BACKGROUND OF THE DISCLOSURE 1. Field of the Disclosure

The present disclosure relates to sunscreen compositions. More particularly, the present disclosure relates to sunscreen compositions having a relatively high amount of alcohol while still retaining one or more favorable viscosity properties.

2. Description of the Related Art

In the field of sunscreen compositions, a rheology modifier or thickener can be used to achieve a desired viscosity. Alcohols, however, particularly ethyl alcohol, can interfere with the viscosity-boosting mechanisms employed by most rheology modifiers. In sunscreen compositions, it can thus be very difficult to use an alcohol, since the composition will be thin, and not provide adequate coverage or UVA/UVB protection to a user. The present disclosure provides a composition that addresses these deficiencies.

SUMMARY OF THE DISCLOSURE

There is provided in one embodiment of the present disclosure a composition that comprises: 0.1 to 10 percent, based on the weight of the total composition, of a rheology modifying agent selected from the group consisting of a copolymer of acryloyldimethyltaurine and vinylpyrrolidone, a copolymer of acrylic acid and

vinylpyrrolidone, acrylic-based anionic polymers, carbomers, and any combinations thereof; 0.01 to 5 percent, based on the total weight of the composition, of a gelling agent selected from the group consisting of starch, modified starch, cellulose, cellulose gum, pectin, gelatin, agar, alginate, gellan gum, and any combinations thereof; and 5 to 40 percent, based on the total weight of the composition, of an alcohol.

There is also provided such a composition that further comprises 0.01 to 5 percent, based on the total weight of the composition, of an emulsion stabilizer comprising natural fibers.

There is further provided in another embodiment of the present disclosure a second composition that comprises: 0.1 to 10 percent, based on the weight of the total composition, of a rheology modifying agent selected from the group consisting of a copolymer of acryloyldimethyltaurine and vinylpyrrolidone, a copolymer of acrylic acid and vinylpyrrolidone, acrylic-based anionic polymers, carbomers, and any combinations thereof; 0.01 to 5 percent, based on the total weight of the composition, of a gelling agent selected from the group consisting of polysaccharides, polysaccharide gums, and a combination thereof; and 20 to 30 percent, based on the total weight of the

composition, of an alcohol selected from the group consisting of aliphatic alcohols having one to four carbons.

There is still further provided for such second composition that it may further comprise 0.01 to 5 percent, based on the total weight of the composition, of an emulsion stabilizer comprising natural fruit fibers.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present disclosure provides a composition containing high amounts of alcohol previously not thought attainable for the above-described reasons (i.e., the adverse effects on viscosity). The compositions of the present disclosure provide protection from both UVA and UVB radiation, but also possess a cooling ability, and desirable feelings to the touch for the user. These latter benefits are provided by the alcohol. The compositions of the present disclosure have alcohol concentrations or amounts in the relatively high ranges discussed below, yet still form a gel-like or viscous structure. Accordingly, the compositions of the present disclosure provide the benefits associated with alcohol, such as cooling, and desirable sensory characteristics, without any of the associated disadvantages. The compositions of the present disclosure also satisfy the broad UVA/UVB spectrum requirements listed in the 2011 Food and Drug Administration's final rules.

"Gel-like" is defined in the present disclosure as referring to a substance or composition having a texture between that of a cream and a rigid, solid structure.

Creams are typically either semi-solid oil-in-water or water-in-oil emulsions. The compositions of the present disclosure are also water-in-oil emulsions or oil-in-water emulsions, preferably the former, but they are more elastic than typical creams. They are not so rigid, however, that they break up upon application to the skin, as solids would. The compositions of the present disclosure are easily spreadable upon application. The compositions of the present disclosure comprise an alcohol compatible rheology modifying agent. The rheology modifying agent may be a copolymer obtained by copolymerization of acryloyldimethyltaurine and vinylpyrrolidone, a copolymer obtained by copolymerization of acrylic acid and vinylpyrrolidone, acrylic-based anionic polymers, carbomers, and any combination thereof. The rheology modifying agent is present in an amount of 0.1 to 10 weight percent, based on the weight of the total composition.

The compositions of the present disclosure also have a gelling agent that forms a fluid elastic gel-like texture. The gelling agent can be a starch, modified starch, cellulose, cellulose gum, pectin, gelatin, agar, alginate, gellan gum, or any combinations thereof, in one embodiment, the gelling agent is a polysaccharide, polysaccharide gum, or a combination thereof. The gelling agent is present in an amount of 0.01 to 5 weight percent, based on the total weight of the composition. Typically, these gelling agents are used in fragrance or food applications, not in cosmetic products such as

sunscreens. The present disclosure has discovered that the gelling agent works particularly well with any of the above-described rheology modifiers to stabilize the compositions of the present disclosure.

The compositions of the present disclosure also have an emulsion stabilizer. The emulsion stabilizer can comprise natural fibers, such as those from leaves, flowers, wood, or fruits. In one embodiment, the emulsion stabilizer is made from fruit pulp. An example of an emulsion stabilizer including fruit pulp is citrus surantium sinensis

(orange) fiber, sold under the tradename Imulsi-Fi™ A30. The Imulsi-Fi™ A30 stabilizer has natural fibers, including tightly bound soluble and insoluble fibers, together in a matrix with proteins and sugars. It also has a distinctive cellular structure and a unique chemical composition that enables both hydrophilic and lipophilic properties to stabilize the emulsion. The emulsion stabilizer helps to prevent the composition from becoming too hard or solid, which would break up upon application to the user's skin. The emulsion stabilizer, particularly the above-described fibers, helps to keep the

composition gel-like. The emulsion stabilizer is present in an amount of 0.01 to 5 weight percent, based on the total weight of the composition.

The compositions of the present disclosure also have one or more alcohols. In one embodiment, the alcohols are volatile aliphatic alcohols having from 1 to 4 carbon atoms, or any mixtures of alcohols having from 1 to 4 carbon atoms. The term "volatile" refers to a liquid that quickly evaporate after contact with the user's skin. Ethanol is an example of a volatile alcohol. The alcohols are present in an amount of 5 to 40 weight percent, 10 to 40 weight percent, or 20 to 30 weight percent, based on the total weight of the composition. Above the stated ranges, the observed sensory benefits provided by the alcohol (e.g., cooling sensation) start to drop off or plateau. Below the stated weight ranges, the benefits are not observed.

In the above stated weight ranges for each component, each range includes all subranges therebetween. For example, 10 to 40 weight percent includes that range and all subranges between 10 and 40 weight percent.

As previously discussed, the one or more rheology modifiers or thickeners can be used to achieve a desired viscosity in a composition. Common rheology modifiers come from both natural and synthetic sources. Examples of natural rheology modifiers are starch, cellulose, alginate, agar, carageenan, gelatin, guar gum, pectin and xanthan gum. Examples of synthetic rheology modifier are fumed silica, sodium

carboxymethylcellulose (CMC), acrylic-based anionic polymers, carbomer,

hydrophobically modified acrylic-based polymers, hydrophobic ally modified

hydroxyethylcellulose, hydroxyethylcellulose, and hydrophobic modified ethoxylated urethane resins (the rheology modifiers suitable in the present disclosure are those described above).

There are several common thickening mechanisms employed by rheology modifiers. These include: creating polymer entanglements when dispersed in water; creating hydrogen-bonding between thickeners and water; creating ionic repulsion by neutralizing anionic polymers with common bases such as sodium hydroxide (NaOH) or triethanolamine (TEA); creating hydrophobic association; and the combination of any of the above.

The addition of alcohol, particularly ethyl alcohol, to an emulsion can interfere with all thickening mechanisms mentioned above and, as a result, reduce emulsion viscosity. Without being bound by any theory, it is believed that the alcohol interferes with at least the hydrogen-bonding thickened mechanism discussed above. Table I below is an example of the impact of 30% ethyl alcohol on composition viscosity. The results show that the viscosity of the emulsion containing ethyl alcohol (Sample 2) is reduced by approximately 37% from the control (Sample 1), which contains no alcohol.

Table 1 - The Impact of 30% Ethyl Alcohol on Emulsion Viscosity wt.% wt.%

INCI NAME FUNCTION/DESCRIPTION Sample 1 Sample 2

Dl Water Solvent 75.43 45.43

Disodium EDTA Chelating Agent 0.05 0.05

Sodium

Acryloyldimethyltaurate/VP

Crosspolymer Thickener 0.85 0.85

Glycerin Humectant 3.00 3.00

Ethylhexyl Palmitate Solvent 5.00 5.00

Dimethicone Skin Conditioning Agent 1.00 1.00

Octocrylene Sunscreen Active 4.00 4.00

Oxybenzone Sunscreen Active 3.00 3.00

Avobenzone Sunscreen Active 2.50 2.50

Cetearyl Alcohol

Dicetyl Phosphate Emulsifier

Ceteth-10 Phosphate 2.50 2.50

Methylparaben,

Propylparaben,

Phenoxyethanol Preservative 1.10 1.10

Triethanolamine pH Adjuster 0.23 0.23

Acrylates/C12-22 Alkyl

Methacrylate Copolymer Film Former 1.00 1.00

Sodium Ascorbl phosphate

Antioxidant

and Tocopheryl Acetate 0.02 0.02

Aloe Barbadensis Leaf Juice,

Panthenol, and water Skin Conditioning Agent 0.02 0.02

Fragrance Fragrance 0.30 0.30

Ethanol Solvent 0.00 30.00

VISCOSITY in centipoise @ shear rate =1 79670 50400 The viscous alcohol-containing sunscreen composition of the present disclosure enables the formation of an elastic fluid gel-like structure, to entrap the volatile alcohol within its network, to quickly release volatile alcohol under stress, and to provide instant cooling during the application. This viscous alcohol-containing sunscreen composition is a shear-thinning emulsion, meaning that it thins as stress is applied, and is capable of providing good sensory properties. When applied on skin, it spreads easily and leaves skin with non-tacking feel.

The composition of the present disclosure can be measured by a rheometer (model: Anton Paar MCR301). Combining the sensory information and the rheology profile, the present disclosure has determined that the following parameters can be used to determine ideal ranges for viscosity or rheological characteristics of the composition: (1) a ratio of the loss (or viscous; G") modulus to the storage (or elastic; G') modulus lower than 0.19, preferably, lower than 0.18; (2) a flow point range from 20 Pa to 200 Pa, preferably, from 30 Pa to 100 Pa; and (3) at shear rate = 1 , a viscosity of 10,000 to 90,000 centipoise, preferably, 40,000 to 60,000 centipoise. These desirable properties can be achieved in the compositions of the present disclosure by balancing the rheology modifying agent, gelling agent, and emulsion stabilizer. When the term "high viscosity" is used in the present disclosure, it refers to a composition having one or more of the three characteristics described immediately above.

In Table II below, base formula A according to the present disclosure is shown. Table III shows base formula A with several different rheology modifiers. Rheology measurements in conjunction with sensory measurements are conducted to determine favorable thickeners for this invention discussed above. As shown in Table III, Sample 5 and Sample 6 are within the optimum range mentioned in the disclosure and have the advantages in rub-in and more cooling sensation, when compared to other Samples listed in Table III. Table II - Base Formula A

wt.%

Base

INCI NAME FUNCTION/DESCRIPTION Formula

Dl Water Solvent QS. To 100

Ethanol Solvent 30.00

Disodium EDTA Chelating Agent 0.05

Glycerin Humectant 1.0-5.0

Triethanolamine pH Adjuster 0.15-1.0

Ethylhexyl Palmitate Solvent 3.0-8.0

Dimethicone Skin Conditioning Agent 1.0-5.0

Octocrylene Sunscreen Active 4.0

Oxybenzone Sunscreen Active 3.0

Avobenzone Sunscreen Active 2.5

Cetearyl Alcohol

Dicetyl Phosphate Emulsifier

Ceteth-10 Phosphate 2.0-4.0

Acrylates/C12-22 Alkyl

Methacrylate Copolymer Film Former 0.5-2.0

Fragrance Fragrance 0.3

U 2013/035100

The compositions of the present disclosure may also comprise one or more additional ingredients selected from sunscreen active, skin conditioner, cooling enhancer, fragrance, and emollient. Including these ingredients in the present composition can change its rheology profile, and the amounts of thickener should be adjusted accordingly. The additional ingredients can be present in an amount of up to 30 percent, based on the total weight of the composition, or any subranges thereof. The sunscreen active may be at least one UVA and/or UVB sunscreen comprising one or more hydrophilic organic screening agent, and/or one or more lipophilic organic screening agent, and/or one or more inorganic physical blocker. The physical blocking sunscreen active reflects or scatters ultraviolet radiation. Typical examples of physical blockers include titanium dioxide and zinc oxide. Sunscreen actives according to the present disclosure can also be chemical absorbers that absorb harmful ultraviolet radiation. Chemical absorbers are classified, depending on the type of radiation they protect against, as either UVA or UVB

absorbers. UVA absorber generally absorbs radiation in the 320 to 400 nm region of the ultraviolet spectrum, and UVB absorber generally absorbs radiation in the 280 to 320 nm region of the ultraviolet spectrum. Examples of sunscreen actives in the UV A and/or UVB range include anthranilate, benzophenone, dibenzoyl methane (avobenzone), p- aminobenzoic acid derivative, camphor derivative, cinnamate, salicylate, arnyldimethyl PABA, digalloyl trioleate, dioxybenzone, ethyl 4-bis(hydroxypropyl)aminobenzoate, 2- ethylhexyl-2-cyano-3,3-diphenylacrylate, glyceryl aminobenzoate, 3-imidazol-4-ylacrylic acid and ethyl ester, methyl anthranilate, octyldimethyl PABA, 2-phenylbenzimidazole-5- sulfonic acid and salt, sulisobenzone, N,N,N-trimethyl-4-(2-oxobom- 3-ylidene

methyl)anillinium methyl sulfate, and any combinations thereof. The sunscreen agent is present in an amount of 5 to 30 percent, based on the total weight of the composition, or any subranges therebetween. The sunscreen agent can also be present in an amount of 11.5 to 19 percent, based on the total weight of the composition, or any subranges therebetween The composition of the present disclosure may further comprise one or more skin conditioners selected from the group consisting of glycols (e.g., caprylyl glycol), silicones (e.g., dimethicone), aloe, vitamin C, derivatives of vitamin C, vitamin B, derivatives of vitamin B (e.g., panthenol) or a combination thereof. The skin

conditioners may be present in an amount of from 1 to 8 percent, based on the total weight of the composition, or any subranges therebetween.

The composition of the present disclosure may further comprise one or more cooling enhancers consisting of menthol, menthol derivatives, menthyl lactate, menthyl PCA (pyrrolidone carboxylic acid), isopulegol, 3-(menthoxy)propane-1 ,2-diol, p- menthane-3,8-diol, vanillyl butyl ether, and ethyl methane carboxamide. The cooling enhancer is present in an amount of 0.01 to 1 percent, based on the total weight of the composition, or any subranges therebetween.

Table IV shows another base formula of the present disclosure, namely base formula B. Base formula B differs from base formula A in that the former includes some of the other ingredients discussed above, such as sunscreen active, conditioner, cooling enhancer, and fragrance. Table V shows how a stable viscous composition can be achieved by combining the thickener (the Aristoflex® previously identified in Table IV) with a gelling agent and emulsion stabilizer. The gelling agent used in Table V is a Gellan Gum (Kelcogel™ CG-HA) that is a polysaccharide produced by fermentation of a pure culture of Sphingomonas elodea. The emulsion stabilizer used in Table V is a Citrus Aurantium Sinensis (Orange) Fiber (lmulsi-Fi™ A30) that is an all-natural emulsion stabilizer made from orange pulp. Its distinctive cellular structure and unique protein and polysaccharide composition give this biopolymer an amphiphilic character (both hydrophilic and lipophilic properties), enabling it to lower the interfacial tension and stabilizing the oil/water interface very efficiently at ambient temperature.

It is shown in Table V that the rheology profiles of all these formulas are within the optimum range previously mentioned. It was also confirmed by an internal sensory panel, that Sample 8 and Sample 9 are spreadable, have fast rub-in, are not

significantly whitening, and have cooling sensation.

Table IV - Base Formula B

wt.%

Base

INCI NAME FUNCTION/DESCRIPTION Formula

Dl Water Solvent QS. To 100

Ethanol Solvent 30.00

Disodium EDTA Chelating Agent 0.05

Glycerin Humectant 1.0-5.0

Triethanolamine pH Adjuster 0.15-1.0

Ethylhexyl Palmitate Solvent 3.0-8.0

Octocrylene Sunscreen Active 4.0-6.0

Homosalate Sunscreen Active 5.0-10.0

Avobenzone Sunscreen Active 2.5-3.0

Cetearyl Alcohol

Dicetyl Phosphate Emulsifier

Ceteth-10 Phosphate 2.0-4.0

Acrylates/C12-22 Alkyl

Methacrylate Copolymer Film Former 0.5-2.0

Silica Opacifying Agent 0.1-2.0

Cooling enhancer 0.01-1.0

Skin Conditioning Agent 1.0-8.0

Fragrance Fragrance 0.35

Table V - Example of Obtaining Viscous Alcohol-Containing Composition Using Rheology Profile

Viscosity (cP)

@ shear rate = Flow point Sensory Result (HPT11-

Ref# Description 1 (Pa) G"/G' 172)

Base formula B + 1% More spreadable, less Aristoflex AVS + 0.1% whitening, faster rub-in,

Sample 8 55640 56 0.162

Gellen gum + 0.1% and more cooling feel after orange fiber immediately rub-in

Base formula B + 1% More spreadable, less Aristoflex AVS + 0.1% whitening, faster rub-in,

Sample 9 48920 73 0.158

Gellen gum + 0.15% and more cooling feel after orange fiber immediately rub-in

Has the same spread ability

Base formula B + 1% and rub-in but has less

Sample 10 Aristoflex AVS + 0.1% 51560 72 0.163 whitening and more

Gellen gum + 0.2% cooling feel after orange fiber immediately rub-in

Base formula B + 1% Has the same spread ability Aristoflex AVS + 0.1% and rub-in but has more

Sample 11 56920 91 0.155

Gellen gum + 0.25% cooling feel after orange fiber immediately rub-in

Table VI shows another series of sample compositions for SPF 50 compositions. The rheology profiles of three compositions or formulas (Sample 12, Sample 13, and Sample 15) are within the optimum range. In comparing to current commercial products, the compositions of the present disclosure exhibit similar spreadability but have faster rub-in, less whitening, and more cooling sensation after immediately rubbing in. The rheology profile of Sample 14 is not within the optimum range. This formula became unstable over time. The reason for this is that it is SPF 60, meaning that it has a higher amount of sunscreen actives than Sample 12 and Sample 3, which are SPF 50.

Sample 15 is also SPF 60, but it has slightly more gelling agent (0.15% as opposed to 0.1%). The additional amount of gelling agent accounts for the favorable viscosity characteristics in Sample 15. Table VI - Example of Obtaining Viscous Alcohol-Containing Composition Using Rheology Profile

Viscosity (cP)

@ shear rate = Flow point

Ref# Description 1 (Pa) G"/G' Sensory Characteristics

Base formula B + 1% Has the same spread ability Aristoflex AVS + but less whitening, faster rub-

Sample 12 55660 91 0.162

0.15% Gellen gum + in and more cooling feel after 0.3% orange fiber immediately rub-in

Base formula B + 1% Similar spread ability but less Aristoflex AVS + 0.1% whitening, faster rub-in, and

Sample 13 53790 73 0.162

Gellen gum + 0.3% more cooling feel after orange fiber immediately rub-in

more spreadable, less

Base formula B + 1% whitening, faster rub-in, and

Sample 14 Aristoflex AVS + 0.1% 27120 115 0.215 more cooling feel after

Gellen gum + 0.3% immediately rub-in but not orange fiber stable

Base formula B + 1% Less spreadable but faster Aristoflex AVS + rub-in, less whitening, has

Sample 15 41870 104 0.176

0.15% Gellen gum + more cooling feel after 0.3% orange fiber immediately rub-in

While the present disclosure has been described with reference to one or more particular embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope thereof. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the scope thereof. Therefore, it is intended that the disclosure not be limited to the particular embodiment(s) disclosed as the best mode contemplated for carrying out this disclosure.