Self-tanning compositions containing alkyl sulfonates and methods thereof

Abstract

(A) Reducing sugars, (B) Optionally substituted C8 12 A topical skin care composition comprising an alkyl sulfonate and (C) a carrier. The composition may further comprise an aromatic sulfonate. A method for enhancing skin color appearance (e.g., hue angle, value, saturation) is also disclosed, comprising applying the topical skin care composition to the skin. When applied to the skin, the topical skin care composition can provide a deep, rich, long-lasting artificial tan while maintaining or adjusting a customizable hue.

Description

[Technical Field]

[0001] The present invention relates to topical skin care compositions, particularly topical skin care compositions comprising (A) a reducing sugar, (B) an alkyl sulfonate, and (C) a carrier, and methods of self-tanning using the topical skin care compositions. [Background technology]

[0002] The "Background" description provided herein is generally intended to provide a background to the present invention. To the extent described in this Background section, and to the extent that aspects of the description do not qualify as prior art at the time of filing, the inventors' work is not expressly or implicitly admitted as prior art to the present invention.

[0003] Consumers worldwide enjoy spending time in the sun for a variety of reasons, including outdoor recreation, sports, and tanning (skin darkening). Unfortunately, exposure to UV radiation is known to potentially promote skin cancer. Furthermore, localized exposure to UV radiation can result in uneven skin tone across the body. Therefore, there are health and aesthetic motivations to seek alternatives to achieve a natural-looking, even skin tone while avoiding the hazards of sun exposure.

[0004] Despite the known risks, sunbathing remains the most common method for darkening skin in the United States and the EU. Sunless tanning agents and glow moisturizers are also popular, but many consumers are dissatisfied with these products because they often produce unnatural colors, insufficiently dark colors, or fade quickly. For example, many conventional self-tanning products containing dihydroxyacetone (DHA) tanning agents produce an undesirable orange hue. In addition to darkening the skin, some consumers prefer to maintain their natural skin tone, while others desire to shift the tone to a more aesthetically pleasing bronze / red hue.

[0005] Several skin tanning compositions have been reported that utilize azole compounds, pigments (e.g., carmine), crosslinked cationic copolymers, and vanillin polymers to enhance skin coloration (U.S. Pat. Nos. 5,705,145, 6,214,322, 7,780,954, and 7,935,331, each of which is incorporated herein by reference in its entirety). However, there remains a need for improved compositions that can effectively darken skin color while preserving the skin's natural hue. Summary of the Invention [Problem to be solved by the invention]

[0006] As previously mentioned, there is a need for topical skin care compositions that produce deeper, richer color and are long-lasting without altering the initial hue of the skin.

[0007] Accordingly, one object of the present invention is to provide novel topical skin care compositions that meet these criteria.

[0008] Another object of the present invention is to provide a novel method for modulating the appearance of skin color of a subject by topically applying a topical skin care composition to the subject's skin. [Means for solving the problem]

[0009] These and other objects, which will become apparent in the detailed description below, have been realized by the inventors' unexpected discovery that a combination of a reducing sugar, an alkyl sulfonate, and a carrier provides a topical skin care composition that promotes a long-lasting, rich, intense (i.e., dark), natural-looking tanning color by increasing saturation and darkness while maintaining the original hue of skin color after topical application. Furthermore, when an aromatic sulfonate is included, the topical skin care composition provides a custom tan by shifting hue in addition to darkening and saturating skin color.

[0010] Thus, the present invention provides the following: (1) (A) about 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) Optionally substituted C8 12 alkyl sulfonates, and (C) Carrier 1. A topical skin care composition comprising: Optionally substituted C8 12 The weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:20 to 20:1. Topical skin care compositions.

[0011] (2) Optionally substituted C8 12 The topical skin care composition of (1), wherein the alkyl sulfonate (B) is an unsubstituted alkyl sulfonate.

[0012] (3) Optionally substituted C8 12 The topical skin care composition according to (1) or (2), wherein the alkyl sulfonate (B) is an alkali metal alkyl sulfonate.

[0013] (4) Optionally substituted C8 12 The topical skin care composition according to any one of (1) to (3), wherein the alkyl sulfonate (B) is sodium 1-octanesulfonate, sodium 1-decanesulfonate, or both.

[0014] (5) Optionally substituted C8 12 The topical skin care composition according to any one of (1) to (4), wherein the alkyl sulfonate (B) is sodium 1-octanesulfonate.

[0015] (6) Optionally substituted C8 12 The topical skin care composition according to any one of (1) to (5), wherein the weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:20 to 20:1.

[0016] (7) The topical skin care composition according to any one of (1) to (6), wherein the carrier (C) comprises an aromatic alcohol.

[0017] (8) The topical skin care composition according to any one of (1) to (7), wherein the carrier (C) comprises benzyl alcohol.

[0018] (9) The topical skin care composition according to any one of (1) to (8), further comprising (D) an organic solvent.

[0019] (10) The topical skin care composition according to (9), wherein the organic solvent (D) is at least one selected from the group consisting of 1,3-propanediol, 1,2-propanediol, and 1,3-butanediol.

[0020] (11) The topical skin care composition according to any one of (1) to (10), which is substantially free of a cationic copolymer.

[0021] (12) (E) further comprising an aromatic sulfonate, wherein the aromatic sulfonate (E) is 100 Å or less. 2 The topical skin care composition according to any one of (1) to (11), having a topological polar surface area (tPSA) of less than 1000 nm.

[0022] (13) The topical skin care composition of (12), wherein the aromatic sulfonate (E) is an optionally substituted phenyl sulfonate, an optionally substituted naphthyl sulfonate, or both.

[0023] (14) The topical skin care composition according to (12) or (13), wherein the aromatic sulfonate (E) is at least one selected from the group consisting of sodium 2-naphthalenesulfonate, sodium p-toluenesulfonate, and sodium cumenesulfonate.

[0024] (15) The topical skin care composition according to any one of (12) to (14), wherein the weight ratio of the alkyl sulfonate (B) to the aromatic sulfonate (E) ((B):(E)) is 1:100 to 100:1.

[0025] (16) A method for darkening and maintaining the color of a subject's skin, comprising: topically applying the topical skin care composition according to any one of (1) to (15) to the skin of a subject; Including, Topical application reduces the color lightness, L, compared to the lightness and hue angle before topical application, respectively. * decreases by at least 10% and the hue angle of the color (h°) changes by less than 2°; method.

[0026] (17) The method of (16), wherein the topical skin care composition is topically applied to the subject 1 to 3 times daily for 1 to 7 consecutive days.

[0027] (18) A method for darkening the skin color of a subject, comprising: topically applying the topical skin care composition according to any one of (1) to (15) to the skin of a subject; Including, Topical application resulted in a significant decrease in color brightness L compared to before topical application. * decreases by at least 10%, method.

[0028] (19) A method for adjusting skin color saturation in a subject, comprising: topically applying the topical skin care composition according to any one of (1) to (15) to the skin of a subject; Including, Topical application resulted in a significant decrease in color saturation (C) compared to before topical application. * increases by at least 10%, method.

[0029] (20) A collection of topical skin care products for retail sale, comprising: (a) (A) about 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) Optionally substituted C8 12 alkyl sulfonates, and (C) Carrier Including, Optionally substituted C8 12 The weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:20 to 20:1. a first topical skin care composition; and (b) (A) about 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) Optionally substituted C8 12 alkyl sulfonates, and (C) Carrier Including, Optionally substituted C8 12 The weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:20 to 20:1. a second topical skin care composition; and Including, the content of reducing sugar (A) present in the first topical skin care composition (a) is less than the content of reducing sugar (A) present in the second skin care composition (b), each based on the total weight of the first and second topical skin care compositions; collection.

[0030] (21) The collection of (20), wherein the first topical skin care composition (a) and the second topical skin care composition (b) are packaged separately.

[0031] (22) The collection according to (20) or (21), wherein the content of reducing sugar (A) relative to the total weight of the first topical skin care composition (a) is less than 5%, and the content of reducing sugar (A) relative to the total weight of the second topical skin care composition (b) is more than 5%.

[0032] (23) (A) about 0.1 to 30 wt. % of a reducing sugar, based on the total weight of the topical skin care composition; (B) Optionally substituted C8 12 alkyl sulfonates, and (C) Carrier 1. A topical skin care composition comprising: the reducing sugar (A) is dihydroxyacetone, erythrulose, or both; Optionally substituted C8 12 the alkyl sulfonate (B) is an unsubstituted alkyl sulfonate; The carrier (C) contains an aromatic alcohol; Optionally substituted C8 12 The weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:20 to 20:1. Topical skin care compositions.

[0033] (24) The topical skin care composition according to (23), further comprising (D) an organic solvent.

[0034] (25) The topical skin care composition according to (23), which is substantially free of cationic copolymers.

[0035] (26) (E) further comprising an aromatic sulfonate, wherein the aromatic sulfonate (E) is 100 Å 2 23. The topical skin care composition of claim 22, wherein the topical skin care composition has a topological polar surface area (tPSA) of less than 1000 nm.

[0036] (27) (A) about 0.1 to 10 wt. % of a reducing sugar, based on the total weight of the topical skin care composition; (B) about 0.1 to 10 wt. % of an optionally substituted C8- 12 alkyl sulfonates, and (C) about 0.1 to 5 wt. % of a carrier, based on the total weight of the topical skin care composition 1. A topical skin care composition comprising: the reducing sugar (A) is dihydroxyacetone, erythrulose, or both; Optionally substituted C8 12the alkyl sulfonate (B) is an unsubstituted alkyl sulfonate; The carrier (C) contains an aromatic alcohol; Optionally substituted C8 12 The weight ratio of the alkyl sulfonate (B) to the reducing sugar (A) ((B):(A)) is 1:5 to 5:1. Topical skin care compositions.

[0037] (28) The topical skin care composition according to (27), further comprising (D) an organic solvent.

[0038] (29) The topical skin care composition according to (27), which is substantially free of cationic copolymers.

[0039] (30) (E) further comprising an aromatic sulfonate, wherein the aromatic sulfonate (E) is 100 Å 2 27. The topical skin care composition of claim 26, wherein the topical skin care composition has a topological polar surface area (tPSA) of less than 1000 nm.

[0040] The foregoing paragraphs have been provided by way of general introduction and are not intended to limit the scope of the claims that follow. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description.

[0041] This patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0042] A more complete appreciation of the present invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings. [Brief explanation of the drawings]

[0043] [Figure 1]1A-1B are bar graphs illustrating the change in skin darkness 6 and 24 hours after application of a control composition containing only DHA (A), and a topical skin care composition containing DHA and sodium 1-decanesulfonate (SDS) (B), respectively. [Figure 2] Color-corrected images showing human skin after treatment with a control composition containing only DHA ("Control") (upper circle) and a topical skin care composition containing DHA and SDS ("SDS") (lower circle), where color correction was performed using the CASMATCH method (Bear Medic Co.). [Figure 3] 1 is a bar graph showing the change in skin darkness after three daily applications (one application per day for three consecutive days), and after seven daily applications (one application per day for seven consecutive days), and after three days of fading after seven daily applications, of a control composition containing only DHA (A), and a topical skin care composition containing DHA and sodium 1-octanesulfonate (SOS) (B), respectively. [Figure 4] 1A-B are bar graphs showing the change in skin hue angle after three daily applications (one application per day for three consecutive days), and after seven daily applications (one application per day for seven consecutive days), and after three days of fading after seven daily applications, of a control composition containing only DHA (A), and a topical skin care composition containing DHA and SOS (B), respectively. [Figure 5] 1 is a bar graph summarizing the change in skin darkness 4 hours, 24 hours, and 48 hours after application of a control composition containing only DHA (A), and topical skin care compositions containing, respectively, (B) DHA and SOS, (C) DHA and sodium 1-decanesulfonate (SDS), (D) DHA and sodium dodecylbenzenesulfonate (SDBS), and (E) DHA and sodium lauryl sulfoacetate (SLSA). [Figure 6A]1 is a bar graph summarizing the change in skin darkness following application of a control composition containing only DHA (DHA), a topical skin care composition containing DHA and SOS (+SOS), a control composition containing DHA and sodium 2-naphthalenesulfonate (NSA) (+NSA), and a topical skin care composition containing DHA, SOS, and NSA (+NSA / SOS), respectively. [Figure 6B] 1 is a photograph showing human skin after treatment with a topical skin care composition containing DHA and SOS. [Figure 6C] 1 is a photograph showing human skin after treatment with a control composition containing DHA and NSA. [Figure 6D] 1 is a photograph showing human skin after treatment with a topical skin care composition containing DHA, SOS, and NSA. [Figure 7] 1 is a bar graph showing the relative α-helix / β-sheet index ratio of keratin upon exposure to aqueous solutions containing SOS, SDS, and sodium lauryl sulfate (SLS), respectively. [Figure 8] Part of a chromaticity diagram drawn using the CIE L*C*h° and CIE L*a*b* color space models. [Figure 9A] 1 is a graph summarizing the different degrees of darkening (L*) induced by DHA in the presence of SOS, SDS, and sodium lauryl sulfate (SLS), respectively. [Figure 9B] FIG. 1 shows the structural change of keratin from α-helix to β-sheet. [Figure 10A] 1 is a photograph showing the dry stratum corneum. [Figure 10B] 1 is a photograph showing the stratum corneum upon exposure to deionized water. [Figure 10C] 1 is a photograph showing the stratum corneum upon exposure to a control composition containing only DHA. [Figure 10D] 1 is a photograph showing the stratum corneum upon exposure to a topical skin care composition containing DHA and SOS. [Figure 10E]1 is a photograph showing the stratum corneum upon exposure to a topical skin care composition containing DHA, SOS, and 5% by weight of 1,3-propanediol (PD). [Figure 10F] 1 is a photograph showing the stratum corneum upon exposure to a topical skin care composition containing DHA, SOS, and 10% by weight PD. [Figure 10G] 1 is a bar graph summarizing the different degrees of darkening (L*) induced by a control composition containing only DHA (DHA), a topical skin care composition containing DHA and SOS (DHA / SOS), a topical skin care composition containing DHA, SOS, and 5% by weight PD (+5%PD), and a topical skin care composition containing DHA, SOS, and 10% by weight PD (+10%PD), respectively. DETAILED DESCRIPTION OF THE INVENTION

[0044] In the following description, it is understood that other embodiments may be utilized and structural and operational changes may be made without departing from the scope of the present embodiments disclosed herein.

[0045] definition As used herein, words such as "a" and "an" mean "one or more."

[0046] Where numerical limits or ranges are stated within the description herein, the endpoints are included, and all values ​​and subranges within the numerical limits or ranges are specifically included as if expressly written.

[0047] When referring to a topical skin care composition, the phrase "substantially free," unless otherwise specified, indicates that the amount of a particular ingredient present in the topical skin care composition is less than about 1 wt. %, preferably less than about 0.5 wt. %, more preferably less than about 0.1 wt. %, even more preferably less than about 0.05 wt. %, and even more preferably 0 wt. %, based on the total weight of the topical skin care composition.

[0048] As used herein, the word "about" may be used when describing a size and / or location to indicate that the stated value and / or location is within a reasonably expected range of the value and / or location. For example, a numerical value may have a value that is + / - 0.1% of the stated value (or range of values), + / - 1% of the stated value (or range of values), + / - 2% of the stated value (or range of values), + / - 5% of the stated value (or range of values), or + / - 10% of the stated value (or range of values).

[0049] As used herein, the term "any" or "optionally" means that the subsequently described event may or may not occur, or that the subsequently described ingredient may or may not be present (e.g., 0% by weight).

[0050] As used herein, the term "substituted" refers to at least one hydrogen atom replaced with a non-hydrogen group, provided that the normal valence is maintained and the substitution results in a stable compound.

[0051] As used herein, the term "alkyl," unless otherwise specified, refers to a straight-chain, branched, or cyclic aliphatic fragment having at least 1, preferably at least 2, preferably at least 3, preferably at least 4 carbon atoms, and up to 22, preferably up to 20, preferably up to 18, preferably up to 12, preferably up to 8 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl), n-tetradecyl (myristyl), n-pentadecyl, n-hexadecyl (cetyl), n-octadecyl (stearyl), and the like. cycloalkyl, n-eicosanyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and the like, as well as Guerbet-type alkyl groups (e.g., 2-methylpentyl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, 2-nonyltridecyl, 2-decyltetradecyl, and 2-undecylpentadecyl). Cycloalkyl is a type of cyclic alkyl group. Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl.

[0052] As used herein, the term "aryl" refers to aromatic groups containing only carbon in the aromatic ring, for example, phenyl, biphenyl, naphthyl, anthracenyl, and the like.

[0053] As used herein, the term "arylalkyl" refers to a straight-chain, branched, or cyclic alkyl moiety (as defined above) substituted by an aryl group (as defined above), which itself may be optionally substituted by an alkyl group, examples of which include, but are not limited to, benzyl, phenethyl, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2-phenylbutyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2-(4-ethylphenyl)ethyl, 3-(3-propylphenyl)propyl, and the like.

[0054] As used herein, the term "alkoxy" refers to a straight or branched chain alkyl group attached to an oxygen atom. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy.

[0055] As used herein, the term "alkoxycarbonyl" refers to an alkoxy group attached to a carbonyl group (ie, >C=O).

[0056] As used herein, the term "halogen" means fluoro, chloro, bromo and iodo.

[0057] As used herein, unless otherwise specified, the term "alkenyl" refers to a straight-chain, branched, or cyclic aliphatic fragment having 2 to 22 carbon atoms, preferably 3 to 20 carbon atoms, and preferably 4 to 18 carbon atoms, and containing at least one site of unsaturation. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, oleyl, linoleyl, and the like, including cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl.

[0058] As used herein, the term "skin" refers to the skin present on humans and other mammals.Skin is present in many different body parts, and it is recognized that the application of the topical skin care composition herein is not limited to the skin found in a specific body part.For example, the topical skin care composition can be applied to any area of ​​the skin that is intended for self-tanning, including the face, limbs, feet, neck, trunk, etc.In addition, the topical skin care composition can be applied to the whole body as a moisturizer in daily skin care routines.

[0059] Various topical skin care composition ingredients are listed throughout this specification and are organized according to their primary or most desirable function, benefit, or use.However, the classification of an ingredient under a particular function, benefit, or use does not mean that the ingredient is limited to only that function, benefit, or use.For example, even if benzyl alcohol is listed as a carrier, benzyl alcohol may also impart other beneficial properties, such as acting as a preservative and / or fragrance, so the usefulness of benzyl alcohol is not limited to its usefulness as a carrier.

[0060] Topical Skin Care Compositions The present invention relates to a sunless tanning topical skin care composition that reduces lightness, increases color saturation, and creates a customized hue for skin appearance. The topical skin care composition is easy to apply and can be used to darken skin color, maintain or adjust skin's natural tone, and provide a rich, long-lasting tan.

[0061] Therefore, topical skin care compositions contain ingredients that enable skin tanning, as well as ingredients that facilitate the delivery of the tanning agent, allow for easy application of the topical skin care composition, and reduce skin brightness and maintain color. Such compositions generally contain the following ingredients: (A) a tanning agent, preferably a reducing sugar; (B) an alkyl sulfonate; (C) a carrier; and optionally (D) an organic solvent; (E) an aromatic sulfonate; (F) water; (G) a thickener; (H) a preservative; and (I) an acidulant. In a preferred embodiment, all ingredients are compatible with the reducing sugar (i.e., do not react with or cause a reaction of the reducing sugar) and are homogeneously dispersed or dissolved throughout the topical skin care composition. Surprisingly, it has been found that adding an alkyl sulfonate to the reducing sugar enhances the self-tanning effect of the composition. For example, the presence of an alkyl sulfonate in a composition containing a reducing sugar can improve the darkness and saturation (C) of the color of the treated skin. * ) is increased while maintaining the original hue angle (h°).

[0062] The topical skin care composition may be in the form of a liquid, solution, emulsion, lotion, cream, gel, paste, spray, foam, or any other form suitable for topical application to the skin. Preferably, the topical skin care composition is in the form of a lotion, cream, gel, spray, or foam. More preferably, the topical skin care composition is in the form of a cream or gel that can be applied evenly.

[0063] tanning agents To act as an effective self-tanning agent, the topical skin care compositions herein comprise a "tanning agent," which is any coloring molecule capable of staining the skin when in contact with the skin, or any non-coloring molecule capable of reacting with the skin and staining the skin, particularly a molecule capable of darkening the skin in a manner similar to the darkening effect achieved by exposing the skin to solar radiation (i.e., natural tanning).

[0064] In a preferred embodiment, the tanning agent is (A) a reducing sugar. Certain reducing sugars, such as monosaccharides (e.g., dihydroxyacetone), react with amino acids naturally present on the skin surface via the Maillard reaction to form pigmented melanoidins, which alter skin color (Bobin et al., J. Soc. Cosmet. Chem., 35, pp. 265-272, 1984; Maillard LC, CRAcad. Sci., 154, 66-68, 1912, each incorporated by reference in its entirety).

[0065] Various amino acids react differently with various reducing sugars to produce various shades of coloration, ranging from yellow to brown. Any reducing sugar capable of reacting with amino acids found in skin (e.g., naturally occurring amino acids) to produce darkened skin can be used as a tanning agent in the present invention. The reducing sugar (A) can be a monosaccharide, such as an aldose having 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, more preferably 3 to 4 carbon atoms, and even more preferably 3 carbon atoms, or a ketose having 3 to 6 carbon atoms, preferably 4 to 5 carbon atoms, and more preferably 3 to 4 carbon atoms, including mixtures of such aldoses and / or ketoses. Exemplary reducing sugars include, but are not limited to, dihydroxyacetone (DHA), erythrulose, glycoaldehyde, glyceraldehyde, meso-tartaraldehyde, glucose, gulose, xylose, fructose, ribose, arabinose, allose, talose, altrose, idose, mannose, galactose, and erythrose. In a preferred embodiment, the reducing sugar (A) is dihydroxyacetone, erythrulose, or both. Most preferably, the reducing sugar (A) is dihydroxyacetone. Dihydroxyacetone is available, for example, from EMD Millipore.

[0066] The amount of tanning agent present in a topical skin care composition can vary depending on the desired skin coloration (e.g., brightness, hue angle, color saturation) and the amount and nature of other ingredients. In some embodiments, the tanning agent is present in an amount of at least about 0.05 wt.%, preferably at least about 0.1 wt.%, preferably at least about 0.5 wt.%, preferably at least about 1 wt.%, more preferably at least about 1.5 wt.%, even more preferably at least about 1.75 wt.%, even more preferably at least about 2 wt.%, and up to about 10 wt.%, preferably up to about 8 wt.%, preferably up to about 6 wt.%, preferably up to about 4 wt.%, preferably up to about 3.5 wt.%, more preferably up to about 3 wt.%, even more preferably up to about 2.5 wt.%, and even more preferably up to about 2.25 wt.%, based on the total weight of the topical skin care composition.

[0067] In preferred embodiments, the topical skin care composition is substantially free of tanning agents other than reducing sugars, which includes being substantially free, and preferably completely free (i.e., 0% by weight), of color-imparting synthetic dyes and natural pigments. Alternatively, the topical skin care composition may include other tanning agents, such as synthetic dyes and / or natural pigments, in the amounts previously recited.

[0068] Examples of synthetic dyes that may be included as tanning agents include, but are not limited to, acid dyes (e.g., Yellow No. 203 (D&C Yellow No. 10, Color Index indicated as CI (CI) 47005), Orange No. 205 (D&C Orange No. 4, CI 15510), Red No. 3 (Erythrosine B, CI 45430), Red No. 94 (Rose Bengal, CI 45440), and Red No. 227 (D&C Red No. 33, CI 17200)); quinone dyes (e.g., anthraquinone, 1-N-methylpropional, Folinium propylamino-4-hydroxyanthraquinone, 1-aminopropylamino-4-methylaminoanthraquinone, 1-aminopropylaminoanthraquinone, 5-β-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1,4-bis(β,γ-dihydroxypropylamino)anthraquinone, lawsone, juglone, alizarin, purpurin, carminic acid, carmine, kermesic acid, spinulosin, Disperse Red 15, Solvent Violet 13, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99); azo dyes (e.g., 1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium chloride, 1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium chloride, 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methyl sulfate, Disperse Red 17, Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17, Disperse Black 9);and indoamine dyes (for example, 2-β-hydroxyethylamino-5-[bis(β-4'-hydroxyethyl)amino]anilino-1,4-benzoquinone, 2-β-hydroxyethylamino-5-(2'-methoxy-4'-amino)anilino-1,4-benzoquinone, 3-N-(2'-chloro-4'-hydroxy)phenylacetamino-6-methoxy-1,4-benzoquinoneimine, 3-N-(3'-chloro-4'-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine, 3-[4'-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine);

[0069] The topical skin care composition may include natural pigments as tanning agents. Non-limiting examples of natural pigments include caramel, beta-carotene, beetroot extract, blue-green algae, cocoa powder, walnut extract, melanin, and curcumin.

[0070] (B) Alkyl sulfonate The topical skin care compositions of the present invention may include an alkyl sulfonate (B). Preferably, the alkyl sulfonate (B) is a compound represented by formula (I):

[0071] [ka] or a solvate thereof, a tautomer thereof, a stereoisomer thereof, or a mixture thereof, wherein (i) R1 is an optionally substituted alkyl or an optionally substituted arylalkyl, and (ii) X is a cation selected from the group consisting of a hydrogen ion, an ammonium ion, and an alkali metal ion.

[0072] The term "cation" includes, but is not limited to, hydrogen ions, ammonium ions (i.e., NH4 +), quaternary ammonium ions (e.g., tetraethylammonium, tetrabutylammonium), lithium ions, sodium ions, potassium ions, and silver ions. Preferably, the alkyl sulfonate (B) is an alkali metal alkyl sulfonate. In a preferred embodiment, X is an alkali metal ion, such as a lithium ion, a sodium ion, or a potassium ion. Most preferably, X is a sodium ion.

[0073] In some embodiments, R1 is an optionally substituted C1 22 Alkyl, preferably optionally substituted C 20 Alkyl, preferably optionally substituted C 18 Alkyl, preferably optionally substituted C 16 Alkyl, preferably optionally substituted C 14 Alkyl, preferably optionally substituted C 12 Alkyl, preferably optionally substituted C 10 Alkyl, preferably optionally substituted C8-9 alkyl. The number of carbon atoms described in this specification indicates the number of carbon atoms in the alkyl group of R1 excluding carbon atoms of any substituents.

[0074] In a preferred embodiment, R1 is an unsubstituted alkyl, preferably a linear alkyl, preferably a linear C1- 18 Alkyl, preferably linear C2 to 16 Alkyl, preferably linear C3 to 14 Alkyl, preferably linear C4 to 12 Alkyl, preferably linear C5 to 10Alkyl, preferably a linear C6-9 alkyl, preferably a linear C7-8 alkyl. Exemplary linear alkyls include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, and n-eicosanyl. Alternatively, R1 is branched or cyclic alkyl, such as isopropyl, sec-butyl, isobutyl, isobutyl, tert-butyl, isopentyl, neopentyl, isohexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, 2-nonyltridecyl, 2-decyltetradecyl, 2-undecylpentadecyl, and cyclohexyl. In some embodiments, R1 is alkyl substituted with at least one substituent, such as alkoxy, alkoxycarbonyl, carboxy, amino, hydroxy, thiol, and halogen. Most preferably, R1 is n-octyl or n-decyl.

[0075] Disadvantages associated with using common reducing sugars (e.g., dihydroxyacetone, erythrulose) alone as tanning agents include poor and rapidly fading coloration, an unnatural orange undertone, and uneven coverage. It has been unexpectedly discovered that the combination of a reducing sugar (A) (e.g., dihydroxyacetone) and an alkyl sulfonate (B) results in an intense, long-lasting artificial tan that, as can be seen, retains the natural color of the treated skin.

[0076] Exemplary alkyl sulfonates include, but are not limited to, unsubstituted alkyl sulfonates, such as potassium methanesulfonate, potassium trifluoromethanesulfonate, sodium ethanesulfonate, sodium 1-propanesulfonate, sodium 1-butanesulfonate, 1-pentasulfonic acid sodium salt, 1-hexanesulfonate, sodium 1-heptanesulfonate, sodium 1-octane sulfonate, sodium 1-nonanesulfonate, sodium 1-decanesulfonate, sodium 1-undecanesulfonate, sodium 1-dodecanesulfonate, sodium 1-tetradecanesulfonate, 1-pentadecanesulfonate sodium salt, 1-hexadecanesulfonate sodium salt, 1-octadecanesulfonate, and sodium cyclohexanesulfonate; substituted alkyl sulfonates, such as sodium 2-bromoethanesulfonate, 2-chloroethanesulfonate, and sodium 2-chloroethanesulfonate. sodium ethanesulfonate, 2-hydroxyethanesulfonic acid sodium salt, 2-hydroxyethanesulfonic acid ammonium salt, 3-hydroxy-1-propanesulfonic acid sodium salt, 3-bromopropanesulfonic acid sodium salt, 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 3-mercapto-1-propanesulfonate, sodium 3-(N-ethyl-3-methylanilino)propanesulfonate, N-ethyl-N-(3-sulfopropyl)-m-anisidine sodium salt, N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3,5-dimethoxyaniline sodium salt, 3-(N,N-dimethyltetradecylammonio)propanesulfonate, 3-(N,N-dimethyloctadecylammonio)propanesulfonate, dioctyl sulfosuccinate sodium salt, and dicyclohexyl sulfosuccinate sodium salt, and mixtures thereof.

[0077] In some embodiments, alkenyl sulfonates (i.e., where R1 in formula (I) is instead an alkenyl group), such as 1-octene-1-sulfonic acid sodium salt, 2-octene-1-sulfonic acid sodium salt, 1-hydroxy-3,7-dimethyl-6-octene-1-sulfonic acid sodium salt, 1-decene-1-sulfonic acid sodium salt, 1-dodecene-1-sulfonic acid sodium salt, 2-dodecene-1-sulfonic acid sodium salt, 1-tetradecene-1-sulfonic acid sodium salt, and 1-hexadecene-1-sulfonic acid sodium salt, may be used in addition to or in place of the alkyl sulfonates mentioned above.

[0078] In a preferred embodiment, the alkyl sulfonate (B) is sodium 1-octanesulfonate, sodium 1-decanesulfonate, or both. More preferably, the alkyl sulfonate (B) is sodium 1-octanesulfonate.

[0079] The stratum corneum is the outermost layer of the skin epidermis, which contains keratinocytes with keratin filaments embedded in a structurally organized water-lipid matrix.Keratin swelling can occur when certain chemicals, such as strong surfactants, penetrate into the stratum corneum and interact with keratin, causing the destruction of the secondary and tertiary structure of keratin and excessive water diffusion.This process also depletes the natural moisturizing components, such as amino acids and lipids, inherent in keratinocytes.As a result, excessive keratin swelling can cause skin dryness, redness, itching and irritation.

[0080] As used herein, the relative keratin swelling degree of a compound is determined by comparing the swelling degree of the stratum corneum exposed to an aqueous solution containing 2% (w / w%) of the compound with the swelling degree of the stratum corneum exposed to water.For example, the relative keratin swelling degree is calculated by the following formula (A):

[0081]

number

[0082] The alkyl sulfonates (B) applicable to the present invention may have a relative keratin swelling index at a concentration of 2% by weight of less than 1.28, for example from about 0.6, preferably from about 0.62, preferably from about 0.64, preferably from about 0.66, preferably from about 0.68, more preferably from about 0.70, even more preferably from about 0.72, even more preferably from about 0.74, and up to about 1.2, preferably up to about 1.15, preferably up to 1.1, preferably up to 1.05, preferably up to 1.0, preferably up to 0.95, preferably up to 0.9, preferably up to 0.85, more preferably up to 0.8, even more preferably up to 0.78, even more preferably up to 0.76.

[0083] Keratin is classified into α-helical keratin and β-sheet keratin according to its secondary structure. Like other α-helical proteins, α-helical keratin adopts a stable coiled-coil structure. Compared with α-helical keratin, β-sheet keratin has a larger number of exposed side chains (e.g., disulfide bonds, hydrogen bonds), which facilitates intercalation of water molecules between sheets. Therefore, β-sheet keratin tends to swell more easily than α-helical keratin. The α-helix / β-sheet ratio of keratin can serve as an indicator of keratin swelling. Compounds that produce a larger α-helix / β-sheet ratio of keratin may have a reduced tendency to cause keratin swelling. Methods for calculating the α-helix / β-sheet ratio of keratin are known to those skilled in the art. For example, the ratio can be determined using Raman spectroscopy (eg, confocal Raman microscopy), IR spectroscopy (eg, ATR / FT-IR), NMR spectroscopy, and wide-angle X-ray scattering.

[0084] As used herein, the relative α-helix / β-sheet index ratio of a compound is determined by comparing the α-helix / β-sheet index of stratum corneum exposed to an aqueous solution containing 2% (w / w%) of the compound with the index of stratum corneum exposed to water (see the Examples section for experimental details regarding the determination of the relative α-helix / β-sheet index ratio).

[0085] The alkylsulfonates (B) applicable to the present invention have a relative α-helix / β-sheet index ratio at a concentration of 2% by weight of more than 0.86, for example from 0.87, preferably from 0.88, preferably from 0.89, preferably from 0.90, preferably from 0.91, preferably from 0.92, more preferably from 0.93, even more preferably from 0.93, and up to 0.99, preferably up to 0.98, preferably up to 0.97, more preferably up to 0.96, even more preferably up to 0.95.

[0086] As shown in Figure 7, exposure of keratin to sodium 1-octanesulfonate (SOS) results in a less severe phase transition from α-helical keratin to β-sheet keratin than exposure to 1-decanesulfonate (SDS), while sodium lauryl sulfate (SLS) induces the greatest degree of such phase transition among the three. Keratin with a lower α-helical / β-sheet ratio tends to have a higher amount of available lysine, which is one of the amino acids in skin that reacts most readily with tanning agents (e.g., dihydroxyacetone) via the Maillard reaction. However, a lower α-helical / β-sheet ratio allows more water to become internal to the keratin protein, which can cause swelling, which can interfere with the Maillard reaction. Therefore, a compound that can balance swelling and structural changes (e.g., SOS) can help tanning agents achieve effective skin darkening by freeing up sufficient lysine residues rather than allowing excessive water to be introduced into keratin proteins. Figure 9A shows that increasing the relative α-helix / β-sheet index ratio of the salt from about 0.86 (i.e., SLS) to about 0.97 (i.e., SOS) increases the skin darkening induced by DHA, while further increasing the relative α-helix / β-sheet index ratio beyond 0.97 can decrease the skin darkening induced by DHA.

[0087] In some embodiments, the alkyl sulfonate (B) is present in an amount of at least about 0.05 wt. %, preferably at least about 0.1 wt. %, preferably at least about 0.5 wt. %, preferably at least about 1 wt. %, more preferably at least about 1.5 wt. %, even more preferably at least about 2 wt. %, still even more preferably at least about 2.5 wt. %, and up to about 10 wt. %, preferably up to about 8 wt. %, preferably up to about 6 wt. %, preferably up to about 5 wt. %, preferably up to about 4 wt. %, more preferably up to about 3.5 wt. %, even more preferably up to about 3 wt. %, and still even more preferably up to about 2.75 wt. %, based on the total weight of the topical skin care composition.

[0088] (C) Carrier The topical skin care compositions of the present invention may also include a carrier (C), which is a material capable of enhancing the uniform delivery and penetration of the tanning agent (and other ingredients of the topical skin care composition) into the skin so that a deeper, richer, and longer-lasting tan can be achieved.

[0089] Examples of suitable carriers (C) for use herein include, but are not limited to, benzyl alcohol, 2-phenylethyl alcohol, phenoxyethanol, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, iso-butanol, tert-butanol, hexanol, n-octanol, 2-octanol, 2-ethylhexanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and mixtures thereof.

[0090] In some embodiments, the carrier (C) comprises an aromatic alcohol. Due to the presence of a polar end (hydroxy group) and a non-polar end (phenyl group), aromatic alcohols (e.g., benzyl alcohol, 2-phenylethyl alcohol, phenoxyethanol) may enable more effective transdermal delivery of tanning agents (and other ingredients of topical skin care compositions) than other short-chain alkyl alcohols such as ethanol and n-butanol. Furthermore, benzyl alcohol is particularly advantageous due to its moderate water solubility, fragrant aroma, antibacterial properties, and low toxicity. In preferred embodiments, the carrier (C) used in the present invention includes benzyl alcohol, 2-phenylethyl alcohol, 1-phenylethanol, phenoxyethanol, or a mixture thereof. Most preferably, the carrier (C) comprises or consists essentially of benzyl alcohol (available from Emerald Kalama Chemical).

[0091] In some embodiments, the amount of carrier (C) present in the topical skin care composition is from about 0.1 wt. % based on the total weight of the topical skin care composition, preferably from about 0.5 wt. %, preferably from about 1 wt. %, preferably from about 1.5 wt. %, preferably from about 2 wt. %, and up to about 5 wt. %, preferably up to about 4 wt. %, preferably up to about 3 wt. %, preferably up to about 2.5 wt. %.

[0092] The weight ratio between the reducing sugar (A) (e.g., dihydroxyacetone), the alkyl sulfonate (B) (e.g., sodium 1-octanesulfonate, sodium 1-decanesulfonate), and the carrier (C) (e.g., benzyl alcohol) can vary depending on the shade (e.g., darkness, hue angle, color saturation) of the tanning. Typically, however, the weight ratio of alkyl sulfonate (B) to reducing sugar (A) ((B):(A)) is from 1:20, preferably from 1:15, preferably from 1:10, preferably from 1:8, preferably from 1:6, preferably from 1:5, preferably from 1:4, preferably from 1:3, more preferably from 1:2, even more preferably from 2:3, still even more preferably from 1:1, and up to 20:1, preferably up to 15:1, preferably up to 10:1, preferably up to 8:1, preferably up to 6:1, preferably up to 5:1, preferably up to 4:1, preferably up to 3:1, more preferably up to 2:1, even more preferably up to 3:2, still even more preferably up to 5:4.

[0093] In some embodiments, the weight ratio of alkyl sulfonate (B) to carrier (C) ((B):(C)) is from 1:4, preferably from 2:7, preferably from 1:3, preferably from 2:5, more preferably from 1:2, even more preferably from 2:3, still even more preferably from 1:1, and up to 4:1, preferably up to 7:2, preferably up to 3:1, preferably up to 5:2, more preferably up to 2:1, even more preferably up to 3:2, still even more preferably up to 5:4.

[0094] (D) Organic solvent The topical skin care composition may optionally include an organic solvent (D) that is structurally different from the carrier (C). The organic solvent (D) may aid in solubilizing ingredients that are not sufficiently soluble in said carrier (C), modify the surface properties of the topical skin care composition to enhance processability, viscosity and / or ease of handling, or generally to provide a suitable vehicle for self-tanning operations. Examples of organic solvents useful in the present invention include, but are not limited to, polyols such as ethylene glycol, propylene glycol (e.g., 1,3-propanediol, 1,2-propanediol), butylene glycol (e.g., 1,3-butanediol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol), hexylene glycol, isoprene glycol, diethylene glycol, dipropylene glycol, glycerin, polyol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether), and C1-C4 lower alkanols such as methanol, ethanol, isopropanol, butanol, and mixtures thereof. In some embodiments, the organic solvent (D) comprises at least one polyol selected from the group consisting of 1,3-propanediol, 1,2-propanediol, ethylene glycol, glycerin, and 1,3-butanediol (available from OXEA). In a preferred embodiment, the organic solvent (D) is 1,3-propanediol. When present, polyols (e.g., 1,3-propanediol) can also enhance the Maillard reaction by reducing the amount of water that enters the keratin protein (see Figures 10A-G).

[0095] Alternatively, a mixture of polyols, for example, a mixture of a first polyol and a second polyol different from the first polyol, is used as the organic solvent (D). In some embodiments, the first polyol is 1,3-propanediol. In some embodiments, the second polyol is glycerin. When a mixture of a first polyol (e.g., 1,3-propanediol) and a second polyol (e.g., glycerin) is used, the weight ratio of the first polyol to the second polyol is typically from 1:6, preferably from 1:5, preferably from 1:4, preferably from 1:3, more preferably from 1:2, more preferably from 1:1, even more preferably from 3:2, even more preferably from 2:1, and can be up to 10:1, preferably up to 8:1, preferably up to 6:1, more preferably up to 5:1, even more preferably up to 4:1, even more preferably up to 3:1.

[0096] When present, the organic solvent (D) may be included in the topical skin care composition in an amount ranging from about 0.2 wt. %, preferably from about 0.5 wt. %, more preferably from about 1 wt. %, preferably from about 2 wt. %, more preferably from about 3 wt. %, even more preferably from about 4 wt. %, still even more preferably from about 5 wt. %, and up to about 20 wt. %, preferably up to about 15 wt. %, preferably up to about 12 wt. %, more preferably up to about 10 wt. %, even more preferably up to about 8 wt. %, and still even more preferably up to about 6 wt. %, based on the total weight of the topical skin care composition.

[0097] The weight ratio of carrier (C) (e.g., benzyl alcohol) to organic solvent (D) (e.g., 1,3-propanediol, ethylene glycol, glycerin) may range from 1:200, preferably from 1:150, preferably from 1:100, preferably from 1:50, preferably from 1:25, preferably from 1:20, preferably from 1:10, more preferably from 1:8, even more preferably from 1:6, still even more preferably from 1:5, and up to 25:1, preferably up to 20:1, preferably up to 15:1, preferably up to 10:1, preferably up to 5:1, preferably up to 3:1, preferably up to 2:1, preferably up to 1:1, more preferably up to 1:2, even more preferably up to 1:3, still even more preferably up to 1:4.

[0098] (E) Aromatic sulfonate The topical skin care compositions of the present invention may optionally include an aromatic sulfonate (E). Preferably, the aromatic sulfonate (E) comprises Formula (II):

[0099] [ka] wherein (i) R2 is an optionally substituted aryl or an optionally substituted heteroaryl, and (ii) Y is a cation selected from the group consisting of a hydrogen ion, an ammonium ion, and an alkali metal ion.

[0100] The cation Y can be a hydrogen ion, an ammonium ion (i.e., NH4 + ), quaternary ammonium ions (e.g., tetraethylammonium, tetrabutylammonium), lithium ions, sodium ions, potassium ions, and silver ions. Preferably, the aromatic sulfonate (E) is an alkali metal salt of aromatic sulfonic acid. In a preferred embodiment, Y is an alkali metal ion, such as a lithium ion, a sodium ion, or a potassium ion. Most preferably, Y is a sodium ion.

[0101] The aromatic sulfonate (E) may be an optionally substituted phenyl sulfonate, an optionally substituted naphthyl sulfonate, or both. In preferred embodiments, R2 is an optionally substituted aryl. In some embodiments, R2 is an optionally substituted phenyl. In some embodiments, R2 is an optionally substituted naphthyl. R2 may be substituted with at least one substituent, such as an optionally substituted alkyl, alkoxy, alkoxycarbonyl, carboxy, amino, hydroxy, thiol, halogen, cyano, or nitro. Alternatively, R2 is unsubstituted.

[0102] In some embodiments, R2 is substituted with at least one linear, branched, or cyclic alkyl group having at least 1, preferably at least 2, preferably at least 3, preferably at least 4, preferably at least 5 carbon atoms, and up to 14, preferably up to 12, preferably up to 10, preferably up to 8, preferably up to 6 carbon atoms. In a preferred embodiment, R2 is substituted with at least one linear alkyl group, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl. In a preferred embodiment, R2 is substituted with at least one branched alkyl group, such as isopropyl, sec-butyl, isobutyl, isobutyl, tert-butyl, isopentyl, neopentyl, and isohexyl. Most preferably, R2 is substituted with methyl or isopropyl.

[0103] Exemplary aromatic sulfonates include, but are not limited to, phenyl sulfonates, such as sodium benzenesulfonate, sodium p-toluenesulfonate, sodium cumenesulfonate (i.e., sodium 4-isopropylbenzenesulfonate), sodium 2,3-dimethylbenzenesulfonate, sodium 2,5-dimethylbenzenesulfonate, sodium 2,4,6-trimethylbenzenesulfonate, sodium 4-ethylbenzenesulfonate, sodium 4-propylbenzenesulfonate, sodium 4-tert-butylbenzenesulfonate, sodium 4-chlorobenzenesulfonate, sodium 4-bromobenzenesulfonate, sodium 4-hydroxybenzenesulfonate, sodium dodecylbenzenesulfonate, 3-sulfonylbenzenesulfonate, sodium 4-isopropyl ... sodium benzoate, potassium 4-sulfobenzoate, 4-amino-3,5-dibromobenzenesulfonic acid sodium salt, 4-octylbenzenesulfonic acid sodium salt, and 4-dodecylbenzenesulfonic acid sodium salt; naphthyl sulfonates, such as sodium 1-naphthalenesulfonate, sodium 2-naphthalenesulfonate, sodium 2-methyl-1-naphthalenesulfonate, sodium 4-methyl-1-naphthalenesulfonate, sodium 2-butyl-1-naphthalenesulfonate, sodium 4-hydroxy-1-naphthalenesulfonate, sodium 4-amino-1-naphthalenesulfonate, sodium 6-hydroxy-2-naphthalenesulfonate, and sodium 5-amino-1-naphthalenesulfonate, and mixtures thereof.

[0104] In some embodiments, polymers or oligomers containing an aromatic sulfonate of formula (II) as a repeating unit, such as poly(sodium 4-styrenesulfonate), poly(4-styrenesulfonic acid) ammonium salt, poly(4-styrenesulfonic acid), poly(sodium 2-styrenesulfonate), and polyanetholesulfonate, may be used in place of or in addition to the aforementioned aromatic sulfonates.

[0105] In a preferred embodiment, the aromatic sulfonate (E) is at least one selected from the group consisting of sodium 2-naphthalenesulfonate, sodium p-toluenesulfonate, sodium cumenesulfonate, 4-dodecylbenzenesulfonic acid sodium salt, and poly(sodium 4-styrenesulfonate), more preferably at least one selected from the group consisting of sodium 2-naphthalenesulfonate (available from Sugai Chemical), sodium p-toluenesulfonate, and sodium cumenesulfonate.

[0106] As used herein, the topological polar surface area (tPSA) of a molecule is defined as the sum of the surface contributions of polar atoms (e.g., oxygen and nitrogen atoms, and bonded hydrogen atoms) in a molecule.Methods for calculating tPSA are known to those skilled in the art (see, for example, Ertl, P. et al., "Fast calculation of molecular polar surface area as a sum of fragment-based contributions and its application to the prediction of drug transport properties," J.Med.Chem.2000,43,3714-3717, the entire contents of which are incorporated herein by reference).For example, tPSA can be determined using a desktop computer and commercially available chemical graphics software such as ChemAxon-Marvinview and ChemDraw.Alternatively, tPSA can be found in many chemical databases, such as SciFinder.

[0107] The aromatic sulfonates (E) useful in the present invention are those having a molecular weight of 100 Å or less. 2 less than, for example, about 20 Å 2 to, preferably about 30 Å 2 to, more preferably about 40 Å 2 to, and even more preferably about 50 Å 2 from and up to about 95 Å 2 , preferably up to about 90 Å 2, preferably up to about 80 Å 2 , preferably up to about 70 Å 2 , more preferably up to about 65 Å 2 , and even more preferably up to about 60 Å 2 It has a topological polar surface area (tPSA) of .

[0108] As used herein, a hydrogen bond donor site is a functional group having a hydrogen atom that easily coordinates with an electronegative atom such as oxygen, nitrogen, or sulfur. Exemplary hydrogen bond donor sites include hydroxy, carboxylic acid, thiol, sulfonic acid, primary amine, secondary amine, and NH functional groups in amides. In some embodiments, the aromatic sulfonate (E) has a maximum of two hydrogen bond donor sites, preferably a maximum of one hydrogen bond donor site, and more preferably no hydrogen bond donor sites.

[0109] Without wishing to be bound by theory, aromatic sulfonates (E) with lower tPSA values ​​and / or fewer hydrogen bond donors have better skin penetration and higher skin absorption, which may be advantageous for self-tanning skin care compositions.

[0110] When present, the aromatic sulfonate (E) may be included in the topical skin care composition in an amount of at least about 0.05 wt. %, preferably at least about 0.1 wt. %, preferably at least about 0.5 wt. %, preferably at least about 1 wt. %, more preferably at least about 1.5 wt. %, even more preferably at least about 2 wt. %, still even more preferably at least about 2.5 wt. %, and up to about 10 wt. %, preferably up to about 8 wt. %, preferably up to about 6 wt. %, preferably up to about 5 wt. %, preferably up to about 4 wt. %, more preferably up to about 3.5 wt. %, even more preferably up to about 3 wt. %, and still even more preferably up to about 2.75 wt. %, based on the total weight of the topical skin care composition.

[0111] Without being bound by theory, it is believed that the aromatic sulfonate (E) in the present invention promotes a high level of Maillard reaction by assisting in the polymerization and / or conjugation of more highly polymerized melanoidins, thereby resulting in intensely pigmented and fade-resistant tanning. The addition of aromatic sulfonate (E) to a topical skin care composition containing a reducing sugar (A) (e.g., dihydroxyacetone) and an alkyl sulfonate (B) synergistically enhances the tanning performance of the composition by providing an intense, long-lasting artificial tan with customizable skin tone adjustment. Specifically, the use of a combination of reducing sugar (A), alkyl sulfonate (B), and aromatic sulfonate (E) produces a significantly darker tan than a mixture of only reducing sugar (A) and alkyl sulfonate (B) or only reducing sugar (A) and aromatic sulfonate (E) (see Figures 6A-D).

[0112] Custom tanning shades can be achieved by varying the weight ratio of alkyl sulfonate (B) to aromatic sulfonate (E). These variations result in topical skin care compositions with adjustable levels of darkness and hue upon application. In some embodiments, the weight ratio of alkyl sulfonate (B) to aromatic sulfonate (E) ((B):(E)) is from 1:100, preferably from 1:90, preferably from 1:80, preferably from 1:70, preferably from 1:60, preferably from 1:50, preferably from 1:40, preferably from 1:30, preferably from 1:20, preferably from 1:10, more preferably from 1:8, preferably from 1:6, preferably from 1:5, preferably from 1:4, preferably from 1:3, even more preferably from 1:40. Preferably from 1:2, even more preferably from 1:1 and up to 100:1, preferably up to 90:1, preferably up to 80:1, preferably up to 70:1, preferably up to 60:1, preferably up to 50:1, preferably up to 40:1, preferably up to 30:1, more preferably up to 20:1, preferably up to 10:1, preferably up to 8:1, preferably up to 6:1, preferably up to 4:1, more preferably up to 3:1, even more preferably up to 2:1, even more preferably up to 3:2.

[0113] (F)Water In some embodiments, the topical skin care compositions of the present invention are aqueous compositions or oil-in-water (o / w) emulsions in which the continuous phase is aqueous. Thus, in preferred embodiments, the topical skin care composition further comprises water (F) in an amount of at least about 10 wt. %, preferably at least about 20 wt. %, preferably at least about 30 wt. %, preferably at least about 40 wt. %, more preferably at least about 50 wt. %, even more preferably at least about 60 wt. %, still even more preferably at least about 70 wt. %, and up to about 95 wt. %, preferably up to about 90 wt. %, more preferably up to about 85 wt. %, and even more preferably up to about 80 wt. %, based on the total weight of the topical skin care composition.

[0114] (G) Thickener The topical skin care composition may optionally include a thickening agent (G), which may improve the stability of the composition and also produce a skin-friendly consistency upon application.

[0115] The thickener (G) may comprise a copolymer containing at least one structural unit selected from the group consisting of hydroxyalkyl acrylate, acrylate, acrylamide, and acryloyldialkyl taurate. Examples of thickening copolymers include copolymers of hydroxyethyl acrylate and sodium acryloyldimethyl taurate, copolymers of acrylate and sodium acryloyldimethyl taurate, copolymers of acrylamide and acrylate, and copolymers of acrylic acid, acrylamide, acrylate, and sodium acryloyldimethyl taurate. Preferably, the thickener (G) comprises an anionic (co)polymer.

[0116] These thickening copolymers are commercially available, for example, from SEPPIC, France. Examples of thickeners containing copolymers of hydroxyethyl acrylate and acryloyldimethyl taurate include SEPINOV™ EMT 10 (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer), SIMULGEL™ NS (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, squalane, polysorbate 60), SIMULGEL™ FL (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, isohexadecane, polysorbate 60), SEPIPLUS™ S (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, polyisobutene, PEG-7 trimethylolpropane coconut ether), and SIMULGEL™ INS 100 (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, isohexadecane, polysorbate 60). Examples of thickeners containing copolymers of acrylate and acryloyldimethyltaurate include SIMULGEL™ EG (sodium acrylate / sodium acryloyldimethyltaurate copolymer, isohexadecane, polysorbate 80), SIMULGEL™ EPG (sodium acrylate / sodium acryloyldimethyltaurate copolymer, polyisobutene, caprylyl capryl glucoside), and SIMULGEL™ SMS 88 (sodium acrylate / acryloyldimethyltaurate / dimethylacrylamide crosspolymer, isohexadecane, polysorbate 60). Examples of thickeners containing copolymers of acrylamide and acrylate include SEPIPLUS™ 265 (acrylamide / ammonium acrylate copolymer, polyisobutene, polysorbate 20). An example of a thickener containing a copolymer of acrylic acid, acrylamide, acrylate, and acryloyldimethyltaurate is SEPIPLUS™ 400 (polyacrylate-13, polyisobutene, polysorbate 20).

[0117] In some embodiments, the thickener (G) contains a copolymer of hydroxyethyl acrylate and sodium acryloyldimethyl taurate. More preferably, the thickener is SEPIPLUS™ S (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, polyisobutene, PEG-7 trimethylolpropane coconut ether).

[0118] Other thickening materials that may be used in addition to or in place of the aforementioned thickeners include carbomers (e.g., Carbomer 980), C 10 ~ 30 Alkyl acrylate crosspolymer (e.g., Pemulen TR-1, Pemulen TR-2 (acrylate / C 10 ~ 30 Alkyl acrylate crosspolymer), SEPIGEL™ 305 (polyacrylamide, C 13 ~ 14 Isoparaffin, Laureth-7), SIMULGEL™ A (ammonium polyacrylate, isohexadecane, PEG-40 castor oil), SIMULGEL™ 600 (acrylamide / sodium acryloyldimethyltaurate copolymer, isohexadecane, polysorbate 80), ARISTOFELX® AVC (ammonium acryloyldimethyltaurate / N-vinylpyrrolidone copolymer), ARISTOFELX® AVS (sodium acryloyldimethyltaurate / N-vinylpyrrolidone copolymer), and modified cellulose polymers (e.g., hydroxyethyl cellulose, methylcellulose).

[0119] As used herein, unless otherwise specified, a cationic copolymer refers to a copolymer that includes as one of the repeating units a cationic monomer that is a methacryloylethyltri(C1-C3 alkyl)ammonium salt or an acryloylethyltri(C1-C3 alkyl)ammonium salt (e.g., acryloylethyltrimethylammonium chloride). Examples of monomers that can be utilized to form cationic copolymers with methacryloylethyltri(C1-C3 alkyl)ammonium salts or acryloylethyltri(C1-C3 alkyl)ammonium salts include acrylamide, methacrylamide, tris(hydroxymethyl)-acrylamidomethane, and those disclosed in U.S. Pat. No. 7,780,954, the entirety of which is incorporated herein by reference.

[0120] In a preferred embodiment, the topical skin care composition is substantially free of cationic copolymers, which includes being substantially free, preferably completely free (i.e., 0 wt. %) of the aforementioned cationic copolymers, such as acrylamide / acryloylethyltrimethylammonium chloride / tris(hydroxymethyl)-acrylamidomethane copolymer.

[0121] (H) Preservatives The topical skin care composition may optionally further comprise a preservative (H). For example, the preservative may be selected to kill bacteria that may otherwise be maintained or grow in the composition, or to prevent deterioration or chemical degradation (e.g., oxidative degradation) of the composition. Preservatives suitable for use in cosmetic compositions are well known to those skilled in the art. In this regard, the preservative selected may vary depending on the specific ingredients present in the topical skin care composition. Examples of suitable preservatives include methylparaben, ethylparaben, propylparaben, EDTA or a salt thereof (e.g., disodium EDTA), phenoxyethanol, DMDM ​​hydantoin, benzyl alcohol, ethyldibromoglutaronitrile-phenoxyethanol / polyquatemium-7 (Euxyl K-400, Calgon), imidazolidinyl urea, diazolidinyl urea, benzalkonium chloride, benzethonium chloride, sodium benzoate, sorbic acid, etc., or combinations thereof.

[0122] Preferably, the preservative (H) is methylparaben and / or ethylparaben, most preferably a mixture of these preservatives. When present, the preservative (H) may be included in an amount of up to about 5 wt. %, preferably up to about 4 wt. %, preferably up to about 3 wt. %, preferably up to about 2 wt. %, preferably up to about 1 wt. %, preferably up to about 0.5 wt. %, for example, from about 0.001 wt. % to about 3 wt. %, or from 0.1 wt. % to about 1.5 wt. %, or from 0.15 wt. % to about 1 wt. %, or from 0.3 wt. % to about 0.45 wt. %, based on the total weight of the topical skin care composition in the present invention.

[0123] (I) Acidulant The topical skin care compositions disclosed herein may optionally be formulated to include an acidulant (I) to adjust the pH to be more acidic / slightly alkaline. Additionally, depending on chemical structure, the acidulant (I) may act as a chelating agent and / or buffering agent to neutralize minerals, enhance the activity of any preservatives present, and stabilize active ingredients (e.g., tanning agents).

[0124] The acidulant used in the present invention may be an inorganic acid or an organic acid, particularly, but not limited to, hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acid such as fumaric acid, acetic acid, and α-hydroxy acid such as tartaric acid, citric acid, malic acid, lactic acid, and glycolic acid, and mixtures thereof.If the acidulant contains an α-hydroxy acid functional group, it can also help exfoliate the skin and soften wrinkles.Preferably, citric acid is used.

[0125] When present, the acidulant (I) may be included in the present invention in an amount of up to about 5 wt.%, preferably up to about 4 wt.%, preferably up to about 3 wt.%, preferably up to about 2 wt.%, preferably up to about 1 wt.%, for example, from about 0.001 wt.% to about 3 wt.%, or from 0.02 wt.% to about 2 wt.%, or from 0.1 wt.% to about 1 wt.%, or from 0.2 wt.% to about 0.5 wt.%, based on the total weight of the topical skin care composition. The pH of the topical skin care composition may vary, but is preferably less than 6.5, e.g., at least 2, preferably at least 2.5, more preferably at least 3, even more preferably at least 3.5, and at most 6, preferably at most 5, more preferably at most 4.

[0126] Other optional ingredients Various optional ingredients frequently used in topical compositions, such as fragrances, propellants, vehicles, adjuvants, anti-aging ingredients, proteins, rheology control agents, dispersants, thickeners, film-forming agents, sequestering agents, cleansing agents, vitamins, botanicals, and sunscreens, as well as other classes of materials whose presence may be cosmetically, medically, or otherwise desirable, may also be included, optionally at their art-established usage levels. For example, the topical skin care compositions of the present invention may optionally be prepared to include one or more fragrances known to those skilled in the cosmetic arts to impart a pleasant scent or to help mask any malodorous ingredients that may be present in the topical skin care composition.

[0127] In preferred embodiments, the topical skin care composition is substantially free of such optional ingredients, but if included, non-limiting examples that may be used include film-forming materials such as petrolatum, hydrolyzed wheat protein / wheat oligosaccharides (e.g., Croda Inc.Cropeptide W by Alzona), hydrolyzed corn protein, hydrolyzed wheat gluten, hydrolyzed yeast protein, hydrolyzed vegetable protein, hydrolyzed soy protein, hydrolyzed rice protein, and hydrolyzed potato protein; moisturizing agents such as glycereth-7-triacetate (Dermol GL-7-A, Alzo), glycerin, glycereth-5-lactate, and glycereth-7-diisononanoate; skin conditioning agents and emollients such as mineral oil, cetearyl alcohol, silicones such as dimethicone, cyclomethicone, phenyl trimethicone, alkyl dimethicone, fluorine-modified silicones, esters of isononanoic acid such as ethylhexyl isononanoate, butylene glycol diisononanoate, cetearyl isononanoate, and cetyl isononanoate, and polyethyl glycol derivatives of castor oil such as PEG-40 castor oil (Surfactol 365, available from Vertellus), PEG-45 castor oil, PEG-50 castor oil, PEG-60 castor oil, and PEG-100 castor oil; surfactants, such as polyoxyalkylene ethers of fatty alcohols, for example, laureth-3, ceteareth-6, ceteareth-11, ceteareth-15, ceteareth-16, ceteareth-17, ceteareth-18, ceteareth-20, ceteareth-23, ceteareth-25, ceteareth-27, ceteareth-28, ceteareth-30, isoceteth-20, laureth-9 / myreth-9, and PPG-3 caprylyl ether, steareth (steareth-2, steareth-4 , steareth-6, steareth-7, steareth-10, steareth-11, steareth-13, steareth-15, steareth-20), and polyethylene glycol esters, such as PEG-14 laurate, PEG-15 laurate, PEG-20 laurate, PEG-32 laurate, PEG-75 laurate, PEG-150 laurate, or other surfactants; and sunscreen or UV light absorbing compounds, such as octyl dimethyl PABA, benzophenone-4, DEA methoxycinnamate, 2-phenyl-benzimidazole-5-sulfonic acid, and triethanolamine salicylate.

[0128] In a preferred embodiment, the topical skin care composition comprises 1-3 wt. % of a reducing sugar (A) (e.g., dihydroxyacetone, erythrulose), 1-3 wt. % of an alkyl sulfonate (B) (e.g., sodium 1-octanesulfonate, sodium 1-decanesulfonate), 1-3 wt. % of a carrier (C) (e.g., benzyl alcohol), 2-8 wt. % of an organic solvent (D) (e.g., 1,3-propanediol, 1,2-propanediol, ethylene glycol, glycerin, 1,3-butanediol), and 70-82 wt. % of water (F), each based on the total weight of the topical skin care composition, with the remainder optionally comprising an aromatic sulfonate (E) (e.g., sodium 2-naphthalenesulfonate, sodium p-toluenesulfonate), a preservative (H) (e.g., a mixture of methylparaben and ethylparaben), an acidulant (I) (e.g., citric acid), and a thickener (G) (e.g., SEPIPLUS S (hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer, polyisobutene, PEG-7 trimethylolpropane coconut ether)).

[0129] In a preferred embodiment, the topical skin care composition comprises 1-3 wt. % of a reducing sugar (A) (e.g., dihydroxyacetone), 1-3 wt. % of an alkyl sulfonate (B) (e.g., sodium 1-octanesulfonate, sodium 1-decanesulfonate, or both), 1-3 wt. % of a carrier (C) (e.g., benzyl alcohol), 2-8 wt. % of an organic solvent (D) (e.g., 1,3-propanediol, 1,2-propanediol, ethylene glycol, glycerin, 1,3-butanediol), 70-82% by weight of water (F), 0.001-1% by weight of a preservative (H) (e.g., a mixture of methylparaben and ethylparaben), 0.001-0.2% by weight of an acidulant (I) (e.g., citric acid), and 1-3% by weight of a thickener (G) (e.g., SEPIPLUS™ S (hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, polyisobutene, PEG-7 trimethylolpropane coconut ether)).

[0130] In a preferred embodiment, the topical skin care composition comprises 1-3 wt. % of a reducing sugar (A) (e.g., dihydroxyacetone), 1-3 wt. % of a mixture of an alkyl sulfonate (B) (e.g., sodium 1-octanesulfonate, sodium 1-decanesulfonate, or both) and an aromatic sulfonate (E) (e.g., sodium 2-naphthalenesulfonate, sodium p-toluenesulfonate, or both) in the weight ratios previously specified, each based on the total weight of the topical skin care composition, 1-3 wt. % of a carrier (C) (e.g., benzyl alcohol), 2-8 wt. % of an organic solvent (D) (e.g., For example, 1,3-propanediol, 1,2-propanediol, ethylene glycol, glycerin, 1,3-butanediol), 70 to 82% by weight of water (F), 0.001 to 1% by weight of a preservative (H) (e.g., a mixture of methylparaben and ethylparaben), 0.001 to 0.2% by weight of an acidulant (I) (e.g., citric acid), and 1 to 3% by weight of a thickener (G) (e.g., SEPIPLUS™ S (hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer, polyisobutene, PEG-7 trimethylolpropane coconut ether)).

[0131] The topical skin care compositions of the present invention can be prepared by any method known to those skilled in the art. For example, a water-containing topical skin care composition can be prepared by (i) combining all water-soluble ingredients except for a tanning agent (e.g., a reducing sugar) together with water in a suitably sized vessel, optionally with heating (e.g., 40-90°C, preferably 50-85°C, more preferably 75-81°C), and stirring until homogeneous; (ii) in a separate vessel, optionally with heating (e.g., 40-90°C, preferably 50-85°C, more preferably 75-81°C), and stirring until homogeneous; (iii) optionally with heating (e.g., 40-90°C, preferably 50-85°C, more preferably 75-81°C), and stirring until homogeneous; The topical skin care composition can be prepared by mixing the homogenous mixture from (i) with the homogenous mixture from (ii), if present, while stirring at a constant temperature (temperature, preferably 50-85°C, more preferably 75-81°C) until a homogenous aqueous composition or a homogenous oil-in-water emulsion is formed; (iv) cooling the homogenous aqueous composition or homogenous oil-in-water emulsion; and (v) once cooled, optionally adding a tanning agent (e.g., a reducing sugar) to the homogenous aqueous composition or homogenous oil-in-water emulsion while mixing under conditions similar to those described above, thereby forming the topical skin care composition. If present, a thickening agent may be added during step (i) or after step (iii) and before the addition of the tanning agent (i.e., before step (v)). Once cooled, the resulting topical skin care composition may then be filled into the desired packaging. Mixing may be performed by a propeller, such as a high-shear mixer and a high-speed dissolver.

[0132] How to self-tan In one or more embodiments, the present invention provides a method of adjusting skin color by topically applying a topical skin care composition to the skin of a subject.

[0133] To achieve an acceptable degree of coloring or tanning, a person desiring such coloring or tanning can apply an effective amount of the topical skin care composition evenly over the desired body surface area for an effective application time. Thus, the topical skin care composition can be applied to produce a subtle change in skin color or a more dramatic tanning effect.

[0134] The topical skin care composition can be applied topically to wet or dry skin. Preferably, the desired skin area is cleansed and / or exfoliated before application. During application, the topical skin care composition can be spread directly onto the integumentary skin, for example, by hand or using an applicator such as a wipe, puff, roller, or spray. The topical skin care composition can be used as a single treatment to color the skin, or can be applied in layers, with the skin tanning becoming more intense with each subsequent application, until the desired color intensity is achieved.

[0135] The topical skin care composition may be applied to the desired area as needed, preferably 1 to 4 times daily, preferably 2 to 3 times daily. Application may be for at least 1 day, preferably at least 2 consecutive days, more preferably at least 3 consecutive days, even more preferably at least 4 consecutive days, and up to 14 consecutive days, preferably up to 7 consecutive days, more preferably up to 6 consecutive days, even more preferably up to 5 consecutive days. Alternatively, application may be intermittent. Application frequencies outside these ranges may be used to vary the intensity of coloring, as needed.

[0136] Color appearance (e.g., skin color) can be described in terms of its hue (color), lightness (brightness), and saturation (vividness). Hue is the primary attribute of color vision used to represent "unique hues" (e.g., red, yellow, blue), which are considered to be completely distinct hues. Saturation (also called chroma or colorfulness) indicates the "purity" of a particular hue. Highly saturated hues have vivid and intense colors, while less saturated hues appear duller and duller. Without any saturation, a hue becomes a shade of gray. Lightness represents the lightness or darkness of color vision. For example, an image with a higher lightness value reflects a greater amount of light.

[0137] The quantification of these color attributes (hue, saturation, and lightness) is based on the International Commission on Illumination (CIE) L * a * b * (CIELAB) color space model, CIE L * C * It can be implemented using a variety of color models, including the h° (CIEHCL) color space model, the CIE XYZ model, the RGB color model, and the like.

[0138] In some embodiments, skin color herein is measured by the CIE L * a * b * is measured using the model, where: (i) L * indicates the color brightness, with values ​​ranging from 0 representing black to 100 representing white, and (ii) a * denotes the red / green value of the color, and (iii) b * indicates the yellow / blue value of a color. In some embodiments, skin color herein is measured using the CIE L * C * h° model, where: (i) L * indicates the lightness of the color, and CIE L * a * b * Model L * is the same as (ii) C *denotes chroma, with values ​​starting from 0 indicating no saturation and reaching 60 indicating full saturation, and (iii) h° denotes hue angle. As shown in the chromaticity diagram (FIG. 11), the hue angle of skin colors herein is expressed in degrees, and +a * axis. Specifically, a hue angle of 0° corresponds to red (+a * ) and a hue angle of 90° is yellow (+b * ) Skin color attributes herein can be measured by a spectrophotometer such as a CM-700d, CM-2500d, or CM-2600d spectrophotometer manufactured by Konica Minolta.

[0139] In some embodiments, the methods disclosed herein produce a rich, deep, natural-looking, long-lasting tan to the skin by preserving the original hue while increasing the saturation and darkness of the skin's color.

[0140] The method of the present invention can preserve the original hue of the skin after application of the topical skin care composition. In some embodiments, the method of the present invention changes the hue angle h° of the skin color by less than 2°, preferably less than about 1.5°, preferably less than about 1.2°, preferably less than about 1°, preferably less than about 0.8°, preferably less than about 0.6°, preferably less than about 0.4°, preferably less than about 0.3°, more preferably less than about 0.2°, even more preferably less than about 0.1°, and even more preferably less than about 0.05° compared to the hue angle before topical application (see Figure 4).

[0141] The method of the present invention may darken the skin color after application of the topical skin care composition. In some embodiments, the method of the present invention may darken the skin color lightness L *is reduced by at least about 1%, preferably at least about 2%, preferably at least about 3%, preferably at least about 4%, more preferably at least about 5%, even more preferably at least about 6%, still even more preferably at least about 7%, and at most about 20%, preferably at most about 15%, preferably at most about 12%, more preferably at most about 10%, and even more preferably at most about 8%, compared to the brightness before topical application.

[0142] In a preferred embodiment, the method of the present invention simultaneously maintains the hue angle and reduces the lightness of the treated skin according to the ranges specified above.

[0143] It is noteworthy that the combination of a reducing sugar (A) (e.g., dihydroxyacetone, erythrulose) and an alkyl sulfonate (B) (e.g., sodium 1-octanesulfonate, sodium 1-decanesulfonate) provides unexpected tanning results (darker, longer-lasting (i.e., more fade-resistant), and more natural-looking coloration) compared to using a reducing sugar alone.

[0144] For example, as shown in Figure 4, using a reducing sugar alone significantly alters the hue angle of the treated skin, and in some cases, actually increases the hue angle after extended application (e.g., after 7 days of application). This increase in hue angle is typically responsible for the orange hue that many consumers find undesirable after self-tanning. However, combining an alkyl sulfonate (B) with a reducing sugar (A) effectively maintains the original hue angle, thus creating a natural-looking tan on the treated skin.

[0145] As shown in Figure 1, within 24 hours of application, using a reducing sugar alone results in at least 15% less, preferably at least 20% less, more preferably at least 25% less, even more preferably 30% less, and up to 60% less, preferably up to 50% less, and more preferably up to 40% less skin lightness loss than using a combination of a reducing sugar (A) and an alkyl sulfonate (B). Additionally, as shown in Figure 3, the artificial tan produced by this combination fades significantly slower than using a reducing sugar alone (e.g., less than about 40% fade after 3 days vs. at least 80% fade).

[0146] The methods of the present invention may be utilized to adjust the saturation of skin color. In some embodiments, the methods of the present invention adjust the saturation C of the treated skin color. * is increased by at least about 1%, preferably at least about 2%, preferably at least about 3%, preferably at least about 4%, more preferably at least about 5%, even more preferably at least about 6%, still even more preferably at least about 7%, and up to about 20%, preferably up to about 15%, preferably up to about 12%, more preferably up to about 10%, and even more preferably up to about 8%, compared to the saturation before topical application.

[0147] When an aromatic sulfonate (E) is present in a topical skin care composition, the methods herein may provide a synergistic tanning effect by shifting the original hue and further darkening the skin color. For example, as shown in Figures 6A-D, the use of a combination of a reducing sugar (A), an alkyl sulfonate (B), and an aromatic sulfonate (E) results in at least 25% more darkening, preferably at least 28% more darkening, more preferably at least 30% more darkening, even more preferably at least 35% more darkening, and up to 60% more darkening, preferably up to 50% more darkening, and more preferably up to 40% more darkening, than the use of a reducing sugar (A) and an alkyl sulfonate (B) alone. Furthermore, the use of a combination of a reducing sugar (A), an alkyl sulfonate (B), and an aromatic sulfonate (E) results in at least 20% more darkening, preferably at least 25% more darkening, more preferably at least 28% more darkening, even more preferably at least 30% more darkening, and up to 50% more darkening, preferably up to 40% more darkening, and more preferably up to 35% more darkening, than the use of a reducing sugar (A) and an aromatic sulfonate (E) alone. Furthermore, the presence of the aromatic sulfonate (E) imparts an aesthetically pleasing red / bronze hue to the treated skin.

[0148] The following examples are intended to further illustrate topical skin care compositions and are not intended to limit the scope of the claims. [Example]

[0149] Topical Skin Care Compositions Examples of topical skin care compositions, including comparative compositions used in the tanning performance evaluation, are shown in Examples 1-2 below. The amount of each component is expressed as a weight percentage relative to 100% total weight. DHA refers to dihydroxyacetone available from EMD Millipore. SOS refers to sodium 1-octanesulfonate. SDS refers to sodium 1-decanesulfonate. SDBS refers to sodium dodecylbenzenesulfonate. SLSA refers to sodium lauryl sulfoacetate. NSA refers to sodium 2-naphthalenesulfonate available from Sugai Chemical. BA refers to benzyl alcohol available from Kalama. 1,3-butylene glycol, methylparaben, ethylparaben, and SEPIPLUS™ S are available from Oxea, Ueno, Sharon, and Seppic, respectively. * in the tables below indicates that the example is a comparative example.

[0150] Example 1 [Table 1]

[0151] Example 2 [Table 2] TIFF0007791838000006.tif25569

[0152] Manufacturing method An exemplary method for making an example topical skin care composition is as follows. Part A: Deionized water and 1,3-butylene glycol were first added to the main vessel and mixed thoroughly. The main vessel was heated to a temperature of 75-81°C. Once the vessel temperature reached 75°C, the parabens, BA, and SOS were added to the main vessel and mixed until clear. The heat was then removed. SEPIPLUS™ S was added to the main vessel and mixed for approximately 20 minutes. After the addition of SEPIPLUS™ S, incremental mixing was optionally applied as the mixture thickened. The main vessel was cooled to a temperature below 40°C, thereby forming Part A.

[0153] Part B: Deionized water and DHA were added to a separate vessel and mixed until clear to form Part B.

[0154] After Part A was cooled to a temperature below 40° C., Part B was added to Part A to form Part AB, which was mixed for approximately 5 minutes.

[0155] Finally, citric acid was added to Part AB to adjust the pH to 3.5-4.0, thereby obtaining the topical skin care composition.

[0156] Procedure for collecting stratum corneum from the heels of volunteers: (i) The heel was cleaned with an alcohol-soaked cotton swab to remove any residue on the skin surface; (ii) waited 5–10 min to ensure the skin was dry; (iii) Heel file * The stratum corneum was collected onto a piece of aluminum foil using * Preferably use the following heel file by Panasonic: https: / / www.amazon.com / Panasonic-ES2502P-Electric-Heel-Buffer / dp / B001CS69NQ); (iv) the collected fragments were mixed, especially if the fragments were collected from two or more volunteers; (v) The pieces were dried at room temperature and humidity conditions for more than 3 hours.

[0157] Determination of relative keratin swelling: (i) Test and control samples were prepared by adding 20 mg of dried stratum corneum powder to an appropriate number of NMR tubes (Wilmad-LabGlass WG-1000-7, inner diameter 4.1 mm); (ii) NMR tubes were placed in a test tube rack, each tube or rack position was labeled, the rack was placed in a light box, and a photograph was taken with a digital camera; (iii) An aqueous solution containing deionized water and 2% (w / w%) of the test compound was prepared, and test samples were prepared by adding 1.5 mL of the solution to an appropriately labeled NMR tube; (iv) A control sample was prepared by adding 1.5 mL of deionized water to an appropriately labeled NMR tube; (v) Each NMR tube sample was gently shaken manually without inversion for approximately 1 minute to uniformly disperse the stratum corneum powder in the solution; (vi) The NMR tube was sealed and placed in a test tube rack, and the rack was placed in a temperature-controlled room at 40°C for 1 hour; (vii) The test tube rack with all samples was then placed in a light box and photographed with a digital camera; (viii) The height of the stratum corneum powder for each sample was measured using the image analysis function of ImageJ (NIH) software; (ix) The keratin swelling index of the test compound was calculated according to the following formula (A):

[0158]

number

[0159] Determination of relative α-helix / β-sheet index ratio (i) Test and control samples were prepared by adding 20 mg of dried stratum corneum powder to an appropriate number of NMR tubes (Wilmad-LabGlass WG-1000-7, inner diameter 4.1 mm); (ii) NMR tubes were placed in a test tube rack and each tube or its position in the rack was labeled; (iii) An aqueous solution containing deionized water and 2% (w / w%) of the test compound was prepared, and test samples were prepared by adding 1.5 mL of the solution to an appropriately labeled NMR tube; (iv) A control sample was prepared by adding 1.5 mL of deionized water to an appropriately labeled NMR tube; (v) Each NMR tube sample was gently shaken manually without inversion for approximately 1 minute to uniformly disperse the stratum corneum powder in the solution; (vi) The NMR tube was sealed and placed in a test tube rack, and the rack was placed in a temperature-controlled room at 40°C for 96 hours; (vii) The sample was then gently shaken manually without inversion for approximately 1 minute; (viii) The supernatant was removed, and 1.5 mL of deionized water was added to the tube and allowed to stand at room temperature for more than 15 minutes; (ix) Step (viii) was repeated two more times; (x) The stratum corneum was scraped off with a spatula and transferred to a clean 8-dram vial; (xi) drying the stratum corneum at room temperature and humidity conditions for more than 12 hours; (xii) Each dried sample was then analyzed by FT-IR (Nicolet iS50, Thermo Fisher Scientific Inc., MA, USA) equipped with a ZeSe ATR accessory and a DTGS detector. -1 Resolution of 4000~650cm -1 32 scans were performed at wavenumbers in the range of ; (xiii) The spectra were analyzed using in-house developed software (S. Takada, S. Naito, J. Sonoda, Y. Miyauchi. Non-invasive in vitro measurement of natural moisturizing factor content in the stratum corneum of human skin by attenuated total reflection infrared spectroscopy. Applied Spectroscopy 2012;66:26-32, the entire contents of which are incorporated herein by reference), which provides an α-helix / β-sheet index corresponding to changes in protein secondary structure (H. Takahashi, H. Tsuji, M. Minami-Hori, Y. Miyauchi, H. Iizuka, Defective barrier function accompanied by structural changes of psoriatic stratum corneum, The Journal of Dermatology 2014;41:144-148, the entire contents of which are incorporated herein by reference). The relative α-helix / β-sheet index ratio of the test sample was calculated by dividing the α-helix / β-sheet index of the test sample by the α-helix / β-sheet index of the control sample.

[0160] Methods for evaluating topical skin care compositions Skin testing An example of the composition is 2 mg / cm 2 The skin color parameters (e.g., lightness L * , hue angle h°) were measured before application and at various times after application of the test composition specified for each test, followed by the change in each parameter (ΔL * , ΔC * , Δh°) was calculated. Specifically, a CM-2600d manufactured by Konica Minolta, Inc. was used as the colorimeter.

[0161] Skin testing can be carried out as a consumer home use study.For example, the data of Figures 3 and 4 is collected by the following method.Consumers apply one lotion product containing DHA only ("Control DHA") or DHA and SOS ("+SOS") to their arms and legs once a day for 7 days.Color measurements are taken on arms and legs at baseline (day 0), day 3 and day 7.Starting on day 7, panelists stop using the test composition.Another color measurement is taken on arms and legs on day 10.

[0162] The present invention also contemplates other embodiments that "comprise," "consist," and "consist essentially of" the embodiments or elements presented herein, whether explicitly stated or not.

[0163] Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

[0164] All patents and other references mentioned above are incorporated herein by this reference in their entirety as if fully set forth.

Claims

1. (A) 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) optionally substituted C 8 ~ 12 alkyl sulfonates, and (C) Carrier 1. A topical skin care composition comprising: the reducing sugar (A) is dihydroxyacetone, erythrulose, or both; The carrier (C) comprises an aromatic alcohol; Topical skin care compositions.

2. Optionally substituted C 8 ~ 12 The topical skin care composition of claim 1 , wherein the alkyl sulfonate (B) is an unsubstituted alkyl sulfonate.

3. Optionally substituted C 8 ~ 12 3. The topical skin care composition of claim 1, wherein the alkyl sulfonate (B) is an alkali metal alkyl sulfonate.

4. Optionally substituted C 8 ~ 12 4. The topical skin care composition of claim 1, wherein the weight ratio of alkyl sulfonate (B) to reducing sugar (A) ((B):(A)) is from 1:20 to 20:

1.

5. The topical skin care composition of any one of claims 1 to 4, wherein the carrier (C) comprises benzyl alcohol.

6. The topical skin care composition of any one of claims 1 to 5, further comprising (D) an organic solvent.

7. 7. The topical skin care composition of claim 6, wherein the organic solvent (D) is at least one selected from the group consisting of 1,3-propanediol, 1,2-propanediol, and 1,3-butanediol.

8. (E) further contains an aromatic sulfonate, wherein the aromatic sulfonate (E) has a molecular weight of 100 Å or more. 2 The topical skin care composition of any one of claims 1 to 7, having a topological polar surface area (tPSA) of less than

9. 9. The topical skin care composition of claim 8, wherein the aromatic sulfonate (E) is an optionally substituted phenyl sulfonate, an optionally substituted naphthyl sulfonate, or both.

10. 10. The topical skin care composition of claim 8 or 9, wherein the weight ratio of alkyl sulfonate (B) to aromatic sulfonate (E) ((B):(E)) is from 1:100 to 100:

1.

11. 1. A method for darkening and maintaining the color of a subject's skin, comprising: topically applying the topical skin care composition of any one of claims 1 to 10 onto the skin of a subject. Including, Topical application reduces the color lightness, L, compared to the lightness and hue angle before topical application, respectively. * decreases by at least 10% and the hue angle h° of the color changes by less than 2°; method.

12. 1. A method for darkening the skin color of a subject, comprising: topically applying the topical skin care composition of any one of claims 1 to 10 onto the skin of a subject. Including, Topical application resulted in a decrease in color brightness L compared to before topical application. * decreases by at least 10% method.

13. 1. A method for adjusting skin color saturation in a subject, comprising: topically applying the topical skin care composition of any one of claims 1 to 10 onto the skin of a subject. Including, Topical application results in a decrease in color saturation C compared to before topical application. * increases by at least 10% method.

14. 1. A collection of topical skin care products for retail sale, comprising: (a) (A) 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) optionally substituted C 8 ~ 12 alkyl sulfonates, and (C) Carrier Including, the reducing sugar (A) is dihydroxyacetone, erythrulose, or both; The carrier (C) contains an aromatic alcohol; Optionally substituted C 8 ~ 12 the weight ratio of alkyl sulfonate (B) to reducing sugar (A) ((B):(A)) is 1:20 to 20:1; a first topical skin care composition; and (b) (A) 0.1 to 30% by weight of a reducing sugar, based on the total weight of the topical skin care composition; (B) optionally substituted C 8 ~ 12 alkyl sulfonates, and (C) Carrier Including, the reducing sugar (A) is dihydroxyacetone, erythrulose, or both; The carrier (C) contains an aromatic alcohol; Optionally substituted C 8 ~ 12 the weight ratio of alkyl sulfonate (B) to reducing sugar (A) ((B):(A)) is 1:20 to 20:1; a second topical skin care composition; and Including, the content of reducing sugar (A) present in the first topical skin care composition (a) is less than the content of reducing sugar (A) present in the second skin care composition (b), each based on the total weight of the first and second topical skin care compositions; collection.

15. 15. The collection of claim 14, wherein the first topical skin care composition (a) and the second topical skin care composition (b) are packaged separately.

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