed to the sun.

Additionally, the photoprotection of keratinous materials, including both skin and hair, is considered of great importance in order to protect from sun-damage, sunburn, photo-aging, as well as to decrease the chances of skin cancer development caused by exposure to ultraviolet (“UV”) radiation. There are typically two types of UVA/UVB cosmetic sunscreen compositions used to accomplish photoprotection, namely, inorganic UV filters and organic UV filters.

The degree of UV protection afforded by a cosmetic composition is directly related to the amount and type of UV filters contained therein. Particularly, cosmetic sunscreen compositions must provide good protection against the sun, a measure of which is the Sun Protection Factor (SPF) value, a desirable balance between UVA and UVB protection, particularly a minimum UVA protection factor, yet have satisfactory sensory perception, such as a smooth and dry touch but not greasy feel upon application.

Furthermore, it is also desirable to produce a cosmetic composition that not only confers photoprotection of keratinous materials, but also provides additional properties. For example, it is desired to produce a cosmetic composition with high SPF and UVA/UVB protection and high concentration of pigments, with the capability of tinting the skin and providing a makeup similar coverage, preferably with medium to high coverage that is capable of suiting different skin tones without the drawbacks of the state- of-the art.

Among these drawbacks of the state-of-the-art, apart from the known challenges of developing a cosmetic composition with UV filters and high concentration of pigments due to the stability of formulas and the proper matching of skin tones with the tinted product, there is an additional challenge related to the market, since there are limited options available of cosmetic products with UV filters, particularly tinted cosmetic sunscreen compositions, which mostly do not offer a satisfactory medium to high coverage and are not suitable for skin phototypes 5 and 6.

Particularly regarding tinted cosmetic sunscreen compositions directed for skin phototypes 5 and 6, the consumers who identify with these prototypes usually notice that the state-of-the-art compositions leave the skin looking ashy (grayish color on the skin after the product is applied). Also, the white cast which is mainly noticed in photographs is more noticeable in dark skin tones, even in broad day light. These negative effects are commonly associated with the presence of pigment titanium dioxide and/or zinc oxide in the composition. Hence, there is a need for stable cosmetic composition for providing dark color shades adapted for skin phototypes 5 and 6 without compromising desirable sunscreen benefits neither the satisfactory sensorial perception, that is also capable of attracting the makeup consumer to the suncare market.

The inventors of the present invention have surprisingly managed to develop a stable cosmetic composition for providing dark color shades with SPF and UVA/UVB protection and high amounts of colored pigments that gives medium to high color coverage suitable for skin phototypes 5 and 6, due to an specific and narrow combination of yellow, black and red iron oxides that provides an intense and dark color.

SUMMARY OF THE INVENTION

The present invention relates to a cosmetic composition for providing dark color shades, comprising (a) from 5.0 to 20.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition, of yellow, black and red iron oxides; (b) at least one UV filter; wherein the relative weight ratio between the iron oxides is from 52.0 to 65.0 % of yellow iron oxide, from 20.0 to 26.0 % of red iron oxide, and from 10.0 to 22.0 % of black iron oxide. The present invention is also directed to a use of a cosmetic composition for providing dark color shades, and to processes for manufacturing a cosmetic composition for providing dark color shades. The composition for providing dark color shades of the present invention is suitable for skin phototypes 5 and 6.

Other features and advantages of the present invention will be apparent from the following more detailed description of the desirable embodiments which illustrates, by way of example, the principles of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a comparative image between a state-of-the-art composition of Example 1 (Fig. 1 a) with the cosmetic composition for providing dark color shades of the present invention of Example 2 (Fig. 1 b).

Fig. 2 is a comparative image between the cosmetic composition for providing dark color shades of the present invention, according to Example 2, with the state-of-the-art composition of Example 1 . As it is clearly shown, the inventive composition provides a darker shade and does not have a white residual.

Fig. 3 relates to Example 8, in which the compositions of Example 2 and Examples 3 to 5 were applied onto the skin of a subject having a dark skin tone, from left to right respectively.

DETAILED DESCRIPTION OF THE INVENTION In an embodiment, the cosmetic composition for providing dark color shades of the present invention comprises:

(a) from about 5.0 to about 20.0 % by weight, including all ranges and subranges there between, based on the total weight of the composition, of yellow, black and red iron oxides,

(b) at least one UV filter, wherein the relative weight ratio between the iron oxides is

- from about 52.0 to about 65.0 % of yellow iron oxide,

- from about 20.0 to about 26.0 % of red iron oxide, and

- from about 10.0 to about 22.0 % of black iron oxide.

The cosmetic composition for providing dark color shades of the present invention, comprising ingredients (a) and (b) above offers color shades suitable for skin phototypes 5 and 6 and is suitable for manufacturing different types of cosmetic compositions, such as water-in-oil or oil-in-water emulsions.

Terms

The term “stable” used herein refers to a physical and/or chemical properties of a cosmetic composition, such as a cosmetic composition for providing dark color shades according to the present invention, that is stable after performing a study of 2 month- length to support 3 years of shelf life (normal conditions) at three different temperatures, such as 4 e C, room temperature and 45 e C, evaluated in time points of 1 and 2 months. Also, an extra study is performed during one week at 55 e C as a screening of stability. After this period, the physical and/or chemical properties such as appearance, color, odor, pH, viscosity and images of optical microscopy are evaluated and must remain satisfactory.

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

As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. Thus, a range from 1 -5, includes specifically 1 , 2, 3, 4 and 5, as well as sub ranges such as 2-5, 3-5, 2- 3, 2-4, 1 -4, etc. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc. The terms “comprising,” “having,” and “including” are used in their open, non-limiting sense.

The compositions and methods of the present disclosure can comprise, consist of, or consist essentially of the essential elements and limitations of the disclosure described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful.

The terms “a,” “an,” and “the” are understood to encompass the plural as well as the singular. Thus, the term “a mixture thereof” also relates to “mixtures thereof.” Throughout the disclosure, the term “a mixture thereof’ is used, following a list of elements as shown in the following example where letters A-F represent the elements: “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture thereof.” The term, “a mixture thereof’ does not require that the mixture include all of A, B, C, D, E, and F (although all of A, B, C, D, E, and F may be included). Rather, it indicates that a mixture of any two or more of A, B, C, D, E, and F can be included. In other words, it is equivalent to the phrase “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture of any two or more of A, B, C, D, E, and F.”

All percentages, parts and ratios herein are based upon the total weight of the compositions of the present disclosure, unless otherwise indicated.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about” which can encompass +/- 10 %, +/- 8 %, +/- 6 %, +/- 5 %, +/- 4 %, +/- 3 %, +/- 2 %, +/- 1 %, or +/- 0.5 %.

Likewise, the term “a salt thereof” also relates to “salts thereof.” Thus, where the disclosure refers to “an element selected from the group consisting of A, B, C, D, E, F, a salt thereof, and a mixture thereof,” it indicates that that one or more of A, B, C, D, and F may be included, one or more of a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included, or a mixture of any two of A, B, C, D, E, F, a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included.

The salts referred to throughout the disclosure may include salts having a counter-ion such as an alkali metal, alkaline earth metal, or ammonium counter-ion. This list of counter-ions, however, is non-limiting.

For the purposes of the present invention, the expression “water-in-oil composition” and similar mean a water-in-oil (W/O) emulsion, also referred as inverse emulsion. Similarly, the expression “oil-in-water composition” and similar mean an oil-in- water (O/W) emulsion.

All components and elements positively set forth in this disclosure can be negatively excluded from the claims. In other words, the compositions of the instant disclosure can be free or essentially free of all components and elements positively recited throughout the instant disclosure.

All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. In the event of an inconsistency between the present disclosure and any publications or patent application incorporated herein by reference, the present disclosure controls.

Pigments

The cosmetic composition for providing dark color shades of the present invention comprises at least three pigments selected from yellow, black and red iron oxides.

In the context of the present invention, the iron oxides of the cosmetic composition for providing dark color shades of the present invention are coated or uncoated iron oxides. Examples of coated iron oxides that may be mentioned more particularly include iron oxides coated with aluminium stearoyl glutamate, sold, for example, under the reference NAI by the company Miyoshi Kasei. Other preferred examples of coated iron oxides include iron oxides coated with disodium stearoyl glutamate and aluminium hydroxide.

For the purposes of the invention, the "coating" of a pigment according to the invention generally denotes the total or partial surface treatment of the pigment with a surface agent, absorbed, adsorbed or grafted onto said pigment.

The coating may represent from about 0.1 to about 20.0 % by weight and in particular from about 0.5 to about 5.0 % by weight, relative to the total weight of the coated pigment.

The coating may be performed, for example, by adsorption of a liquid surface agent onto the surface of the solid particles by simple mixing with stirring of the particles and of said surface agent, optionally with heating, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating may be performed, for example, by chemical reaction of a surface agent with the surface of the solid pigment particles and creation of a covalent bond between the surface agent and the particles. This method is in particular described in patent US 4 578 266.

The chemical surface treatment may consist in diluting the surface agent in a volatile solvent, dispersing the pigments in this mixture and then slowly evaporating off the volatile solvent, so that the surface agent is deposited at the surface of the pigments.

The cosmetic composition for providing dark color shades of the present invention comprises from about 5.0 to about 20.0 % by weight, from about 6.0 to about

18.5 % by weight, from about 7.0 to about 17.0 % by weight, from about 10.0 to about

15.5 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of yellow, black and red iron oxides.

The relative weight ratio between the iron oxides of the cosmetic composition for providing dark color shades of the present invention is from about 52.0 to about 65.0 % of yellow iron oxide, from about 20.0 to about 26.0 % of red iron oxide, and from about 10.0 to about 22.0 % of black iron oxide.

In a preferred embodiment, the relative weight ratio between the iron oxides of the cosmetic composition for providing dark color shades of the present invention is from about 50.0 to about 55.0 % of uncoated yellow iron oxide, from about 22.0 to about 26.0 % of uncoated red iron oxide, and from about 15.0 to about 22.0 % of uncoated black iron oxide.

In another preferred embodiment, the relative weight ratio between the iron oxides of the cosmetic composition for providing dark color shades of the present invention is from about 60.0 to about 65.0 % of coated yellow iron oxide, from about 20.0 to about 25.0 % of coated red iron oxide, and from about 10.0 to about 15.0 % of coated black iron oxide.

Furthermore, the cosmetic composition for providing dark color shades of the present invention may comprise additional pigments.

The term “pigments” is intended to mean white or coloured, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to colour and/or opacify the resulting composition and/or deposit. These pigments may be white or coloured, and mineral and/or organic.

According to a particular embodiment, the additional pigments used according to the invention are chosen from mineral pigments.

The term “mineral pigment” is intended to mean any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on inorganic pigments, except pigment titanium dioxide. Among the additional mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also zinc oxide, additional iron oxides (i.e. , different than yellow, red and black iron oxides) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders, for instance aluminium powder and copper powder. The following mineral pigments may also be used: Ta2Os, TisOs, Ti20s, TiO, ZrC as a mixture with ZrC , Nb20s, CeO2, ZnS.

Titanium Dioxide

As mentioned, the presence of titanium dioxide in cosmetic compositions is associated with the ashy appearance after the application onto the skin and the white cast effect, especially in photographs. Nonetheless, it is important to differentiate the titanium dioxide used as a pigment, herein called as “pigment titanium dioxide”, from the titanium dioxide used as a UV filter, herein called as “UV-filter titanium dioxide”.

Titanium dioxide can form several different shapes, which have different properties. Particularly, the main difference between the pigment titanium dioxide and the UV-filter titanium dioxide is their particle size, being the pigment bigger than the UV-filter. At small sizes and at low concentrations, titanium dioxide appears as a minimal or nonwhite residual, allowing for effective sunscreens that do not appear white.

Pigment titanium dioxide is the most widely used white pigment because of its brightness and very high refractive index, in which it is surpassed only by a few other materials. Pigment titanium dioxide crystal size is ideally bigger than 220 nm, even reaching a micrometric scale, such as about 7.000 nm (measured by electron microscope) to optimize the maximum reflection of visible light. Pigment titanium dioxide is also an effective opacifier in powder form, where it is employed as a pigment to provide whiteness and opacity to products such as paints, coatings, plastics, papers, inks, foods, medicines (i.e. pills and tablets), and most toothpastes. Pigment titanium dioxide is able to scatter the light, making it of more use for pigments.

Moreover, nanosized titanium dioxide, which should herein also be considered as a synonym to “UV-filter titanium dioxide”, is found in the majority of physical sunscreens because of its strong UV light absorbing capabilities and its resistance to discoloration under ultraviolet light. This advantage enhances its stability and ability to protect the skin from ultraviolet light. Nano-scaled (particle size smaller than 200 nm) titanium dioxide particles are primarily used in sunscreen compositions because they scatter visible light much less than titanium dioxide pigments and can give UV protection.

For the objective of the present invention, the cosmetic composition for providing dark color shades is substantially free of pigment titanium dioxide, but the composition may comprise titanium dioxide as a UV filter.

UV Filters

The at least one UV filter of the cosmetic composition for providing dark color shades of the present invention can be selected from the group consisting of oil-soluble organic sunscreen ingredients and water-soluble organic sunscreen ingredients. Nonlimiting suitable organic UV filters of the present invention are further described below.

Oil-soluble organic sunscreen ingredient

The “oil-soluble organic sunscreen ingredient” means any organic compound for screening out UV radiation, which can be fully dissolved in molecular form or miscible in an oil phase or which can be dissolved in colloidal form (for example in micellar form) in an oil fatty phase.

Non-limiting examples of oil-soluble organic sunscreen ingredients useful in the invention include, for example, cinnamic derivatives; anthranilates; salicylic derivatives; dibenzoylmethane derivatives; camphor derivatives; benzophenone derivatives; diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives, especially those cited in patent US5624663; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US2463264; p-aminobenzoic acid (PABA) derivatives; methylene bis(hydroxyphenylbenzotriazole) derivatives as described in applications US5237071 , US5166355, GB2303549, DE19726184 and EP893119; benzoxazole derivatives as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; screening polymers and screening silicones such as those described especially in patent application WO 93/04665; dimers derived from alkyl-styrene such as those described in patent application DE 19855649; 4,4-diarylbutadienes such as those described in patent applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP1133981 , merocyanine derivatives such as those described in patent applications WO 04/006878, WO 05/058269 and WO 06/032741 ; and mixtures thereof, the entire contents of the patents and patent applications being incorporated by reference in their entirety.

As examples of other suitable oil-soluble organic sunscreen ingredients, mention may be made of those denoted hereinbelow under their INCI name:

Cinnamic derivatives:

Examples of suitable cinnamic derivatives include, but are not limited to, ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl ethylhexanoate dimethoxycinnamate.

Dibenzoylmethane derivatives:

Examples of suitable dibenzoylmethane derivatives include, but are not limited to, butyl methoxydibenzoylmethane and isopropyl dibenzoylmethane.

Salicylic derivatives:

Examples of suitable salicylic derivatives include, but are not limited to, homosalate, ethylhexyl salicylate, dipropylene glycol salicylate and TEA salicylate.

Beta, beta -Diphenylacrylate derivatives:

Examples of suitable beta, beta -diphenylacrylate derivatives include, but are not limited to, octocrylene and etocrylene.

Benzophenone derivatives:

Examples of suitable benzophenone derivatives include, but are not limited to, benzophenone-1 , benzophenone-2, benzophenone-3 or oxybenzone, benzophenone- 4, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone-12, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate +” or as a mixture with octyl methoxycinnamate.

Benzylidenecamphor derivatives:

Examples of suitable benzylidenecamphor derivatives include, but are not limited to, 3-benzylidene camphor manufactured, 4-methylbenzylidene camphor, polyacrylamidomethyl benzylidene camphor manufactured. Phenylbenzotriazole derivatives:

Examples of suitable phenylbenzotriazole derivatives include, but are not limited to, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutyl-phenol, or in micronized form as an aqueous dispersion.

Triazine derivatives:

Examples of suitable triazine derivatives include, but are not limited to, bisethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylhexyl butamido triazone, 2,4,6-tris(dineopentyl 4’-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4’-aminobenzalmalonate)s triazine, 2,4-bis(dineopentyl 4'-aminobenzalmalonate)-6-(n- butyl 4'-aminobenzoate)-s-triazine, symmetrical triazine screening agents described in patent US 6,225,467, patent application WO 2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives" IP.COM Journal, IP.COM Inc., West Henrietta, NY, US (20 September 2004), especially 2,4,6-tris(biphenyl)-1 ,3,5-triazines (in particular 2,4,6-tris(biphenyl-4-yl)-1 ,3,5-triazine and 2,4,6-tris(terphenyl)-1 ,3,5-triazine, which is included in patent applications WO 06/035000, WO 06/034982, WO 06/034991 , WO 06/035007, WO 2006/034992 and WO 2006/034985).

Anthranilic derivatives:

An example of a suitable anthranilic derivative includes, but is not limited to, menthyl anthranilate.

Imidazoline derivatives:

An example of a suitable imidazoline derivative includes, but is not limited to, ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

Benzalmalonate derivatives:

An example of a suitable Benzalmalonate derivative includes, but is not limited to, polyorganosiloxane containing benzalmalonate functions, for instance polysilicone-15.

4,4-Diarylbutadiene derivatives:

An example of a suitable 4,4-diarylbutadiene derivative includes, but is not limited to, 1 -Dicarboxy(2,2’-dimethylpropyl)-4,4-diphenyl-butadiene.

Benzoxazole derivatives:

An example of suitable benzoxazole derivative includes, but is not limited to, 2,4-bis[5-(1 -dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylh exyl) imino- 1 ,3,5-triazine, and mixtures thereof.

Water-soluble organic sunscreen ingredient

The “water-soluble organic sunscreen ingredient” means any organic compound for screening out UV radiation, which can be fully dissolved in molecular form or miscible in a liquid aqueous phase or which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

Non-limiting examples of water-soluble organic sunscreen ingredients useful in the invention include, for example, terephthalylidene dicamphor sulfonic acid (Ecamsule), phenylbenzimidazole sulfonic acid (Ensulizole), benzophenone-4, aminobenzoic acid (PABA), 4-Bis(polyethoxy)-para-aminobenzoic acid polyethoxyethyl ester (PEG-25 PABA), camphor benzalkonium methosulfate, methylene bis- benzotriazolyl tetramethylbutylphenol (Bisoctrizole), disodium phenyl dibenzimidazole tetrasulfonate (Bisdisulizole disodium), and tris-biphenyl triazine; their derivatives and corresponding salts; naphthalene bisimide derivatives such as those described in European patent application EP1990372 A2, the entire contents of which is hereby incorporated by reference; and cinnamido amine cationic quaternary salts and derivatives such as those described in United States Patent 5,601 ,81 1 , the entire contents of which is hereby incorporated by reference, and mixtures thereof.

The salts of the compounds that may be used according to the invention are chosen in particular from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; salts of ammonium of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2- hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts. Salts chosen from sodium, potassium, magnesium, strontium, copper, manganese or zinc salts are preferably used. The sodium salt is preferably used.

In a preferred embodiment, the at least one UV filter of the cosmetic composition for providing dark color shades of the present invention is selected from the group of octocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl salicylate, ethylhexyl triazone, butyl methoxydibenzoylmethane, UV-filter titanium dioxide, bisethylhexyloxyphenol methoxyphenyl triazine, homosalate and mixtures thereof. In a preferred embodiment, the amount of the at least one UV filter in the cosmetic composition for providing dark color shades of the present invention ranges from about 15.0 to about 25.0 % by weight, from about 16.0 to about 24.0 % by weight, from about 17.0 to about 23.0 % by weight, from about 18.0 to about 22.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

Additional Ingredients

In addition to the essential components described hereinbefore, the cosmetic composition for providing dark color shades of the present invention may further comprise any usual cosmetically acceptable ingredient, which may be chosen especially from additional pigments, active compounds, fatty compounds, fillers, perfume/fragrance, polymers, preserving and/or chelating agents, solvents, surfactants, vitamins, silicones and mixtures thereof.

A person skilled in the art will take care to select the optional additional ingredients and/or the amount thereof such that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

In a preferred embodiment, the cosmetic composition for providing dark color shades of the present invention further comprises from about 1 .0 to about 5.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition, of Copernicia cerifera (carnauba) wax.

In a preferred embodiment, additional ingredients of the cosmetic composition for providing dark color shades of the present invention are selected from the group of magnesium sulfate, caffeine, triethanolamine, Citrus limon (lemon) fruit extract, and mixtures thereof.

In a preferred embodiment, the fatty compounds of the cosmetic composition for providing dark color shades of the present invention is selected from isononyl isononanoate, stearyl alcohol, and mixtures thereof.

In a preferred embodiment, the filler of the cosmetic composition for providing dark color shades of the present invention is selected from silica, silica silylate, disteardimonium hectorite, polylactic acid, mica, and kaolin. Preferred embodiments of mica include synthetic mica having INCI name synthetic fluorphlogopite, and mixtures thereof. In a preferred embodiment, the polymer of the cosmetic composition for providing dark color shades of the present invention is selected from styrene/acrylates copolymer, ammonium acryloyldimethyltaurate/vp copolymer, aluminum starch octenylsuccinate, aery lates/Ci 0-30 alkyl acrylate crosspolymer, and mixtures thereof.

In a preferred embodiment, the preserving and/or chelating agent of the cosmetic composition for providing dark color shades of the present invention is selected from phenoxyethanol, chlorphenesin, disodium EDTA and mixtures thereof.

In a preferred embodiment, suitable solvents, humectants and emollients of the cosmetic composition for providing dark color shades of the present invention is selected from caprylyl glycol, water, glycerin, propanediol, alcohol, propylene glycol, pentylene glycol, C12-15 alkyl benzoate and mixtures thereof.

The water used may be sterile demineralized water and/or deionized water and/or a floral water such as rose water, cornflower water, chamomile water or lime water, and/or a natural thermal or mineral water such as, for example: water from Vittel, water from the Vichy basin, water from Uriage, water from La Roche Posay, water from La Bourboule, water from Enghien-les-Bains, water from Saint Gervais-les-Bains, water from Neris-les-Bains, water from Allevar-les-Bains, water from Digne, water from Maizieres, water from Neyrac-les-Bains, water from Lons-le-Saunier, water from Eaux-Bonnes, water from Rochefort, water from Saint Christau, water from Les Fumades, water from Tercis- les-Bains or water from Avene. Water may also comprise reconstituted thermal water, that is to say a water comprising trace elements such as zinc, copper, magnesium, etc., reconstituting the characteristics of a thermal water.

In a preferred embodiment, the surfactant of the cosmetic composition for providing dark color shades of the present invention is selected from glyceryl stearate (and) PEG-100 stearate, potassium cetyl phosphate, sodium methyl stearoyl taurate, poloxamer 338, stearic acid, polyglyceryl-4 diisostearate/polyhydroxystearate/sebacate, PEG-30 dipolyhydroxystearate, and mixtures thereof.

In a preferred embodiment, the vitamin of the cosmetic composition for providing dark color shades of the present invention is selected from ascorbyl glucoside, tocopherol, niacinamide, and mixtures thereof.

In a preferred embodiment, the silicone of the cosmetic composition for providing dark color shades of the present invention is selected from dimethicone, vinyl dimethicone/methicone silsesquioxane crosspolymer, among others, and mixtures thereof.

In a preferred embodiment, the additional cosmetically acceptable ingredient of the cosmetic composition for providing dark color shades of the present invention ranges from about 55.0 to about 80.0 % by weight, from about 60.0 to about 75.0 % by weight, from about 60.0 to about 65.0 % by weight, from about 70.0 to about 75.0 % by weight, including all ranges and sub-ranges there between, based on the total weight of the composition.

By way of non-limiting illustration, the invention will now be described with reference to the following examples.

EMBODIMENTS

An example of a suitable cosmetic composition for providing dark color shades according to the present invention, in the form of an oil-in-water emulsion, comprises:

- from 5.0 % to 10.0 % of uncoated yellow, red and black iron oxides, wherein the relative weight ratio between the iron oxides is:

- from 50.0 to 55.0 % of uncoated yellow iron oxide,

- from 22.0 to 26.0 % of uncoated red iron oxide, and

- from 15.0 to 22.0 % of uncoated black iron oxide.

- from 1 .6 % to 1 .9 % of glyceryl stearate (and) peg-100 stearate;

- from 1 .45 % to 1 .6 % of potassium cetyl phosphate;

- from 18.0 % to 22.0 % of ethylhexyl triazone, titanium dioxide, octocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl salicylate and butyl methoxydibenzoylmethane;

- from 0.1 % to 1 .0 % of triethanolamine and disodium EDTA;

- from 8.0 % to 12 % of isononyl isononanoate, stearyl alcohol and Copernicia cerifera (carnauba) wax;

- from 2.0 % to 3.0 % of silica and silica silylate;

- from 0.1 % to 1 .0 % of fragrance;

- from 1 .5 % to 3.5 % of ammonium acryloyldimethyltaurate/vp copolymer, aluminum starch octenylsuccinate and aery lates/C 10-30 alkyl acrylate crosspolymer;

- from 0.5 % to 1 .5 % of phenoxyethanol and chlorphenesin; - from 0.5 % to 3.0 % of glycerin and caprylyl glycol;

- from 45.0 % to 55.0 % of water;

- from 0.3 % to 3.0 % of sodium methyl stearoyl taurate, poloxamer 338 and stearic acid;

- from 0.05 % to 0.2 % of a citrus limon (lemon) fruit extract; and

- from 0.01 % to 0.2 % of ascorbyl glucoside and tocopherol.

Another example of a suitable cosmetic composition for providing dark color shades according to the present invention, in the form of a water-in-oil emulsion, comprises:

- from 9.0 to 16.0 % by weight, based on the total weight of the composition, of coated yellow, red and black iron oxides. wherein the relative weight ratio between the iron oxides is:

- from 60.0 to 65.0 % of coated yellow iron oxide,

- from 20.0 to 25.0 % of coated red iron oxide, and

- from 10.0 to 15.0 % of coated black iron oxide.

- from 1 .0 to 3.0 % by weight, based on the total weight of the composition, of synthetic fluorphlogopite;

- from 20.0 to 25.0 % by weight, based on the total weight of the composition, of octocrylene, ethylhexyl salicylate, butyl methoxydibenzoylmethane, bisethylhexyloxyphenol methoxyphenyl triazine, and homosalate;

- from 10.0 to 15.0 % by weight, based on the total weight of the composition, of dimethicone;

- from 20.0 to 30.0 % by weight, based on the total weight of the composition, of water;

- from 0.1 to 2.0 % by weight, based on the total weight of the composition, of propylene glycol;

- from 1 .0 to 3.0 % of magnesium sulfate and caffeine;

- from 0.1 to 2.0 % of disteardimonium hectorite;

- from 0.1 to 1 .5 % of phenoxyethanol;

- from 1 .0 to 5.0 % by weight, based on the total weight of the composition, of vinyl dimethicone/methicone silsesquioxane crosspolymer;

- from 0.1 to 3.0 % by weight, based on the total weight of the composition, of polyglyceryl-4 diisostearate/polyhydroxystearate/sebacate and PEG-30 di polyhyd roxystearate ;

- from 1 .0 to 5.0 % by weight, based on the total weight of the composition, of niacinamide and tocopherol; and

- from 5.0 to 15.0% of propanediol and ethanol.

Another suitable water-in-oil cosmetic sunscreen composition according to the present invention comprises:

- from 1 .0 to 10.0 % by weight, based on the total weight of the composition, of iron oxides (and) disodium stearoyl glutamate (and) aluminum hydroxide;

- from 8.0 to 15.0 % by weight, based on the total weight of the composition, of titanium dioxide (and) disodium stearoyl glutamate (and) aluminum hydroxide;

- from 1 .0 to 3.0 % by weight, based on the total weight of the composition, of synthetic fluorphlogopite;

- from 20.0 to 25.0 % by weight, based on the total weight of the composition, of octocrylene, ethylhexyl salicylate, butyl methoxydibenzoylmethane, bisethylhexyloxyphenol methoxyphenyl triazine, and homosalate;

- from 10.0 to 15.0 % by weight, based on the total weight of the composition, of dimethicone;

- water, wherein the weight ratio between water and dimethicone ranges from 1 :0.35 to 1 :0.50;

- from 0.1 to 2.0 % by weight, based on the total weight of the composition, of propylene glycol;

- from 1 .0 to 3.0 % of magnesium sulfate and caffeine;

- from 0.1 to 2.0 % of disteardimonium hectorite;

- from 0.1 to 1 .5 % of phenoxyethanol;

- from 1 .0 to 5.0 % by weight, based on the total weight of the composition, of vinyl dimethicone/methicone silsesquioxane crosspolymer;

- from 0.1 to 3.0 % by weight, based on the total weight of the composition, of polyglyceryl-4 diisostearate/polyhydroxystearate/sebacate and PEG-30 di polyhyd roxystearate ;

- from 1 .0 to 5.0 % by weight, based on the total weight of the composition, of niacinamide and tocopherol; and - from 5.0 to 15.0 % by weight, based on the total weight of the composition, of propanediol and ethanol.

In one embodiment, the cosmetic composition for providing dark color shades is used for the manufacture of a dark tinted sunscreen cosmetic composition, suitable for skin phototypes 5 and 6.

A person skilled in the art would be capable of selection suitable processes for manufacturing a cosmetic composition for providing dark color shades depending on the needs. Nonetheless, a suitable a process for manufacturing a cosmetic composition for providing dark color shades comprises the steps of:

Step (A): Main Vessel - Hot oily phase comprising oil raw materials in a temperature ranging from 75 e C to 80 e C;

Step (B): Side Vessel - room temperature or 75-80 e C aqueous phase comprising aqueous raw materials;

(C): the aqueous phase of step (B) is added to the oil phase of step (A), after which the emulsifier is subsequently added, followed by mixing the mixture;

(D): the polymers are added to the mixture obtained in step (C), subsequently followed by a neutralization;

(E): the fillers are gradually added to the mixture obtained in step (D) and mixed until homogeneity, at a temperature of below 30 e C.

Another suitable a process for manufacturing a cosmetic composition for providing dark color shades comprises the steps of:

(A) mixing the aqueous phase ingredients with each other in a main vessel, therefore forming an aqueous phase, and

(B) adding the oily ingredients to the aqueous phase, individually, therefore forming an emulsion, and

(C) adding the pigments.

EXAMPLES

Example 1

Example 1 related to a tinted cosmetic sunscreen composition of the state- of-the-art, direct to dark skin tones, comprising titanium dioxide and other cosmetically acceptable ingredients, as follows: C12-15 alkyl benzoate, dibutyl adipate, methylene bis- benzoatriazolyl tetramethylbutylphenol, butyl methoxyolbenzoylmethane, 4- methylbenzylidene camphor, butylene glycol cocoate, ethylhexyl triazone, methyl methacrylate crosspolymer, triacontanyl PVP, polyamide-5, potassium cetyl phosphate, tribehenin PEG-20 esters, yellow iron oxide, bis-ethylhexyloxyphenol methoxyphenyl triazine, cetearyl alcohol, cyclopentasiloxane, glycerin saccharide isomerate, decyl glucoside, phenoxyethanol, caprylyl glycol, disodium lauriminodipropionate tocopheryl phosphates, red iron oxide, dimethicone, dipotassium glycyrrhizate, triethanolamine, carnosine, black iron oxide, hydroxyacetophenone, caprylhydroxamic acid, BHT, PEG-12 dimethicone, propylene glycol, xanthan gum, disodium EDTA, sodium hydroxide, artemia extract, oryza sativa extract, aqua.

Example 2

Example 2 is related to a particular concretization of the cosmetic composition for providing dark color shades according to the present invention, in which the composition is in the form of a tinted cosmetic sunscreen composition comprising the following ingredients:

- about 6.20 % by weight, based on the total weight of the composition of uncoated yellow, red and black iron oxides, wherein the relative weight ratio between the iron oxides is:

- about 53.5 % of uncoated yellow iron oxide,

- about 25.5 % of uncoated red iron oxide, and

- about 22.0 % of uncoated black iron oxide.

- about 20.5% of UV filters comprising ethylhexyl triazone, titanium dioxide, octocrylene, diethylamino hydroxybenzoyl hexyl benzoate, ethylhexyl salicylate and butyl methoxydibenzoylmethane;

- the remaining amount being cosmetically acceptable ingredients according to the present invention.

Examples 3 to 5

Examples 3, 4 and 5 are related to similar compositions of Example 2, with the same overall amount of pigments of about 6.20 % by weight, based on the total weight of the composition. However, these compositions comprise pigment titanium dioxide.

Particularly, the composition of Example 3 comprises about 2.5 % by weight of pigment titanium dioxide and about 3.7 % by weight of iron oxides (yellow, red and black). The composition of Example 4 comprises about 3.9 % by weight of pigment titanium dioxide and about 2.3 % by weight of iron oxides (yellow, red and black). The composition of Example 5 comprises about 4.9 % by weight of pigment titanium dioxide and 1.3 % by weight of iron oxides. The pigments of the composition of Example 3 comprises about 4.9 % by weight of pigment titanium dioxide and 1 .3 % by weight of iron oxides.

Example 6 - Comparative

The compositions of Example 1 and Example 2 were applied to subjects with dark skin tone. As it can be seen in Figure 1 , the cosmetic composition for providing dark color shades of the present invention (Example 2) matched the color of the subject without the drawbacks of the state-of-the-art (Fig. 1 b), whereas the state-of-the-art composition of Example 1 left an ashy look and a white cast (Fig. 1 a).

Example 7 - Comparative

The compositions of Example 1 and Example 2 were applied onto the skin of the same subject, on the arm. As it is clearly shown in Fig. 2, the inventive composition of Example 2 provides a darker shade and does not have a white undertone when compared to the state-of-the-art composition of Example 1 .

Example 8 - Comparative

The compositions of Example 2 and Examples 3 to 5 were applied onto the skin of a subject having a dark skin tone, from left to right respectively. As it is demonstrated by Fig. 3, the inventive composition of Example 2 provides a better match to the subject’s skin tone. Therefore, the composition for providing dark color shades of the present invention is suitable for skin phototypes 5 and 6.

Example 9

A hybrid instrumental and perception test was performed with subjects who identify as having phototypes 5 and 6, in order to access if the composition according to the present invention was suitable to dark skin tones. A high percentage of the subjects agreed that the shade of the inventive composition according to Example 2 matches their skin color, which was corroborated by the instrumental assay. It was demonstrated that the application of the composition of Example 2 resulted in a non-relevant color change when compared to the product-free skin.