Polyester film-forming polymers for alcohol-based sunscreen formulations

Abstract

Disclosed is a sunscreen formulation comprising: (a) a volatile solvent; and (b) at least one film-forming polymer, the film-forming polymer being the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having from 4 to 30 carbon atoms; and (iii) at least one fatty acid having from 8 to 30 carbon atoms. The sunscreen formulation is used in a method for protecting the skin from damage of the sun.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 401,220, filed on August 26, 2022, the entire contents of which are expressly incorporated herein by reference. Technical Field

[0003] The present disclosure relates to film-forming polymers for use in sunscreen formulations and to methods of using the sunscreen formulations. Background Art

[0004] Polymers used in sunscreen applications have traditionally been made using synthetic materials. In order for polymers to be suitable for such sunscreen applications, they must be soluble in alcohol-based systems and, for aerosol-based sunscreen sprays, they must also be compatible with the propellant. Traditional synthetic polymers are generally inexpensive and have acceptable performance. However, because they are not made from renewable resources and are not biodegradable, traditional synthetic polymers are not sustainable. In addition, it is not easy to replicate the cost and performance of synthetic polymers.

[0005] Therefore, there is a need for biodegradable polymers made from renewable resources that provide the same or better performance at a cost comparable to their synthetic alternatives and that are soluble in alcohol-based systems such as ethanol-based systems and optionally compatible with propellants such as dimethyl ether.

[0006] Sunscreen formulations based on biodegradable polyesters are the subject of the following recent patent publications: US 2021 / 0259930; US 2021 / 0259945; and US 2021 / 0259946.

[0007] In particular, US2021 / 0259946 describes the preparation of polyesters for waterproof anhydrous sunscreen formulations, for example, by a process comprising a substantially non-sequential reaction of the following components: (i) at least one polyglycerol; (ii) at least one dimer acid; and (iii) at least one fatty acid having 8 to 30 carbon atoms, wherein the molar ratio of (iii) to (i) is less than 2:1. Preferably, C36 dimer acid is used. Some polyesters prepared in this manner are incompatible with ethanol spray formulations or do not provide the desired SPF performance when delivered from an ethanol system.

[0008] Overall, the compatibility of bio-based film-forming polymers with alcohol-based (especially ethanol-based) sunscreen formulations remains a significant issue for formulators, and there remains a pressing need for bio-based film-forming polymers that are readily biodegradable but at the same time soluble and compatible in alcohol-based systems. Summary of the invention

[0009] The present disclosure provides a sunscreen formulation comprising:

[0010] (a) volatile solvents; and

[0011] (b) at least one film-forming polymer which is the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms.

[0012] The present disclosure also provides a method of protecting a user who is to be exposed or has been exposed to sunlight from the damaging effects of exposure to sunlight, wherein the method comprises the step of applying a sunscreen formulation to the skin. DETAILED DESCRIPTION

[0013] It should be understood that, except for the actual examples, all numerical values ​​provided herein are approximations with endpoints or particular values ​​that are intended to be understood as "about" or "approximately" the stated value.

[0014] An object of the present disclosure is to provide a film-forming polymer which is readily biodegradable, exhibits excellent compatibility with alcohol-based formulations, especially ethanol-based formulations, and can therefore be formulated into a stable sunscreen formulation having biodegradability.

[0015] In US2021 / 0259946, it is noted that C36 or higher dimer acids are preferably used to provide a greater hydrophobic content to achieve water resistance.

[0016] Surprisingly, it was discovered that the use of the diacids disclosed herein results in formulations having excellent ethanol solubility and a high degree of biodegradability.

[0017] Thus, in one embodiment, the present disclosure relates to a sunscreen formulation comprising:

[0018] (a) volatile solvents; and

[0019] (b) at least one film-forming polymer which is the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms; but wherein the at least one film-forming polymer is not formed from a dimer acid.

[0020] In another embodiment, the present disclosure relates to a sunscreen formulation comprising:

[0021] (a) volatile solvents; and

[0022] (b) at least one film-forming polymer which is the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; (iii) at least one fatty acid having 8 to 30 carbon atoms; and (iv) at least one dimer acid.

[0023] In typical embodiments, the diacid has from 4 to 24 carbon atoms. Suitable diacids include succinic acid (e.g., succinic acid), pentanedioic acid (e.g., glutaric acid), hexanedioic acid (e.g., adipic acid), heptanedioic acid (e.g., pimelic acid), octanedioic acid (e.g., suberic acid), nonanedioic acid (e.g., azelaic acid), decanedioic acid (e.g., sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (e.g., brassylic acid), hexadecanedioic acid (e.g., thapsic acid), heneicosanedioic acid (e.g., Japanese acid), docosanedioic acid (e.g., styric acid), and octanedioic acid (e.g., octanedioic acid). acid) (e.g., phellogenic acid), crocetin, butenedioic acid (e.g., maleic acid, fumaric acid), butynedioic acid (e.g., acetylenedicarboxylic acid), pentenedioic acid (e.g., glutaconic acid, glutinic acid, citraconic acid, mesaconic acid, itaconic acid), hexenedioic acid (e.g., muconic acid), decanedioic acid, dodecenedioic acid (e.g., traumatic acid), and mixtures thereof.

[0024] In another typical embodiment, the diacid corresponds to formula (I):

[0025] HOOC-X n —COOH(I)

[0026] in

[0027] X stands for -CH 2 -;and

[0028] n represents 2-28, typically 8-22, more typically 10-22; and

[0029] Where X n Optionally substituted with one or more -COOH groups, typically 1 or 2 -COOH groups.

[0030] In another typical embodiment, the diacid corresponds to formula (II):

[0031]

[0032] in

[0033] X and Y independently represent a hydrocarbon group having 1 to 3 carbon atoms, typically an alkyl group having 1 to 3 carbon atoms;

[0034] Z represents a hydrocarbon group having 1 to 20 carbon atoms; and

[0035] X, Y and Z are optionally substituted with additional carboxylic acid functionalities.

[0036] Suitable diacids within this embodiment include N-lauroyl glutamate, N-stearoyl glutamate, and the like.

[0037] In a more typical embodiment, the diacid has 10-24 carbon atoms.

[0038] In an even more typical embodiment, the diacid has 12 to 24 carbon atoms.

[0039] In a most typical embodiment, the diacid is selected from the group consisting of dodecanedioic acid, sebacic acid, N-stearoyl glutamic acid, and mixtures thereof.

[0040] In a typical embodiment, in addition to the diacid, a dimer acid is used to prepare the film-forming polymer. In this regard, it has been found that the addition of a dimer acid increases the hydrophobicity of the polymer molecule, thereby enhancing water resistance.

[0041] In a more typical embodiment, a C36 or higher dimer acid, particularly a C36 dimer acid, is used in addition to the diacid to prepare the film-forming polymer.

[0042] The term "dimer acid" used in the present disclosure refers to a dicarboxylic acid or a higher carboxylic acid prepared by dimerizing an unsaturated acid, in particular a dimer fatty acid prepared by dimerizing an unsaturated fatty acid. This of course includes formulations of dimerized unsaturated acids (including not only dimers but also trimers, tetramers, etc.).

[0043] The term "diacid" as used in this disclosure refers to a dicarboxylic acid or higher carboxylic acid that is not prepared by dimerization of an unsaturated acid.

[0044] In an even more typical embodiment, in addition to the diacid, up to 15% by weight of a C36 or higher dimer acid, typically 1-10% by weight, and in particular 5-6% by weight of a C36 dimer acid is used to prepare the film-forming polymer, the weight % in each case being based on the total weight of the components constituting the film-forming polymer.

[0045] In a particularly typical embodiment, the diacid is selected from dodecanedioic acid, sebacic acid, N-stearoylglutamic acid, and mixtures thereof with each other and / or with at least one C36 or higher dimer acid.

[0046] In another particularly typical embodiment, the diacid is selected from the group consisting of dodecanedioic acid, sebacic acid, N-stearoyl glutamic acid, and mixtures thereof, and does not contain any C36 or higher dimer acid.

[0047] In another embodiment, the diacid is hydrogenated.

[0048] In yet another embodiment, the diacid is selected from dodecanedioic acid, sebacic acid, N-stearoyl glutamic acid, and mixtures thereof with each other and / or with at least one C36 or higher dimer acid, wherein at least one of the diacids and / or the diacid is hydrogenated.

[0049] The polyglycerol may be any low condensation product of glycerol. In one embodiment, the polyglycerol has formula (III):

[0050] H[-O-Gly-]n-OH(III)

[0051] wherein each Gly is independently the residue after removing two hydroxyl groups from a glycerol molecule; and n (average value) is 2 to 10.

[0052] Typically, most Gly groups will have the formula: -CH 2 -CHOH-CH 2 -, although residues including etherification at secondary or even tertiary hydroxyl groups are considered to be within the scope of "Gly" and may therefore also be present. Examples of oligoglycerols include diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol, decaglycerol and mixtures of these. Particularly useful polyglycerols are those of formula (III) wherein n is particularly 2 to 7, more particularly 2 to 5 and especially 2, 3 or 4, or mixtures of oligoglycerols within these ranges.

[0053] Particularly suitable polyglycerols include mixtures of oligoglycerols having the following oligomer distribution:

[0054] Glycerol: 0 to 30% by weight, typically 0 to 20% by weight, most typically 0 to 15% by weight;

[0055] Diglycerol: 10 to 40% by weight, typically 15 to 35% by weight, most typically 20 to 32% by weight;

[0056] Triglycerol: 10 to 65% by weight, typically 15 to 60% by weight, most typically 18 to 55% by weight;

[0057] Tetraglycerol: 2 to 25% by weight, typically 5 to 20% by weight, most typically 8 to 20% by weight;

[0058] Pentaglycerol: 0 to 15% by weight, typically 0 to 10% by weight, most typically 0 to 5% by weight;

[0059] Hexaglycerol: 0 to 15% by weight, typically 0 to 10% by weight, most typically 0 to 5% by weight;

[0060] Heptaglycerol: 0 to 10% by weight, typically 0 to 5% by weight, most typically 0 to 3% by weight;

[0061] Octaglycerol: 0 to 10% by weight, typically 0 to 5% by weight, most typically 0 to 3% by weight;

[0062] Nonaglycerol: 0 to 5% by weight, typically 0 to 3% by weight, most typically 0 to 2% by weight;

[0063] Decaglycerol: 0 to 5% by weight, typically 0 to 3% by weight, most typically 0 to 2% by weight;

[0064] All weight percentages are based on the total content of polyglycerol.

[0065] In one embodiment, the polyglycerol comprises the following oligomer distribution:

[0066] Glycerol: 0 to 30% by weight;

[0067] Diglycerol: 15 to 40% by weight;

[0068] Triglycerol: 10 to 55% by weight;

[0069] Tetraglycerol: 2 to 25% by weight;

[0070] Pentaglycerol and higher components: 0 to 15% by weight;

[0071] All weight percentages are based on the total content of polyglycerol.

[0072] In one embodiment, the polyglycerol is composed of at least 40 weight percent, or at least 45 weight percent, or at least 50 weight percent of a combination of diglycerol and triglycerol, based on the total weight of the polyglycerol.

[0073] In one embodiment, the polyglycerol is composed of at least 20% by weight or at least 25% by weight of diglycerol; at least 15% by weight or at least 18% by weight of triglycerol; at least 10% by weight or at least 12% by weight of tetraglycerol; wherein all weight percentages are based on the total content of the polyglycerol.

[0074] Particularly typical polyglycerols contain at least 25% by weight of diglycerol, at least 45% by weight of triglycerol and at least 10% by weight of tetraglycerol.

[0075] Any such polyglycerol composition may be analyzed to determine the median, mean or "average" of the polyglycerol values. The above examples of oligoglycerols having both narrow and broad distributions may be equivalently designated as polyglycerol-3, since this is the integer closest to the mean and / or median value.

[0076] The fatty acid reactant is normally a fatty monoacid and as an end-capping agent for polymerization, provides adjustable hydrophobic content, and contributes to polymer performance. Although all monoacids with 8-30 carbon atoms, especially monoacids with 12-30 carbon atoms can be used, it is preferred to use C18 or larger monoacids to provide larger hydrophobic content, thereby achieving waterproofing. These can include naturally occurring or refined fatty acids, such as hydrolyzed rapeseed oil, sunflower seed oil, etc. However, these include lower and higher MW chains.

[0077] Useful fatty monoacids can be linear, branched, saturated, unsaturated and aromatic materials whose acidity is provided by the carboxylic acid portion. Useful acids include caprylic acid (C8), nonanoic acid (C9), capric acid (C10), undecanoic acid (C11), lauric acid (C12), tridecanoic acid (C13), myristic acid (C14), pentadecanoic acid (C15), palmitic acid (C16), heptadecanoic acid (C17), stearic acid (C18), isostearic acid (C18), nonadecanoic acid (C19), arachidic acid (C20), behenic acid (C22) and lignoceric acid (C24). Lower molecular weight organic acids can also be used to replace fatty monoacids, including butyric acid (C4), valeric acid (C5), caproic acid (C6), heptanoic acid (C7). The raw materials can be derived from tall oil and rapeseed oil, but other natural sources can also be used, including linseed, soybean, pumpkin, walnut. For example, in a typical embodiment, the fatty acid utilized is rapeseed fatty acid.

[0078] Comparing stearic acid with isostearic acid, branching results in a lower melting point of isostearic acid and results in a lower viscosity at room temperature, whereas stearic acid is a solid material. This lower viscosity aids in material handling of the raw materials and also helps ensure liquid properties of esters made using this acid. Isostearic acid can be obtained as a reaction byproduct in the formation of the dimer acid described above.

[0079] Another way to obtain liquid products is to use unsaturated linear or branched fatty monoacids. These unsaturated acids can include palmitoleic acid (C16:1), vaccenic acid (C18:1), oleic acid (C18:1), elaidic acid (C18:1), linoleic acid (C18:2), translinolelaidic acid (C18:2), alpha-linolenic acid (C18:3), gamma-linolenic acid (C18:3), octadecatetraenoic acid (C18:4), palmitic acid (C20:1), cis-11-eicosenoic acid (C20:1), dihomo-gamma-linolenic acid (C20:3), mead acid (C20:3), arachidonic acid (C20:4), eicosapentaenoic acid (C20:5), erucic acid (C22:1), docosatetraenoic acid (C22:4), docosahexaenoic acid (C22:6), and nervonic acid (C24:1). As is well known to those skilled in the art, the notation "CX:Y" means that the length of the carbon chain is X carbon atoms; and there are Y double bonds in the chain.

[0080] All of these acids and their mixtures are hydrophobic when esterified with polyglycerol. Saturated fatty acids will also reduce manufacturing side reactions and extend the long-term storage time of the finished product, as oxidation of unsaturated bonds can lead to color and other byproducts.

[0081] In one embodiment, the fatty acid is stearic acid (a straight chain saturated C18 fatty acid) or oleic acid (a monounsaturated C18 fatty acid). However, the unsaturated sites may provide late oxidative instability, while straight chain C18 fatty acids may cause polymer crystallization.

[0082] In another embodiment, the fatty acid is selected from the group consisting of canola fatty acid, stearic acid, behenic acid, isostearic acid, lauric acid, and mixtures thereof.

[0083] In a particularly typical embodiment, the water-repellent polymer is a substantially or completely non-sequential reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms.

[0084] "Substantially non-sequential reaction product" refers to a product prepared by a substantially non-sequential reaction of reaction components (i)-(iii) (and (iv), if dimer acid is used). Substantially non-sequential reaction of reaction components (i)-(iii) (and (iv), if dimer acid is used) means that substantially the total content of each of the reactants (i)-(iii) (and (iv), if dimer acid is used) to be reacted is added to the reaction vessel before the reaction is started. This process is different from the method described in, for example, U.S. Patent No. 6,242,499, in which polyglycerol is esterified with fatty acids in a first step, and after most or all of the fatty acids have reacted, a multifunctional carboxylic acid is added in a second step and the esterification reaction is continued. In one embodiment of the present disclosure, the total content of each reactant (i)-(iii) (and (iv), if dimer acid is used) to be reacted is added to the reaction vessel before the reaction is started, that is, the reaction is completely non-sequential and the polymer is a completely non-sequential reaction product of components (i)-(iii) (and (iv), if dimer acid is used). In other embodiments, at least 60-100%, or 75-100%, or 80-100%, or 85-100%, or 90-100%, or 95-100%, or 97-100% of each of reactants (i)-(iii) (and (iv) if a dimer acid is used) is added to the reaction vessel prior to starting the reaction.

[0085] In another particularly typical embodiment, the water-repellent polymer is a substantially or completely non-sequential reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; (iii) at least one fatty acid having 8 to 30 carbon atoms; and (iv) at least one dimer acid, particularly a dimer acid having at least 36 carbon atoms.

[0086] In another particularly typical embodiment, the water-repellent polymer is the substantially or completely non-sequential reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms; but does not include (iv) any dimer acid.

[0087] It has been found that the water resistance of the polymer is best when the polyglycerol contains an excess of OH groups relative to acid groups, the acid groups being added by a combination of diacid and fatty acid materials. As mentioned above, a wide variety of polyglycerols have been used in blended form and these polyglycerols impart unique properties to the material.

[0088] In one embodiment, the molar ratio of the reaction components is 1 mole of polyglycerol, 0.5 to 1 mole of dimer acid, and 0.2 to 1.7 moles of fatty acid.

[0089] In another embodiment, the molar ratio of the reaction components is 1 mole of polyglycerol, 0.5 to 0.75 moles of dimer acid, and 0.4 to 1.35 moles of fatty acid.

[0090] In another embodiment, the molar ratio of the reaction components is 1 mole of polyglycerol, 0.5 to 0.7 moles of dimer acid, and 0.65 to 1 mole of fatty acid.

[0091] In one embodiment, the components are reacted in a molar ratio of 1 mole of C36 or higher dimer acid to 1-20 moles of C30 or lower diacid.

[0092] In another embodiment, the components are reacted in a molar ratio of 1 mole of C36 or higher dimer acid to 1-15 moles of C30 or lower diacid.

[0093] In another embodiment, the components are reacted in a molar ratio of 1 mole of C36 or higher dimer acid to 2-10 moles of C30 or lower diacid.

[0094] By adjusting the fatty acid end-capping molar ratio and balancing the amounts of polyglycerol, dimer acid and lower diacid, the extent of dimer acid-polyglycerol chain extension and end-capping can be controlled, leading to much higher viscosities, for example, through trimer acid cross-linking.

[0095] The disclosed sunscreen formulations additionally contain a volatile solvent. Examples of volatile solvents include one or more alcohols such as methanol, ethanol, and isopropanol; volatile hydrocarbons such as isooctane, isododecane, and isohexadecane; volatile aldehydes; volatile silicones; and volatile ketones such as acetone and methyl ethyl ketone. Hydrofluoroolefins may also be used as carrier solvents in the formulations.

[0096] In a typical embodiment, the volatile solvent is an alcohol-based solvent system, wherein the alcohol-based solvent system comprises at least one C 1-6 Straight or branched chain alcohols.

[0097] In another exemplary embodiment, the volatile solvent is a ketone.

[0098] In a particularly typical embodiment, the volatile solvent is selected from ethanol, methanol, isopropanol, acetone, and mixtures thereof.

[0099] In another particularly typical embodiment, the sunscreen formulation comprises ethanol.

[0100] In a more typical embodiment, the sunscreen formulation comprising ethanol is anhydrous. The terms "non-aqueous" and "anhydrous" are used interchangeably herein and refer to compositions comprising less than about 10% by weight of water, particularly less than about 5% by weight of water, or less than 1% by weight of water, or even 0% water.

[0101] In the most typical embodiments, the sunscreen formulation comprises ethanol, but does not contain any other alcohol or water.

[0102] In an alternative embodiment, when water is present, such small amounts of water may be desirable, for example as a processing aid or co-solvent. In certain exemplary embodiments, the water content of the composition will be no greater than about 9% in order to prevent the active ingredient from phase separation or precipitation out of solution. One of ordinary skill in the art will recognize that different active ingredients have different tolerances to water in solution and will adjust the water content accordingly.

[0103] In one embodiment, the polymer is completely soluble in ethanol or a predominantly ethanolic mixture containing 0-20% by weight (typically 0-10%) of water, co-solvents and / or UV sunscreen actives.

[0104] In some cases, the polymer may not dissolve in ethanol after 24 hours.

[0105] However, in a more typical embodiment, the polymer is dissolved in a formulation comprising one or more sunscreen actives, one or more emollients and ethanol immediately after the polymer is added to the formulation. As used throughout this disclosure, the phrase "immediately after" means one hour or less, typically half an hour or less, and most typically 15 minutes or less.

[0106] In another more typical embodiment, the polymer remains completely dissolved in the formulation 24 hours after the polymer is added to the formulation.

[0107] In a particularly typical embodiment:

[0108] (a) upon addition of the polymer to the formulation, the polymer completely dissolves in the formulation immediately; and

[0109] (b) The polymer completely dissolved in the formulation immediately 24 hours after it was added to the formulation.

[0110] In one embodiment, the sunscreen formulation further comprises a propellant.

[0111] In certain embodiments disclosed in the present invention, the disclosed formulation can be stored in a pressurized container by combining with a propellant, and the disclosure also extends to such pressurized containers including the disclosed formulation. The formulation stored in this way can be applied by opening the valve in the container, thereby generally releasing the propellant and the composition in the form of a spray or mist. The propellant used in the composition can be any suitable gas or gas combination that can be compressed or liquefied in a distribution spray can and expand or volatilize to a vapor or gas form under exposure to ambient temperature and pressure conditions so as to deliver the composition in the form of an aerosol. Suitable propellants include hydrocarbons with 1 to 5 carbon atoms, including but not limited to methane, ethane, propane, isopropane, butane, isobutane, butylene, pentane, isopentane, neopentane and pentene, hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrofluoroolefins (HFOs), nitrogen, ethers (including dimethyl ether) and any mixture thereof. Those of ordinary skill in the art recognize that in a closed container such as an aluminum can or a glass bottle, a propellant such as dimethyl ether condenses into a liquid state at ambient temperature. Therefore, the composition in the aerosol container is a liquid formulation, which may include dissolved propellant, undissolved liquid propellant and gaseous propellant. All of these are under pressure due to the vapor pressure of the propellant. In the practice of this aspect of the present disclosure, the propellant may be present in an amount of up to about 90% by weight, typically about 2% by weight to about 50% by weight, more typically about 5% by weight to about 40% by weight, more typically about 30% by weight, based on the total weight of the aerosol composition.

[0112] In another embodiment, the propellant is an ether derived from a hydrocarbon.

[0113] In another embodiment, the propellant is isobutane.

[0114] In typical embodiments, the polymer is fully compatible with isobutane.

[0115] In a particularly typical embodiment,

[0116] (a) upon addition of the polymer to a formulation comprising one or more sunscreen actives, one or more emollients and ethanol, the polymer completely dissolves in the formulation;

[0117] (b) the polymer is completely dissolved in the formulation 24 hours after the polymer is added to the formulation; and

[0118] (c) The polymer is completely compatible with isobutane.

[0119] In one embodiment, the personal care formulation disclosed herein is dispensed from a bag-on-valve device. Typically, the bag-on-valve device includes a spray can equipped with an aerosol valve and includes a welded bag. The product is placed in the bag, and the propellant is filled in the space between the bag and the can. When the spray button is pressed, the product can be dispensed by the propellant by simply squeezing the bag.

[0120] Typically, the compositions according to the present disclosure are prepared as non-aqueous, volatile solvent-based compositions. However, in some embodiments, the compositions comprise a single liquid phase, which may also comprise dispersed particles, such as a UV active agent in particulate form.

[0121] In one embodiment, film-forming polymers are added to sunscreen formulations to impart water resistance thereto.

[0122] In one embodiment, the water-resistant polymer is added to the sunscreen formulation in an amount of 0.1 to 10% by weight, based on the total weight of the formulation.

[0123] In another embodiment, the water-resistant polymer is added to the sunscreen formulation in an amount of 0.5 to 5% by weight, based on the total weight of the formulation.

[0124] In yet another embodiment, the water-resistant polymer is added to the sunscreen formulation in an amount of 1 to 3% by weight, based on the total weight of the formulation.

[0125] The disclosed sunscreen formulations additionally include at least one sunscreen active agent. For the purposes of this disclosure, a "sunscreen active agent" is a material used alone or in combination with other such materials that is considered acceptable for use as an active sunscreen ingredient based on its ability to absorb UV radiation. Such compounds are typically described as UV-A, UV-B, or UV-A / UV-B based on their ability to act as UV active agents and their performance in different spectral regions. The addition of active agents to formulations for human use generally requires approval from regulatory agencies. Active agents that have been or are currently approved for sunscreen use in the United States include organic and inorganic substances, including but not limited to p-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octylsalicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, triethanolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digalloy trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, lawsone containing dihydroxyacetone, and red petrolatum. Examples of other sunscreen active ingredients that have not been approved in the United States but are permitted for use in formulations sold outside the United States include ethylhexyl triazone, dioctyl butamido triazone, benzalmalonate polysiloxane, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexyl benzoate, bis diethylamino hydroxybenzoyl benzoate, bis benzoxazolylphenyl ethylhexyl iminotriazine, drometrizole trisiloxane, methylene bisbenzotriazolyl tetramethylbutylphenol, bis ethylhexyloxyphenol methoxyphenyl triazine, 4-methylbenzylidene camphor, and isopentyl 4-methoxycinnamate. However, as the list of currently approved sunscreens continues to expand, one of ordinary skill in the art will recognize that the present disclosure is not limited to sunscreen actives currently approved for use in humans, but is readily applicable to sunscreen actives that may be permitted for use in the future.

[0126] In various embodiments, sunscreen actives include, but are not limited to, benzophenones, such as benzophenone-3 (BP3) and benzophenone-4 (BP4); salicylates, such as homosalate (HMS) and 2-ethylhexyl salicylate (EHS); para-aminobenzoic acid and its derivatives, such as ethylhexyl dimethylpara-aminobenzoate (OD-PABA) and 4-para-aminobenzoic acid (PABA); benzimidazole derivatives, such as phenylbenzimidazole sulfonic acid (PMDSA) and disodium phenyldibenzimidazole tetrasulfonate (Bisdisulizole disodium); Disodium); triazines, such as ethylhexyl triazone (OT), diethylhexyl butamido triazone (DBT) and bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT); benzotriazoles, such as drometrizole trisiloxane (DRT) and methylene bisbenzotriazolyl tetramethylbutylphenol (MBP, Biscotrizole); dibenzoylmethane derivatives, such as 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM, Avobenzone ); cinnamate esters, for example, ethylhexyl methoxycinnamate (OMC) and isoamyl p-methoxycinnamate (IMC, amiloxate); and camphor derivatives, for example, terephthalylidene dicamphor sulfonic acid (PDSA), 3-benzylidene camphor (3BC), benzyl camphor sulfonic acid (BCSA), 4-methylbenzylidene camphor (4-MBC), polyacrylamidomethylbenzylidene camphor (PBC) and camphor benzalkonium chloride methylsulfate (CBM).

[0127] In one embodiment of the present disclosure, the sunscreen active comprises a photoprotective effective amount of particles of at least one inorganic pigment or nanopigment, non-limiting examples of which include titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, or mixtures thereof.

[0128] In a particularly typical embodiment, the at least one sunscreen active is selected from avobenzone, homosalate, octylsalicylate, octocrylene and oxybenzone.

[0129] Typically, sunscreen actives are present in sunscreen formulations in amounts known in the art to be effective in protecting users who are about to be exposed or have been exposed to the sun from the damaging effects of exposure to the sun. Typically, these contents range from 1 to 35% by weight, typically 3 to 25% by weight, based on the total weight of the sunscreen formulation.

[0130] In one embodiment, the sunscreen active is present in the sunscreen formulation together with an enhancer, typically a UV enhancer, such as ethylhexylmethoxypolyacrylonitrile, diethylhexyl 2,6-naphthalene dicarboxylate, phenethyl benzoate and butyloctyl salicylate.

[0131] Additionally, the solvent may include varying amounts of oils such as mineral oil or vegetable oils as co-solvents or "emollients" as described herein.

[0132] Emollients may include any suitable oil, solvent, ester, triglyceride, etc. suitable for end-use applications. For sunscreen products, typical emollients include triheptanoin, isopropyl palmitate, triheptanoin (and) C13-C16 isoparaffin, heptyl undecylenate, caprylic / capric triglyceride, diisooctyl succinate, C13-C16 isoparaffin (and) heptyl undecylenate, C12-C15 alkyl benzoate, caprylic / capric triglyceride, dibutyl adipate, butylene glycol dicaprylate / dicaprate and other suitable esters. When diluted with an emollient, the addition is completed by keeping the final product at a temperature of about 80°C-100°C under mixing. The combination is then further cooled to 50-70°C for storage.

[0133] In one embodiment, the polymer is diluted to a final polymer concentration of 10% to 99% by weight, wherein the diluent is an emollient composed of an ester or triglyceride suitable for skin and sunscreen applications.

[0134] In another embodiment, the polymer is diluted to a final polymer concentration of 30% to 90% by weight, wherein the diluent is an emollient suitable for skin and sunscreen applications consisting of an ester or triglyceride from the list given above.

[0135] In yet another embodiment, the polymer is diluted to a final polymer concentration of 50% to 80% by weight, wherein the diluent is an emollient composed of an ester or triglyceride suitable for skin and sunscreen applications.

[0136] In addition to the polyesters described herein, the sunscreen formulation may additionally include other film-forming polymers. By way of example only, such other film-forming polymers may be selected from starch ester-based polyglucose polymers, such as described in US11,135,148, the entire contents of which are hereby incorporated by reference in various non-limiting embodiments; polyesters, such as described in US2021 / 0259930, US2021 / 0259945 and US2021 / 0259946, the entire contents of which are hereby incorporated by reference in various non-limiting embodiments; and N-alkyl (meth) acrylamide copolymers, such as described in US20180098930, the entire contents of which are hereby incorporated by reference in various non-limiting embodiments. Additional examples of suitable other film-forming polymers include film-forming polymers containing at least 5% by weight of acid-containing monomers, based on the total weight of the film-forming polymer. In a typical embodiment, the film-forming polymer comprises at least 5% by weight of carboxylic acid-containing monomers. Non-limiting examples of these monomers are acrylic acid, crotonic acid, methacrylic acid, maleic acid, itaconic acid, and combinations and mixtures thereof. Synthetic or natural additional film-forming polymers may be used with the above acid-containing polymers. Non-limiting examples of these additional film-forming polymers are: and LV-71 polymer (octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer), HC polymer (acrylates / octylacrylamide copolymer), 0 / 55 and BALANCE Polymer (Acrylate Copolymer), 47 polymer (octylacrylamide / butylaminoethyl methacrylate copolymer), 28-2930 polymer (VA / crotonate / vinyl neodecanoate copolymer), 28-1310 polymer (VA / crotonate copolymer), Polymer (Sodium Polystyrene Sulfonate), DynamX Polymer (Polyurethane-14 (and) AMP-Acrylates Copolymer), XP polymer (acrylates / octylacrylamide copolymer), 2001 (Acrylates / Steareth-20 Itaconate Copolymer) and 3001 (Acrylates / Ceteth-20 Itaconate Copolymer); OMNIREZ-2000 (PVM / MA Half Ethyl Ester Copolymer) from ISP, P-904 (butylated PVP), V-216 (PVP / hexadecene copolymer), V-220 (PVP / eicosene copolymer), WP-660 (triathionyl PVP), A425 (butyl ester of PVM / MA copolymer), AN-119PVM / MA copolymer, ES225 (ethyl ester of PVM / MA copolymer), ES425 (butyl ester of PVM / MA copolymer), VC-713 (vinyl caprolactam / PVP / dimethylaminoethyl methacrylate copolymer), 755 (Polyquaternium-11), HS-100 (Polyquaternium-28), AQUAFLEX XL-306 (Polyimide-1), SF-40 (PVP / vinyl caprolactam / DMAPA acrylate copolymer), FX-64 (isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer), ALLIANZ LT-120 (acrylates / C1-2 succinate / hydroxyacrylate copolymer), CC-10 (PVP / DMAPA acrylate copolymer), 2000(VP / acrylates / lauryl methacrylate copolymer), W-20 (polyquaternium-55), copolymer series (PVP / dimethylaminoethyl methacrylate copolymer), ADVANTAGE S and ADVANTAGE LCA (vinyl caprolactam NP / dimethylaminoethyl methacrylate copolymer), ADVANTAGE PLUS (VA / butyl maleate / isobornyl acrylate copolymer), Antaron ECo (ethyl cellulose); ULTRAHOLD STRONG (acrylic acid / ethyl acrylate / tert-butyl acrylamide) from BASF, 100P (tert-butyl acrylate / ethyl acrylate / methacrylic acid), LUVIMER 36D (ethyl acrylate / tert-butyl acrylate / methacrylic acid), HM-552 (Polyquaternium-16), HOLD (Polyquaternium-16), K30 (PVP), LUVISKOL K90 (PVP), LUVISKOL VA 64 (PVP / VA copolymer), LUVISKOL VA73W (PVPNA copolymer), LUVISKOL VA, PUR (Polyurethane-1), Clear (VP / methacrylamide vinyl imidazole copolymer), SOFT (Acrylates Copolymer), ULTRA HOLD 8 Acrylates / Acrylamide Copolymer), Plus(polyvinyl caprolactam), Silk (PEG / PPG-25 / 25 Dimethicone / Acrylates Copolymer); from Amerchol DR-25 (acrylic acid / methacrylic acid / acrylate / methacrylate); from Rohm & Haas 258 (acrylic acid / methacrylic acid / acrylate / methacrylate / hydroxyacrylate; from Mitsubishi and distributed by Clariant Z-301、DIA FORMER and DIAFORMER Z-400 (methacryloylethyl betaine / acrylates copolymer), ACUDYNE 180 (acrylates / hydroxy acrylates copolymer), ACUDYNE SCP (vinyl carboxamide / AMPSA / methacrylates copolymer) and Rheology modifiers; from ONDEO Nalco A-30 and FIXOMER N-28 (INCI name: Methacrylic Acid / Sodium Acrylamidomethylpropanesulfonate Copolymer); from Noveon G-100 (AMP-acrylate / allyl methacrylate copolymer), FIXATE PLUS (polyacrylate-X), Ultrez 10 (Carbomer), CARBOPOL Ultrez 20 (Acrylates / C10-30 Alkyl Acrylate Copolymer), AVALURE Series (acrylate copolymers), AVALURE series (polyurethane-2, polyurethane-4, PPG-17 / IPDI / DMPA copolymer); polyethylene glycol; water-soluble acrylic materials; water-soluble polyesters; polyacrylamide; polyamines; polyquaternary amines; styrene maleic anhydride (SMA) resins; polyvinyl amines; C2000 (Polyurethane ethanol solution (INCI-Polyurethane-64)), eco E 1000 (water-based polyurethane), C 1010 (water-based polyurethane), C 1008 (water-based polyurethane), C 1001 (water-based polyurethane); Inolex Lexfilm Sun (INCI-Polyester-7 (and) Neopentyl Glycol Diheptanoate), Inolex Lexfilm Sun Natural MB (INCI-Caprylyl Glycerin / Sebacic Acid Copolymer), Inolex WetFilm MB (INCI-Trimethylpentanediol / Adipic Acid / Glycerin Crosspolymer), Inolex Lexfilm Spray (INCI-Polyester-10 (and) Propylene Glycol Dibenzoate) and Inolex Lexorez 100 MB (INCI-Adipic Acid / Diethylene Glycol Crosspolymer) from Inolex; and other conventional polymers that are soluble in polar solvents or can be made soluble by neutralization with an appropriate base.

[0137] In another embodiment, the sunscreen formulation comprises, in addition to the polyesters described herein, at least one biodegradable polyester film-forming polymer.

[0138] In another embodiment, the sunscreen formulation comprises, in addition to the polyesters described herein, at least one biodegradable diisostearoyl polyglyceryl-3 dimer dilinoleate film-forming polymer.

[0139] In a particularly typical embodiment, the diisostearoyl polyglyceryl-3 dimer dilinoleate film-forming polymer includes diisostearoyl polyglyceryl-3 dimer dilinoleate and caprylic / capric triglyceride.

[0140] When the sunscreen formulation comprises other film-forming polymers in addition to the polyesters described herein, such other film-forming polymers may also be present in the sunscreen formulation in an amount of 0.1 to 10% by weight, based on the total weight of the formulation.

[0141] In a typical embodiment, such other film-forming polymers are added to the sunscreen formulation in an amount of 0.5 to 5% by weight, based on the total weight of the formulation.

[0142] In another typical embodiment, the total amount of all other such film-forming polymers and the polyesters described herein is from 0.1 to 10 weight percent, based on the total weight of the formulation.

[0143] In a particularly typical embodiment, the total amount of all other such film-forming polymers and the polyesters described herein is from 0.5 to 5 weight percent, based on the total weight of the formulation.

[0144] The disclosed sunscreen formulations may include a variety of additional, optional components, which are referred to herein as "cosmetic components", but may also include components commonly referred to as pharmaceutically active agents. The CTFA Cosmetic Ingredient Handbook, Seventh Edition, 1997 and Eighth Edition, 2000, which are incorporated herein by reference in their entirety, describes a variety of cosmetic and pharmaceutical ingredients commonly used in skin care compositions, which are suitable for use in the compositions of the present disclosure. Examples of these functional classes disclosed in the reference include absorbents, abrasives, anticaking agents, defoaming agents, antioxidants, binders, biological additives, buffers, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, pharmaceutical astringents, topical analgesics, film formers, fragrance ingredients, humectants, sunscreens, pH adjusters, plasticizers, reducing agents, skin bleaching agents, skin conditioners (emollients, moisturizers, miscellaneous and occlusives), skin protectants, solvents, foam boosters, hydrators, solubilizers, suspending agents (non-surfactants), SPF boosters, water repellents and viscosity enhancers (aqueous and non-aqueous).

[0145] The compositions of the present disclosure can be applied to the skin as liquid applicators, but are most commonly applied as sprays. However, the compositions are not limited to those compositions that are primarily applied to the skin as sunscreens. The compositions also incorporate sunscreen active agents as those formulations of ingredients for another topical application composition. Some non-limiting examples are lipsticks, cosmetics, lip balms, eye shadows, hair dyes, and conditioners, or any application that may be considered beneficial for sun protection.

[0146] In one embodiment, where the disclosed formulations are to be used in applications where sun protection may be considered beneficial, the disclosed formulations provide a static sun protection factor ("static SPF"). Without limitation, the SPF may be greater than or less than 10, or greater than 20, or greater than 25, or greater than 30, or greater than 35, or greater than 40, or greater than 45, or greater than 50, or greater than 55, or greater than 60, or greater than 65, or greater than 70, or greater than 75, or greater than 80, or greater than 85, or even higher.

[0147] In another embodiment, the disclosed formulation provides a static SPF greater than 60.

[0148] In one embodiment, where the disclosed formulations are to be used in applications where sun protection may be considered beneficial, the disclosed formulations provide a water protection factor ("WR SPF"). Again, without limitation, the SPF may be greater than or less than 10, or greater than 20, or greater than 25, or greater than 30, or greater than 35, or greater than 40, or greater than 45, or greater than 50, or greater than 55, or greater than 60, or greater than 65, or greater than 70, or greater than 75, or even higher.

[0149] In another embodiment, the disclosed formulation provides a WR SPF greater than 60.

[0150] The present disclosure will now be described in more detail with reference to the following non-limiting embodiments.

[0151] Example

[0152] Example 1

[0153] A downward distillation apparatus, a magnetic stirrer, a thermometer and a N 2 The following raw materials were added to a 100 ml three-necked flask with an inlet / atmosphere: 28.8 g polyglycerol-3 (Inovyn / CAS#25618-55-7); 15.64 g dodecanedioic acid (Alfa Aesar / CAS#693-23-2); 6.77 g Radiacid 0960 (hydrogenated dimer acid from Oleon / CAS#68783-41-5); 24.56 g Radiacid 0161 (rapeseed fatty acid from Oleon / CAS#68002-88-0); and 0.48 g NaOH (50% active ingredient). The oil bath temperature was adjusted to 180-200° C. After the solid components of the reaction melted, the stirring rate was set to the highest possible to reduce potential foaming and N 2 Entry is set to start N 2 Bubbling. The oil bath temperature and the speed (rpm) of the magnetic stirrer were gradually increased and the acid value was monitored until the acid value was stable and as low as possible. When the acid value was stable at about 1.44 mgKOH / g, the reaction was stopped and the reaction mixture was poured into a silica gel dish. 71.69 g of product polyester was obtained as a non-sticky, opaque, turbid solid.

[0154] In a similar manner, suitable polyesters may be prepared by reacting the following starting materials in the molar ratios shown:

[0155] Table 1

[0156] Polymer → 2 3 4 5 6 7 8 9 10 11 Ingredients↓ Polyglycerol 3 3 3 3 3 3 3 3 3 3 Dodecanedioic acid 1.5 1.5 1.5 1.8 1.8 Sebacic acid 1.5 1.5 1.7 1.5 2 Hydrogenated dimer acid 0.5 0.5 0.5 0.5 0.5 0.3 0.2 0.2 N-stearoyl glutamate 0.5 Rapeseed fatty acid 2 2 2 2 Stearic acid 2 Behenic acid 90% 1 2 1 1 Behenic acid 47% 2 Isostearic acid 1 Lauric acid 1 1

[0157] Example 2

[0158] Preparation of anhydrous formulations to illustrate spray products: In addition to the following Table 2, an anhydrous concentrate was prepared in a 400 mL beaker, where 63 g of anhydrous ethanol SDA-40B was charged to the beaker and 2 g of polyester derivative or comparative polymer was added under stirring and mixed for about 30 minutes until fully dispersed. Stirring was continued and 3 g of avobenzone (Neo 357, Symrise), 13g homosalate (Neo HMS, Symrise), 5g ethylhexyl salicylate (Neo OS, Symrise), 9g Octocrylene (Neo An oil phase consisting of 5 g of Benzyl 303, Symrise) and 5 g of C12-15 alkyl benzoate (Finsolv TN, Innospec) was added to the beaker and mixed for about 30 minutes, and then the results were observed.

[0159] Table 2

[0160]

[0161] Solubility results

[0162] The desired result is a clear, single-phase and complete solution, which indicates that the formulation is completely dissolved. On the other hand, if the solution is turbid or contains precipitates, it indicates that the formulation is at least partially insoluble. The evaluation is performed immediately after mixing ("initial solubility") and after 24 hours ("24 hour solubility").

[0163] Table 3

[0164]

[0165] 1 Acrylic acid type copolymer from Nouryon

[0166] 2 Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (and) Caprylic / Capric Triglyceride from Nouryon

[0167] The results demonstrate that polymers prepared in a variety of different ways according to the present disclosure can be formulated to form stable solutions in anhydrous ethanol.

[0168] In general, the solubility of any formulation including any disclosed film-forming polymer using any particular solvent or solvent system can be determined in a straightforward manner analogous to this example.

[0169] Example 3

[0170] Selected polymer samples (using the numbers in the table above) were prepared in ethanol solvent along with an oil phase and blended with the propellant according to the following procedure to understand the compatibility with the propellant.

[0171] Preparation procedure:

[0172] 1. Charge all of the ethanol in the formulation into the main mixing vessel.

[0173] 2. Start mixing with propeller stirring (adjust mixing speed until a vortex is formed 2 / 3 of the way along the mixing shaft).

[0174] 3. Slowly add the polymer by sifting the polymer powder into the side of the vortex. Allow the polymer to disperse thoroughly.

[0175] 4. Slowly add the oil phase to the vortex and continue mixing until clear and homogeneous.

[0176] 5. Fill the concentrate into an aerosol container and add the propellant.

[0177] 6. Observe the charged aerosol for clarity, phase behavior, and any precipitate that may form initially and over time.

[0178] In the following examples, the propellant is isobutane, 30% of the total formulation. In each sample formulation recorded herein, unless otherwise stated, the formulation tested includes 1.4 wt % polymer, 44.1 wt % q.s. ethanol, 24.5 wt % UV oil phase and 30 wt % propellant.

[0179] The desired result is a clear, single-phase and complete solution, which indicates that the formulations are compatible. On the other hand, if the solution is cloudy or opaque or contains precipitates, it indicates that the formulations are at least partially incompatible.

[0180] Table 4

[0181]

[0182] The results show that the disclosed film-forming polymers are compatible with isobutane propellant.

[0183] In general, the compatibility of any disclosed film-forming polymer with a particular propellant or solvent-propellant system can be determined in a straightforward manner analogous to this example.

[0184] Example 4

[0185] In order to demonstrate the effectiveness of the sunscreen formulation examples made with the polyesters of the present disclosure, or to demonstrate the lack of effectiveness of formulations made with comparative products, for each formulation prepared, a series of tests were conducted to quantitatively determine the so-called Sun Protection Factor (SPF) and to demonstrate their effectiveness in producing provably water resistant sunscreen formulations.

[0186] Because of the importance of SPF testing for labeling consumer sunscreen products, government agencies regulate the labeling of these products and require that products be tested by human panelists using specific statistical criteria. (Static) SPF measures the time it takes for erythema to appear on an area of ​​the skin protected by sunscreen compared to the time it takes for erythema to appear on an area of ​​the skin not protected by sunscreen on the same human panelist's skin.

[0187] Water-Resistant (WR) SPF measurements are also made after a standard immersion of the skin in 40°C water.

[0188] For laboratory measurements of SPF and WR SPF, a range of in vitro measurements can be performed. Europe uses the Colipa test method. The United States uses FDA 21CFR Section 201 and 320 tests. These measurements involve the use of plastic films or substrates to simulate the roughness and other properties of human skin. In this case, SPF measurements can be made on the substrate using a variety of instruments. The Labsphere UV-1000 spectrophotometer was used. VitroSkin, a partially hydrophilic acrylic polymer material, was used according to the manufacturer's instructions. TM (from Florida Suncare, Inc., formerly IMS Inc).

[0189] Apply 20 drops (5 mg per drop) of sunscreen concentrate to the film, carefully and evenly distributing the concentrate over 55.8 cm 2 The membrane area (i.e. 2 mg / cm 2 The absorbance (or transmittance) of UVA radiation (320-400 nm) and UVB radiation (290-320 nm) is measured using an ultraviolet spectrophotometer. Based on these values, the in vitro SPF of the artificial skin with and without sunscreen products can be measured.

[0190] Results are reported as in vitro SPF and in vitro WR SPF, where the former is also measured after a standard drying time and the latter is measured after immersing the same film in water at 40°C for 80 minutes. These in vitro measurements have been shown to correlate with in vivo data. Other data (such as the ratio of UVA to UVB) can also be determined and used to quantify the protection provided by the sunscreen formulation. Alternatively, for the Colipa Tech method, Helioplate HD6 embossed PMMA plates were provided by Helio Labs Inc. These PPMA plates have a root mean square surface roughness of 6 microns and can be used without hydration. Due to the depth of the roughness, once the same 2 mg / cm 2 Dosed sunscreen lotion applied to the plate and dried will have "peaks" of surface roughness that are covered by relatively little UV-absorbing oil. Therefore, absorbance and calculated SPF may be slightly reduced relative to in vivo and other in vitro measurement techniques. However, both in vitro substrates produce reproducible results and can be compared using appropriate correction factors.

[0191] Therefore, as is standard in the art, the UV absorption of a plastic film coated with a UV absorbing sunscreen formulation is used to simulate human skin and measured with a spectrophotometer to provide a measurement of the Sun Protection Factor (SPF). The SPF is simply the ratio of the initial light to the light transmitted through the UV absorbing film. If 100% is reduced to 10%, the SPF is 10. If 100% is reduced to 1%, the SPF is 100. SPF 50 corresponds to 2% of the UV light passing through the skin.

[0192] In each case, 20 drops (5 mg per drop) of a solution containing the test polymer were applied to a surface area of ​​55.8 cm 2 The UV absorbing film is applied to the substrate and subjected to UV light in the range of 280 to 400 nm to provide a so-called "static" SPF measurement result.

[0193] In vitro water repellent SPF (WR SPF) results were obtained by placing the same film in a water bath, heated to 40°C and gently agitated. The sample was removed, gently dried under reproducible conditions and then the light transmittance was measured again, this time providing the WR SPF data.

[0194] Table 5

[0195]

[0196] Example 5

[0197] Paired comparisons - Eight panelists blindly evaluated two different leave-on products by applying the products to the volar forearm. When applied to the volar forearm, panelists had to select one product that performed better than the other for each performance attribute. Performance data were pooled and statistically analyzed.

[0198] Skin preparation:

[0199] The panelist will use the provided ethanol wipes to clean the entire volar forearm area as well as their evaluation finger. After the ethanol has completely evaporated, a circle approximately 1.50 inches in diameter will be drawn on the forearm as the evaluation site and labeled alphabetically (A or B). Care was taken to avoid the wrist and arm flexion area, and to leave enough space between samples to ensure that the samples did not touch each other during application.

[0200] Application evaluation by panelists:

[0201] 1. Provide evaluation ballots to group members to record their answers.

[0202] 2. While ensuring that the panelists are unaware of the identity of the samples, use an electronic pipette to apply approximately 0.4 μL of each sample (A and B) to the center of the assessment site.

[0203] 3. The panelist spreads a measured amount of product in a circle using the index or middle finger in gentle circular motions (applying approximately 2 times per second).

[0204] 4. The following are the panelists' responses to the experimental sunscreen solutions and control sunscreen solutions in the sunscreen formulations listed above: 79; Acrylates / Octyl Acrylamide Copolymer, Nouryon) Comparative Evaluation:

[0205] Spreadability:

[0206] How easily the product moves across the skin (difficult / resistance to easy / slippery).

[0207] After 10 wipes, evaluate and select which product has the highest strength in the following indicators:

[0208] Tack: How well the residual product adheres to the fingers (not tacky to very tacky).

[0209] The forearm test site was visually analyzed to assess the following:

[0210] Gloss: The amount or degree of light reflected by the skin (none to a lot);

[0211] Immediate aftertouch: Gently stroke skin with clean fingers (1-2 times) and assess the following:

[0212] Slipperiness: How easy it is to move a finger across the skin (difficult / resistance to easy / slippery);

[0213] Residue: The amount of product left on the skin (none to high amounts).

[0214] Oily: slippery, smooth, continuous feel (i.e. baby oil)

[0215] Powder: A very dry, thin, slippery coating (i.e. corn starch)

[0216] After approximately 5 minutes, when the product has been absorbed into the skin, assess the tack again:

[0217] Tackiness 2: How well the residual product sticks to your fingers (not sticky to very sticky)

[0218] At the end of the attribute evaluation, panelists were asked which product they would choose as typical, expressed as an “overall preference.”

[0219] Data / Evaluation Analysis:

[0220] Poor quality samples: The experimental samples showed typical characteristics 0 to 1 times out of 8.

[0221] No statistical difference: experimental samples showed typical characteristics in 2 to 6 out of 8 times.

[0222] Good quality samples: The experimental samples showed typical characteristics 7 to 8 times out of 8.

[0223] Table 6

[0224]

[0225] Example 6

[0226] Several examples of the present disclosure were tested by OECD biodegradability method 301D, details of which are readily available. Testing was performed in river water and activated sludge. [OECD (1992), Test No. 301: Ready Biodegradability, OECD Guidelines for the Testing of Chemicals, Part 3, OECD Publishing, Paris, https: / / doi.org / 10.1787 / 9789264070349-en.].

[0227] Table 7

[0228]

[0229] Table 8

[0230]

[0231] The 301D ratings include “readily biodegradable,” which means 60 to 100 percent biodegradation in 28 days or less, “inherently biodegradable,” which means 20 to 60 percent biodegradation in 28 days, and “non-biodegradable,” which means less than 20 percent biodegradation in 28 days.

[0232] Although the present disclosure has been described in conjunction with the above specific embodiments, many substitutions, modifications and other variations thereof will be apparent to those skilled in the art. All such substitutions, modifications and variations are intended to fall within the spirit and scope of the present disclosure.

Claims

1. A sunscreen formulation comprising: (a) volatile solvents; and (b) at least one film-forming polymer which is the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms.

2. The sunscreen formulation according to claim 1, wherein the volatile solvent comprises at least one C 1-6 Straight or branched chain alcohols.

3. The sunscreen formulation according to claim 1 or 2, wherein the volatile solvent comprises ethanol.

4. The sunscreen formulation according to any one of the preceding claims, comprising from about 1 to about 3% by weight of water.

5. The sunscreen formulation according to any one of the preceding claims, which is free of water.

6. The sunscreen formulation according to claim 5, comprising ethanol but not any other alcohol.

7. The sunscreen formulation according to any one of the preceding claims, further comprising at least one sunscreen active agent selected from the group consisting of p-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, triethanolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digalloyl trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, safflower quinone containing dihydroxyacetone, red petrolatum, ethylhexyl triazone, dioctyl butyramidoyl Triazone, benzalmalonate polysiloxane, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexyl benzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazolyl phenyl ethylhexyl iminotriazine, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutylphenol, bis-ethylhexyloxyphenol methoxyphenyl triazine, 4-methylbenzylidene camphor, homosalate, butyl methoxydibenzoylmethane, octocrylene, octyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine and isopentyl 4-methoxycinnamate, benzophenone- 3 (BP3), Benzophenone-4 (BP4), Homosalate (HMS), 2-Ethylhexyl Salicylate (EHS), Ethylhexyl Dimethylparaben (OD-PABA), 4-paraaminobenzoic acid (PABA), Benzimidazole derivatives, Phenylbenzimidazole sulfonic acid (PMDSA), Disodium phenyl dibenzimidazole tetrasulfonate (Disodium bis-bis-sulizole), Ethylhexyl Triazone (OT), Diethylhexyl Butamido Triazone (DBT), Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (EMT), Drometrizole Trisiloxane (DRT), Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (MBP, Biscotrizole), 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM, Avobenzone), ethylhexyl methoxycinnamate (OMC), isoamyl p-methoxycinnamate (IMC, Amisate), terephthaloyl dicamphor sulfonic acid (PDSA), 3-benzylidene camphor (3BC), benzylidene camphor sulfonic acid (BCSA), 4-methylbenzylidene camphor (4-MBC), polyacrylamidomethylbenzylidene camphor (PBC), titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide and mixtures thereof.

8. The sunscreen formulation according to claim 7, wherein the at least one sunscreen active is selected from avobenzone, homosalate, octylsalicylate, octocrylene, oxybenzone and combinations thereof.

9. The sunscreen formulation according to any one of the preceding claims, further comprising an emollient.

10. The sunscreen formulation according to claim 9, wherein the emollient is selected from the group consisting of alkyl benzoates, capric triglyceride, and combinations thereof.

11. A sunscreen formulation according to any one of the preceding claims, wherein the at least one diacid is selected from dodecanedioic acid, sebacic acid, N-stearoyl glutamic acid and mixtures thereof; and the formulation optionally further comprises a C36 or higher dimer acid.

12. The sunscreen formulation according to claim 11, additionally comprising a C36 or higher dimer acid.

13. The sunscreen formulation according to claim 11, which is free of C36 or higher dimer acids.

14. The sunscreen formulation according to any one of claims 1 to 13, which is a sprayable sunscreen formulation.

15. The sunscreen formulation according to claim 14, further comprising one or more additives selected from the group consisting of plasticizers, UV absorbers, dyes, fragrances, preservatives, viscosity modifiers, vitamins, moisturizers, anti-itch ingredients, and combinations thereof.

16. The sunscreen formulation according to any one of the preceding claims, which is an aerosol formulation and further comprises a propellant.

17. The sunscreen formulation according to claim 16, wherein the propellant is a hydrocarbon.

18. The sunscreen formulation according to claim 17, wherein the hydrocarbon is isobutane.

19. A sunscreen formulation comprising: (a) an alcohol-based solvent system comprising ethanol; (b) at least one film-forming polymer, said film-forming polymer being the reaction product of: (i) at least one polyglycerol; (ii) at least one diacid having 4 to 30 carbon atoms; and (iii) at least one fatty acid having 8 to 30 carbon atoms; (c) at least one sunscreen active; (d) from about 0 to about 3 weight percent water; (e) optionally at least one emollient; (f) optionally at least one C36 or higher dimer acid; (g) optionally at least one propellant; and (h) optionally one or more additives selected from plasticizers, UV absorbers, dyes, fragrances, preservatives, viscosity improvers, vitamins, moisturizers, antipruritic ingredients, and combinations thereof.

20. A method comprising the step of applying to the skin an amount of a sunscreen formulation according to any one of the preceding claims.

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