Biodegradable polyesters for water-resistant water-in-oil sun care formulations

Abstract

To provide a polymer for imparting a high static and water-resistant SPF to a water-in-oil sunscreen formulation.SOLUTION: There is provided a water resistant polymer which is a reaction product 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, where (iii) and (i) are in a molar ratio of less than 2:1. The components are charged to a reaction vessel and subsequently reacted to produce a polyester polymer having excellent waterproofing properties.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates generally to new biodegradable polyesters, methods for their preparation, and their use in waterproof water-in-oil sun care formulations. [Background technology]

[0002] Sunscreen formulations have become important for consumer use, where significant sun exposure must be managed without experiencing severe erythema (sunburn) during prolonged sun exposure, with or without periods of exercise, and where that exercise may be accompanied by or without water immersion. Sunscreens are strictly controlled and measured using standard sun protection factor (SPF) tests. Each product introduced to the market must be labeled with the lesser of two SPF measurements. Static SPF measurements, designated "SPF," are measured immediately after applying a specific amount of sunscreen formulation to the skin, allowing it to dry for a period of time, typically 15 to 30 minutes, and then testing for SPF without further activity. Water-resistant SPF measurements, or "WR SPF," are measured on the same test subject after a specific period of water immersion. "Highly water-resistant" SPF is measured after 80 minutes of immersion in water held at 40°C and is the focal measurement hereafter referred to as "WR SPF." Sunscreen formulations contain so-called active materials that absorb or scatter specific wavelengths of UV light. However, these actives do not exhibit the film-forming or water-resistant properties necessary to provide applied sunscreen formulations with WR SPF values ​​of current interest, particularly in the range of WR SPF 30, 50, 70, 90, or 100. Instead, a class of materials, typically polymers, are used to provide the film-forming and water-resistant properties, and this is the purpose of this disclosure.

[0003] Sunscreen film-formers that provide water resistance have long been known. Synthetic polymers, including PVP / olefin copolymers and acrylate copolymers, have been developed that provide water resistance depending on their dosage (SPF and WR SPFs ranging from SPF 15 to SPF 50 or higher). These materials can have molecular weights ranging from about 50,000 Daltons to over 1,000,000 Daltons (Da). These synthetic polymers provide high SPF and WR SPFs of 50 or higher at polymer loadings of about 2 wt% in emulsions, but they are also non-biodegradable and therefore undesirable for the environment. Currently, all such "microplastics" that are released into water during activities such as swimming and snorkeling and do not degrade in the environment are under increased scrutiny.

[0004] More biodegradable hydrophilic and hydrophobic polyesters have been developed as additives to cosmetics, some of which have been recommended for sunscreens. However, these polyesters appear to be suitable only for low WR SPF formulations (i.e., those with a relatively low level of water resistance and a WR SPF rating of 15 or perhaps 30). When tested with the standard SPF 50 formulation used herein, these materials do not provide an appreciable WR SPF (an SPF of about 2 is measured for a 2 wt% polymer loading).

[0005] Thus, manufacturers of high SPF and WR SPF sports sunscreens are still under pressure from the market and from regulatory agencies to offer more natural products with zero microplastic content. Ganex™ polymers [e.g., Antaron™ V-220F polymer (INCI: VP / Acrylates / Lauryl Methacrylate Copolymer)] are currently very commonly used and can provide sunscreen formulations with high SPF values ​​of 50 or higher, while also providing WR SPF values ​​of 50 or higher, i.e., water and rub resistance, but these polymers are also not biodegradable.

[0006] Gruning et al., U.S. Patent No. 6,242,499, describes polyesters obtained by esterifying a polyglycerol mixture with saturated or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and polyfunctional carboxylic acids having 4 to 54 carbon atoms and an average functionality of 2 to 2.4, with the degree of esterification of the polyglycerol mixture being between 30 and 75%. The only preparation procedure described involves esterifying the polyglycerol with the fatty acids in a first step, and after most or all of the fatty acids have reacted, adding the polyfunctional carboxylic acid in a second step and continuing the esterification reaction. The resulting polyesters are described as useful as water-in-oil emulsifiers in the preparation of cosmetic or pharmaceutical preparations, including sun protection creams, but there is no teaching or suggestion that the polyesters are useful as sunscreen film-formers with respect to water resistance. Indeed, the resulting polyesters, although biodegradable, are characterized by low WR SPF values.

[0007] O'Lenick, U.S. Pat. No. 8,465,730, describes sunscreen formulations characterized by a synergistic effect between a sunscreen active and a waterproof polyester prepared by reacting a mixture of polyglycerol, a diacid, and a mixture of at least two different fatty acids. Data supporting the improvement are very limited. In one case, a polyester prepared by reacting polyglyceryl, stearic acid, isostearic acid, and hydrogenated C34 dimer acid (Example 35) provided a static SPF of 42. In another case, a polyester prepared by reacting polyglyceryl, oleic acid, stearic acid, and azelaic acid (Example 68) provided a static SPF of 39. While these values ​​were somewhat higher than those obtained using polymers prepared according to prior art patents, they focused only on static SPF and were not tested by the standard immersion protocol required for classification as water-resistant or highly water-resistant WR SPF by the FDA and other agencies. These polymers do not provide the value expected by those skilled in the art for water resistance in sun care formulations, such as that provided by the synthetic Ganex™ polymers. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 6,242,499 [Patent Document 2] U.S. Patent No. 8,465,730 [Patent Document 3] U.S. Provisional Application No. 62 / 979,566 [Patent Document 3] US Patent Application Publication No. 2011 / 0091397 [Non-patent literature]

[0009] [Non-Patent Document 1] "The Dimer Acids: The chemical and physical properties, reactions and applications", Ed. EC Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn. [Non-patent document 2] CTFA Cosmetic Ingredient Handbook, Seventh Edition, 1997 and the Eighth Edition, 2000 Summary of the Invention [Problem to be solved by the invention]

[0010] Thus, there is an unmet need in the art to provide bio-based, biodegradable polymers that have excellent sensory, waterproof, and water-resistant Sun Protection Factor (WR SPF) performance in addition to the requisite static SPF (SPF) performance, and that perform strongly in sports emulsion sunscreens that are natural, biodegradable, and resist dilution and removal of the UV absorbers by water after application. These and other objectives are met by the present disclosure. [Means for solving the problem]

[0011] U.S. Provisional Application No. 62 / 979,566, filed February 21, 2020 (hereinafter the "co-pending application"), describes a waterproofing polymer that is a reaction product 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 (iii) and (i) are in a molar ratio of less than 2:1. All details regarding the preparation of the waterproofing polymer, including all individual embodiments described in the co-pending application, as well as all limitations regarding the structure and properties of the waterproofing polymer itself, are incorporated herein by reference. The inventors have discovered that the waterproofing polymer described in the co-pending application as useful for imparting high static and water-resistant SPF to oil-in-water sunscreen formulations is also useful for imparting high static and water-resistant SPF to water-in-oil sunscreen formulations.

[0012] The present disclosure generally relates, in another embodiment, to water-in-oil formulations comprising the disclosed waterproofing polymers.

[0013] The present disclosure generally relates, in another embodiment, to a water-in-oil sunscreen formulation comprising the following individual components: (a) at least one sunscreen active, and (b) at least one waterproofing polymer disclosed herein.

[0014] By "individual components," it is meant that no single component satisfies more than one of the listed components. For example, consider a composition containing individual components (a), (b), and (c). In such an example, there must be a minimum of three components combined to satisfy (a), (b), and (c), where a first component satisfies (a), a second component different from the first component satisfies (b), and a third component different from the first and second components satisfies (c).

[0015] The present disclosure generally relates, in yet another embodiment, to a method for protecting a user who is or has already been exposed to the sun from the damaging effects of sun exposure, comprising applying to the skin of the user an effective amount thereof of a water-in-oil sunscreen formulation disclosed herein.

[0016] The present disclosure generally relates, in still further embodiments, to a method for waterproofing a water-in-oil sunscreen formulation comprising at least one sunscreen active, the method comprising incorporating into the sunscreen formulation a waterproofing amount of at least one waterproofing polymer disclosed herein.

[0017] The present disclosure will now be described in more detail with reference to the following figures: [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a graph showing the benefit of using hydrogenated dimer acid to prepare waterproof polymers according to the present disclosure using the disclosed substantially non-sequential reaction method, and the effect of the weight average molecular weight of the polymer on the WR SPF. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present disclosure generally relates to waterproof polymers that can impart high static and water-resistant SPF to W / O sunscreen formulations.

[0020] A very important benefit of the described invention is the provision of a bio-based, biodegradable polymer with excellent sensory, waterproof, and water-resistant sun protection factor (WR SPF) performance that performs strongly in sports emulsion sunscreens that are natural, biodegradable, and resist dilution and removal of UV absorbers by water after application. An acceptable high WR SPF target is considered to be SPF 50.

[0021] In one embodiment, the disclosed waterproof polymer is a substantially non-sequential reaction product of the following components: (i) at least one polyglycerol, (ii) at least one dimer acid, and (iii) at least one fatty acid having from 8 to 30 carbon atoms, wherein the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 1 mole of hydrogenated dimer acid, and 0.1 moles to less than 2.0 moles of fatty acid.

[0022] The term "substantially non-sequential reaction product" means that the product is produced by a substantially non-sequential reaction of the reacting components (i)-(iii). The term "substantially non-sequential reaction of the reacting components (i)-(iii)" means that substantially the entire content of each of the reactants (i)-(iii) to be reacted is added to the reaction vessel before the reaction is initiated. This process differs from, for example, the process described in U.S. Pat. No. 6,242,499, in which polyglycerol is esterified with a fatty acid in a first step, and after most or all of the fatty acid has reacted, a polyfunctional carboxylic acid is added in a second step and the esterification reaction continues. In one embodiment of the present disclosure, the entire content of each of the reactants (i)-(iii) to be reacted is added to the reaction vessel before the reaction is initiated, i.e., the reaction is completely non-sequential, and the polymer is a completely non-sequential reaction product of the reactants (i)-(iii). In other embodiments, at least 70-100%, or 75-100%, or 80-100%, or 85-100%, or 90-100%, or 95-100%, or 97-100% of each of reactants (i)-(iii) is added to the reaction vessel before initiating the reaction.

[0023] Without wishing to be bound by theory, the inventors believe that the preparation procedure described in U.S. Pat. No. 6,242,499, in which polyglycerol is reacted with a monofunctional fatty acid in the first step, results in undesirable insufficient chain termination or "end-capping." Not only does the reaction with the monofunctional fatty acid reduce the number of free hydroxyl sites available for reaction with the polyfunctional carboxylic acid in the second step, but the fatty acid ester functional groups generated in the first step are substantially inert and therefore unavailable for participating in chain extension or branching. This has a significant effect on the properties of the polymers thus produced. As described herein, by introducing substantially all or the entire contents of components (i)-(iii) into the reaction vessel at the time of and / or prior to the start of the polymer reaction, the inhibition by the fatty acid on the ability of the polyfunctional carboxylic acid to react with the polyglycerol is minimized, resulting in longer polymer chains, more extensive polymer chain cross-linking, higher polymer molecular weight, and higher viscosity.

[0024] With the foregoing in mind, it may be possible to produce the disclosed polymers sequentially, for example, by adding some or most, but not all, of the monofunctional fatty acid to the polyglycerol in a first step, and the remainder with the dimer acid in a second step, or even after the dimer acid in a third step. Any order is possible, as long as the process is carefully designed and monitored to avoid insufficient end-capping.

[0025] The polyglycerol may be any oligocondensation product of glycerol. In one embodiment, the polyglycerol has the formula (I): H[-O-Gly-]n-OH(I) wherein each Gly is independently the residue of a glycerol molecule after removal of two hydroxy groups, and n is an average of 2 to 10. It has.

[0026] Generally, the majority of GIy groups have the formula -CH2-CHOH-CH2-, although residues containing etherification at the secondary or even tertiary hydroxy group are considered within the scope of "GIy" and therefore may also be present. Examples of oligoglycerols include diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol, decaglycerol, and mixtures thereof. Particularly useful polyglycerols are polyglycerols of formula (I), where n is particularly 2 to 7, more particularly 2 to 5, and especially 2, 3, or 4, or mixtures of oligoglycerols within these ranges.

[0027] Particularly suitable polyglycerols include mixtures of oligoglycerols having the following oligomer distribution: Glycerol: 0 to 30% by weight, preferably 0 to 20% by weight, most preferably 0 to 15% by weight Diglycerol: 10 to 40% by weight, preferably 15 to 35% by weight, most preferably 20 to 32% by weight Triglycerol: 10 to 65% by weight, preferably 15 to 60% by weight, most preferably 18 to 55% by weight Tetraglycerol: 2 to 25% by weight, preferably 5 to 20% by weight, most preferably 8 to 20% by weight Pentaglycerol: 0 to 15% by weight, preferably 0 to 10% by weight, most preferably 0 to 5% by weight Hexaglycerol: 0 to 15% by weight, preferably 0 to 10% by weight, most preferably 0 to 5% by weight Heptaglycerol: 0 to 10% by weight, preferably 0 to 5% by weight, most preferably 0 to 3% by weight Octaglycerol: 0 to 10% by weight, preferably 0 to 5% by weight, most preferably 0 to 3% by weight Nonaglycerol: 0 to 5% by weight, preferably 0 to 3% by weight, most preferably 0 to 2% by weight Decaglycerol: 0 to 5% by weight, preferably 0 to 3% by weight, most preferably 0 to 2% by weight (All weight percentages are based on total polyglycerol content).

[0028] In one embodiment, the polyglycerol comprises the following oligomer distribution: Glycerol: 0 to 30% by weight Diglycerol: 15 to 40% by weight Triglycerol: 10 to 55% by weight Tetraglycerol: 2 to 25% by weight Pentaglycerol and higher components: 0-15% by weight (All weight percentages are based on total polyglycerol content).

[0029] In one embodiment, the polyglycerol is composed of at least 40%, or at least 45%, or at least 50% by weight of a combination of diglycerol and triglycerol, based on the total weight of the polyglycerol.

[0030] In one embodiment, the polyglycerol is composed of at least 20% or at least 25% by weight of diglycerol, at least 15% or at least 18% by weight of triglycerol, and at least 10% or at least 12% by weight of tetraglycerol, all weight percentages being based on the total polyglycerol content.

[0031] A particularly preferred polyglycerol comprises at least 25% by weight diglycerol, at least 45% by weight triglycerol, and at least 10% by weight tetraglycerol.

[0032] Any such analysis of polyglycerol composition can be performed to determine its median, average, or "mean" polyglycerol number. The aforementioned oligoglycerol examples having both narrow and broad distributions can equally be designated polyglycerol-3, since this number is the nearest integer to the mean and / or median.

[0033] The dimer acid may be any dicarboxylic acid having at least four carbon atoms. The dimer acid may be linear or branched, such as, for example, dimers prepared from malonic acid, succinic acid, fumaric acid, dimethylglutaric acid, or trimethyladipic acid, and their anhydrides.

[0034] Dimer fatty acids are particularly useful: as is known, they are mixtures of acyclic and cyclic dicarboxylic acids obtained by catalytic dimerization of unsaturated fatty acids having 12 to 22 carbon atoms.

[0035] For the preparation and use of dimer acids and their physical and chemical properties, reference is made to the article "The Dimer Acids: The Chemical and Physical Properties, Reactions and Applications", Ed. E. C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.

[0036] The dicarboxylic acids may also contain, to a lesser extent, trifunctional and polyfunctional carboxylic acids. The functionality of the mixture should not exceed an average value of 2.4 moles.

[0037] The inventors have discovered that the use of higher molecular weight dimer acids provides a beneficial combination of significant hydrophobic characteristics for enhanced waterproofing and significant hydrophilic characteristics for some compatibility with the aqueous phase. Dimer acids are typically derived from triglycerides that are rich in C18 ester groups, which can produce C18 unsaturated monoacid fatty acids upon hydrolysis. The feedstock can be derived from tall oil and rapeseed oil, although other natural sources, including linseed, soybean, pumpkin, and walnut, can be used. The target monoacids used in the reaction are rich in the oleic and linoleic acid forms listed in the list of fatty acids contained below. Dimerization primarily results in the dimerization of unsaturated fatty acids, although trimers are also formed. After the reaction, the product can be retained as a mixture of reaction products or can be further distilled or otherwise separated into molecular weight fractions. In one embodiment, the dimerization reaction produces a majority (at least 60 wt%, more preferably at least 75 wt%) of dimer acids (C36 diacids), but also produces C54 trimer acids (less than 30 wt%, more preferably less than 25%), with the remainder containing C18 acids and C27 1.5 mers.

[0038] In one case, commercially available standard dimer acid Pripol 1025 from Croda is used, which contains a total of 7 wt% C18 monomer and C27 1.5 mer, 72 wt% dimer, and 19 wt% trimer acid. In another case, hydrogenated standard dimer acid Radiacid 0960 from Oleon is used, which contains 3 wt% C18 monomer and C27 1.5 mer, 87 wt% dimer, and 10 wt% trimer acid. In both cases, the described polymers are characterized by higher molecular weight, higher hydrophobicity, and higher viscosity than can be provided by pure lower molecular weight diacids. The presence of trimer acid further enhances the molecular weight and performance of these polymers.

[0039] Hydrogenation of the dimer acid is a very important factor affecting important properties of the polymer. In particular, the use of hydrogenated dimer acid to prepare the disclosed polymers dramatically increases the water resistance and SPF performance of the resulting sun care and cosmetic formulations.

[0040] Thus, in one embodiment, the present disclosure relates to waterproof polymers prepared from at least one hydrogenated dimer acid.

[0041] In another embodiment, the waterproofing polymer is prepared from a hydrogenated dimer acid comprising a hydrogenated dimerized C18 fatty acid, the hydrogenated dimer acid being obtained by dimerization of an unsaturated C18 fatty acid and subsequent hydrogenation.

[0042] It is beneficial if the hydrogenated dimer acid contains a content of trimer acid, as this increases branching and polymer molecular weight.

[0043] In one embodiment, the hydrogenated dimer acid contains a trimer acid content in the range of about 5-25 wt %, based on the total weight of the hydrogenated dimer acid.

[0044] In another embodiment, the hydrogenated dimer acid contains a majority (at least 60 wt%, more preferably at least 75 wt%, but not more than 95 wt%, or better not more than 90 wt%, or even better not more than 85 wt%) of hydrogenated dimer acid (C36 diacid), and also contains C54 hydrogenated trimer acid (less than 30 wt%, more preferably less than 25 wt%, but more than 5 wt%, more preferably more than 10 wt%), with the remainder being C18 hydrogenated acid and C27 hydrogenated 1.5 mer.

[0045] Fatty acid monoacids are desirable because they act as end caps in the polymerization reaction, providing adjustable hydrophobic content and contributing to polymer properties. While all monoacids with 8 to 30 carbon atoms, particularly those with 12 to 30 carbon atoms, can be used, we prefer monoacids with C18 or higher to provide more hydrophobic content for waterproofing. These can include naturally occurring or refined fatty acids, such as hydrolyzed rapeseed oil and sunflower oil, which contain both lower and higher MW chains.

[0046] Useful fatty acids can be linear, branched, saturated, unsaturated, and aromatic, with the acidity provided by the carboxylic acid moiety. Useful acids include caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecylic acid (C11), lauric acid (C12), tridecylic acid (C13), myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), margaric acid (C17), stearic acid (C18), isostearic acid (C18), nonadecylic acid (C19), arachidic acid (C20), behenic acid (C22), and lignoceric acid (C24). (Lower molecular weight organic acids, including butyric acid (C4), valeric acid (C5), caproic acid (C6), and enanthic acid (C7), could also be used in place of fatty acids.)

[0047] A comparison of stearic acid and isostearic acid shows that branching leads to a high melting point and a low viscosity for isostearic acid at room temperature, while stearic acid leads to a solid material. This lower viscosity can aid in the material handling of raw materials and can also help the esters made with this acid retain liquid properties. Branched-chain fatty acids often contain a single methyl branch along a linear carbon chain and are naturally produced by microbial action. Isostearic acid is available as a reaction by-product in the production of the aforementioned dimer acid.

[0048] Another route to obtain a liquid product is to use unsaturated linear and branched fatty monoacids. These unsaturated acids may include palmitoleic acid (C16:1), vaccenic acid (C18:1), oleic acid (C18:1), elaidic acid (C18:1), linoleic acid (C18:2), linoleelaidic acid (C18:2), α-linolenic acid (C18:3), γ-linolenic acid (C18:3), stearidonic acid (C18:4), paulic acid (C20:1), gondoic acid (C20:1), dihomo-γ-linolenic acid (C20:3), mead acid (C20:3), arachidonic acid (C20:4), eicosapentaenoic acid (C20:5), erucic acid (C22:1), docosatetraenoic acid (C22:4), cervonic acid (C22:6), and nervonic acid (C24:1). As is well known to those skilled in the art, the designation "CX:Y" means that the carbon chain is X carbon atoms in length and there are Y double bonds in the chain.

[0049] All of these acids and their mixtures provide hydrophobicity when esterified with polyglycerol. Saturated fatty acids also provide fewer manufacturing side reactions and longer shelf life of the final product due to oxidation of unsaturated bonds that can result in discoloration and other by-products.

[0050] In one embodiment, the fatty acid is stearic acid, a linear saturated C18 fatty acid, or oleic acid, which is a monounsaturated C18. However, the unsaturated point may result in subsequent oxidative instability, and linear C18 fatty acids may result in crystallization of the polymer.

[0051] For this reason, we prefer isostearic acid, which provides long term stability and inhibits crystallization and phase separation of both the raw ingredients and the final polymer.

[0052] In a particularly preferred embodiment, the waterproofing polymer is a substantially or completely non-sequential reaction product of the following components: (i) at least one polyglycerol comprising at least 25 wt. % diglycerol, at least 45 wt. % triglycerol, and at least 10 wt. % tetraglycerol (in each case based on the total weight of the polyglycerol), (ii) at least one hydrogenated dimer acid containing at least 60 wt. % hydrogenated C36 diacid and 5-25 wt. % hydrogenated C54 triacid (in each case based on the total weight of the hydrogenated acid), and (iii) isostearic acid.

[0053] In one embodiment, the waterproofing polymer is prepared by a one-step process in which all reactants are introduced into a reaction vessel and then direct the completely statistical addition of dimer acid and isostearic acid to the polyglycerol.

[0054] The inventors have found that the best waterproofing properties of the polymer are obtained when the polyglycerol contains an excess of OH groups compared to the acid groups added by the combination of isostearic acid and dimer acid materials. As previously mentioned, a wide variety of polyglycerols have been used in blended form to demonstrate the unique performance offered by this material.

[0055] Although the sequential process utilized in US Patent No. 6,242,499 unexpectedly results in insufficient end-capping, the present inventors have discovered that this is not the only problem that prevents the prior art from achieving the beneficial properties described herein.This situation is exacerbated by the high ratio of monofunctional fatty acid to polyglycerol.The present inventors have found that when the molar ratio of fatty acid to polyglycerol is reduced to less than 2:1, waterproofing can be improved, and higher static SPF and WR SPF can be achieved.

[0056] In one embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 1 mole of dimer acid, and 0.2 to 1.7 moles of fatty acid.

[0057] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 0.75 moles of dimer acid, and 0.4 to 1.35 moles of isostearic acid.

[0058] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 0.7 moles of dimer acid, and 0.65 to 1 moles of isostearic acid.

[0059] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 1 mole of hydrogenated dimer acid, and 0.2 to 1.7 moles of isostearic acid.

[0060] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 0.75 moles of hydrogenated dimer acid, and 0.4 to 1.35 moles of isostearic acid.

[0061] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol, 0.5 to 0.7 moles of hydrogenated dimer acid, and 0.65 to 1 moles of isostearic acid.

[0062] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol-3, 0.5 to 1 mole of hydrogenated dimer acid, and 0.2 to 1.7 moles of isostearic acid.

[0063] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol-3, 0.5 to 0.75 moles of hydrogenated dimer acid, and 0.4 to 1.35 moles of isostearic acid.

[0064] In another embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol-3, 0.5 to 0.7 moles of hydrogenated dimer acid, and 0.65 to 1 moles of isostearic acid.

[0065] In the most preferred embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol-3, 0.5 moles of hydrogenated C36 dimer acid, and 1 mole of isostearic acid.

[0066] In another most preferred embodiment, the reacting components are in a molar ratio of 1 mole of polyglycerol-3, 0.67 moles of hydrogenated C36 dimer acid, and 0.67 moles of isostearic acid.

[0067] By adjusting the molar ratio of fatty acid end caps and balancing the amount of polyglycerol and dimer acid, it is also possible to control the degree of elongation and end-capping of the dimer acid-polyglycerol, thus resulting in significant viscosity enhancement, for example, by cross-linking via trimer acid.

[0068] The target viscosity of the pure polymer should be >50,000 cP and less than 5,000,000 cP at 25°C.

[0069] In a preferred embodiment, the target viscosity is >75,000 cP and <2,500,000 at 25°C.

[0070] In another preferred embodiment, the target viscosity is >100,000 cP and <2,000,000 at 25°C.

[0071] In the most preferred embodiment, the target viscosity is >1,000,000 cP and <2,000,000 at 25° C., thereby further improving water resistance.

[0072] The disclosed polymers are characterized by weight-average molecular weights >2500 Da and <1,000,000 Da, as measured by GPC using linear polystyrene standards. The GPC column used for these tests consisted of Phenolgel, 300 x 4.6 mm, with a continuous phase of tetrahydrofuran (THF), injection at 0.35 mL / min, column oven temperature maintained at 40 °C, 50 μL injections, and a Wyatt refractive index Ri detector. The calibration standard used was fully linear polystyrene engineered to be monodisperse. Narrow-range polystyrene GPC calibration standards were prepared in the mobile phase and had peak molecular weights of 1,290,000 Da, 560,000 Da, 65,500 Da, 28,500 Da, 10,100 Da, 1,680 Da, 580 Da, and 208 Da. From standard methods, weight average and number average molecular weights are automatically calculated by standard GPC software. Here, we focus on determining the weight average molecular weight, which we refer to herein as "M w " abbreviated as "M w While the radius of gyration of a fully dissolved crosslinked polymer can be very important information in most cases, it is known that the radius of gyration of a fully dissolved crosslinked polymer is smaller than that of an ideal dissolved linear polymer of the same molecular weight and monomer composition. This reduction in size for a similar actual molecular weight is characterized as the "polymer shrinkage factor." See literature such as the Zimm-Stockmayer shrinkage factor. The magnitude of the shrinkage factor varies depending on the monomer selection, trimer percentage, and conversion percentage, as well as the substantially non-sequential reaction conditions mentioned above. In our analytical studies, we compare the low molecular weight fraction (less than 1000 Da) to both GPC data and measurements of the remaining monomers in the materials used in the polymerization examples, such as polyglycerol-3, hydrogenated dimer acid, and isostearic acid. In this way, we determined that the shrinkage factor for the polyester polymers of the present disclosure is approximately 3. This is an important consideration. However, to be consistent with standard GPC methods, the molecular weight determinations are compared to linear polystyrene, reported without correction for the shrinkage factor, to determine the "measured" M. wInstead, we report the M w We report a novel combination of the viscosity of branched polymers (relative to standard linear polystyrene) combined with the viscosity of the same polymers, where higher viscosities can be measured directly, and for branched polymers the viscosity increases significantly, for example, they can have shrinkage factors of 3 or higher.

[0073] In preferred embodiments, the disclosed polymers have a weight average molecular weight >4000 Da and <250,000 Da, as measured by GPC using linear polystyrene standards.

[0074] In the most preferred embodiment, the disclosed polymers have a weight average molecular weight >5000 Da and <150,000 Da as measured by GPC using linear polystyrene standards.

[0075] As mentioned above, U.S. Patent No. 6,242,499 proposes esterifying polyglycerol with a fatty acid in a first step, allowing most or all of the fatty acid to react, and then adding a polyfunctional carboxylic acid in a second step to continue the esterification reaction, which limits molecular weight development and reduces the viscosity of the polymer, making it unable to provide good waterproofing properties.

[0076] The inventors have demonstrated that M obtained by the one-step process described herein w It has been found that certain combinations of viscosity and viscosity provide excellent waterproofing properties. The polyester polymers of the present disclosure were measured using an MCR302 Rheometer manufactured by Anton Paar Inc. Two 50 mm diameter plates, either rough or flat, were coated with the polymer sample and adjusted to a gap of 0.5 to 1 mm, and both temperature and shear rate sweeps were performed. The polymers of the present disclosure exhibit Newtonian behavior and therefore have a constant viscosity over a wide range of shear rates. The polymers of the present disclosure also demonstrated a decrease in viscosity with temperature. Therefore, viscosity measurements were taken at precisely controlled temperatures and over a period typically of 1 second.-1 The value is reported as a shear rate of 1000 cP. The value is reported in units of centipoise (cP), where 1000 cP is equivalent to 1 Pascal-second (Pa-s). As previously mentioned, the measured viscosity is compared to the M of the polymer measured by GPC using a linear polystyrene standard. w The combination of is one important parameter for defining the waterproof polymers of the present disclosure.

[0077] In one embodiment, the waterproof polymer has an M as measured by GPC using linear polystyrene standards. w It exhibits a combination of neat polymer viscosities of >2500 Da and <1,000,000 Da, and >50,000 cP and <5,000,000 cP at 25°C.

[0078] In another embodiment, the waterproof polymer has an M as measured by GPC using linear polystyrene standards. w It exhibits a combination of neat polymer viscosities of >4000 Da and <250,000 Da, and >75,000 cP and <2,500,000 cP at 25°C.

[0079] In yet another embodiment, the waterproof polymer has an M as measured using GPC using linear polystyrene standards. w It exhibits a combination of viscosity of the neat polymer of >5000 Da and <150,000 Da, and >100,000 cP and <2,000,000 cP at 25°C.

[0080] In a preferred embodiment, the waterproofing polymer is a substantially or completely non-sequential reaction product of the following components: (i) at least one polyglycerol comprising at least 25 wt. % diglycerol, at least 45 wt. % triglycerol, and at least 10 wt. % tetraglycerol (in each case based on the total weight of the polyglycerol), (ii) at least one hydrogenated dimer acid containing at least 60 wt. % hydrogenated C36 diacid and 5-25 wt. % hydrogenated C54 triacid (in each case based on the total weight of the hydrogenated acid), and (iii) isostearic acid, wherein the waterproofing polymer has an M of 100 or less as measured by GPC using linear polystyrene standards. w It exhibits a combination of neat polymer viscosities of >5000 Da and <150,000 Da, and >100,000 cP and <2,000,000 cP at 25°C.

[0081] As extensively described above, the reaction order and non-sequential reactions, the ratio of polyglycerol to dimer acid and monoacid, are critical to achieving the desired combination of viscosity and molecular weight. By definition, these ratios of polyol to monoacid and polyacid, when driven to completion, define the so-called degree of esterification. Polycondensation reactions, such as those based on the polyester polymers of the present disclosure, typically contain an excess of either polyol or polyacid moieties. Monoacids, by definition, cannot lead to polymerization but rather act only as end-caps. The presence of five hydroxy groups in polyglycerol-3 makes the polyol monomers of the present disclosure and their hydroxyl moieties ideally unique candidates to be retained in excess. If one attempted to react all of the hydroxy groups with the large fatty acid groups of the disclosed invention, the reaction would result in both an unwieldy high MW and gelation, making the product difficult to handle and unsuitable for use as a cosmetic ingredient. Thus, from the preferred molar ratios, we can calculate our preferred degree of total esterification of the hydroxyl moieties of available polyglycerols (total esterification) of 24% to 74%, and the degree of esterification of the hydroxyl moieties of available polyglycerols with dimer acids alone (esterification with dimer acids) of 20% to 40%. Most importantly, the degree of esterification with end-capping units (esterification with monoacids) is also described in this disclosure, and it is important to maintain the degree of esterification with monoacids between 4% and 40%.

[0082] The inventors prefer a total esterification of 28% to 57%, with esterification using dimer acids being 20% ​​to 30% and esterification using monoacids being 8% to 27%.

[0083] We find it even more preferred that the total esterification is between 33% and 48%, with 20% to 28% esterification with dimer acids and 13% to 20% esterification with monoacids.

[0084] We find it even more preferable for the total esterification to be between 24% and 74%, with esterification using hydrogenated dimer acid being between 20% and 40% and esterification using monoacid being between 4% and 40%.

[0085] We find it even more preferable for the total esterification to be between 28% and 57%, with esterification using hydrogenated dimer acid being between 20% and 30% and esterification using monoacid being between 8% and 27%.

[0086] We most prefer about 40% total esterification, with about 20% esterification using hydrogenated dimer acid and about 20% esterification using monoacid.

[0087] We also most preferably have about 40% total esterification, with about 27% esterification using hydrogenated dimer acid and about 13% esterification using monoacid.

[0088] In a preferred embodiment, the waterproofing polymer is a substantially or completely non-sequential reaction product of the following components: (i) at least one polyglycerol comprising at least 25 wt. % diglycerol, at least 45 wt. % triglycerol, and at least 10 wt. % tetraglycerol (in each case based on the total weight of the polyglycerol), (ii) at least one hydrogenated dimer acid containing at least 60 wt. % hydrogenated C36 diacid and 5-25 wt. % hydrogenated C54 triacid (in each case based on the total weight of the hydrogenated acid), and (iii) isostearic acid, wherein the waterproofing polymer has an M of 1000 kJ / cm , as measured by GPC using linear polystyrene standards. w Exhibiting a combination of neat polymer viscosities of >5000 Da and <150,000 Da, and >100,000 cP and <2,000,000 cP at 25°C, the waterproof polymer is also characterized by about 40% total esterification, of which about 27% is esterified with hydrogenated dimer acid and about 13% is esterified with monoacid.

[0089] In practice, feedstock components contain varying polyglycerol units and varying dimer and trimer acid contents, so the preceding figures can be adjusted using actual (and non-theoretical) hydroxyl and carboxylic acid moieties, as determined by standard methods, such as mass spectrometry, NMR, and liquid chromatography. The preceding esterification ranges are based on idealized structures of polyglycerol-3 and C36-dimer acid. Therefore, actual ranges may vary slightly from the values ​​presented above and can be calculated based on these analytical analyses.

[0090] It is most practical to define the degree of polymerization in terms of the final acid value. The initial acid value can be reliably calculated using the actual acid values ​​determined by the raw material components used in light of the distribution of polyglycerol, monoacid, and polyacid moieties present.

[0091] In one example, the initial total acid value ("AV," commonly defined as mg KOH / g total reactants) is 135 AV. This includes 68 AV for dimer acid and 67 AV for isostearic acid for a preferred embodiment containing 1 mole of polyglycerol-3, 0.5 moles of hydrogenated C36 dimer acid, and 1 mole of isostearic acid. All of the preferred ratio embodiments described above have a corresponding initial AV that can be calculated. When AV units are reduced during the polymerization reaction, this ratio provides the percent conversion of the reaction from total initial reactive acid moieties to the final remaining acid moieties. Thus, reaction completion is 1 minus the ratio of the final AV to the initial AV.

[0092] In one embodiment, the polymers of the present disclosure have a final acid value of 0.1 to <25 mg KOH / g polymer.

[0093] In a preferred embodiment, the polymer has a final acid value of 0.1 to <10 mg KOH / g polymer.

[0094] In the most preferred embodiment, the polymer has a final acid value of 0.1 to <5 mg KOH / g polymer.

[0095] When reaction completion is expressed as 1-final AV / initial AV, the reaction completion from such a reaction mixture to the final polymer is >80%.

[0096] In a preferred embodiment, the completion of the reaction from such a reaction mixture to the final polymer is >90%.

[0097] In the most preferred embodiment, the completion of the reaction from such a reaction mixture to the final polymer is >95%.

[0098] In particular, the polymer can be combined with an organic solvent to facilitate transport of the polymer.

[0099] In one embodiment, the solvent is selected from the group consisting of volatile solvents that are preferably easily removable, such as, but not limited to, methanol, ethanol, isopropanol, glycerol, propanediol, and the like.

[0100] If necessary, the polymer can also be diluted with various emollients to reduce the viscosity of the blend at room temperature. Emollients can include any suitable oil, solvent, ester, triglyceride, ether, silicone, hydrocarbon, etc., appropriate for the end-use application. Typical emollients for sun care emulsions and products include triheptanoin, isopropyl palmitate, isopropyl myristate, 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, and other suitable esters. Emollients can also include ethers such as dicaprylyl ether. When diluted with an emollient, the addition is performed while mixing and maintaining the final product at approximately 80°C to 100°C. The combination is then further cooled to 50-70°C for discharge from the reactor and storage.

[0101] In one embodiment, the polymer is diluted to a final concentration of 10 wt% to 99 wt% polymer, and the diluent is an emollient suitable for skin and personal care applications consisting of an ester or triglyceride.

[0102] In another embodiment, the polymer is diluted to a final concentration of 30 wt% to 90 wt% polymer, and the diluent is an emollient suitable for skin and personal care applications consisting of an ester or triglyceride from the list above.

[0103] In yet another embodiment, the polymer is diluted to a final concentration of 50% to 80% polymer by weight, and the diluent is an emollient suitable for skin and personal care applications, consisting of an ester or triglyceride.

[0104] The polymer can be incorporated into water-in-oil formulations to impart waterproofing properties to the formulation.

[0105] In one embodiment, the waterproofing polymer is incorporated into the water-in-oil formulation in an amount of 0.1 to 10 wt % based on the total weight of the formulation.

[0106] In another embodiment, the waterproofing polymer is incorporated into the water-in-oil formulation in an amount of 0.5 to 5 wt % based on the total weight of the formulation.

[0107] In yet another embodiment, the waterproofing polymer is incorporated into the water-in-oil formulation in an amount of 1-3 wt % based on the total weight of the formulation.

[0108] At these amounts, when the water-in-oil formulation is a sunscreen formulation and the waterproofing polymer is prepared from hydrogenated dimer acid, the inventors have surprisingly discovered that the sunscreen formulation is characterized by an increased SPF, which is confirmed in both static SPF tests and, in particular, in water-resistant SPF (WR SPF) tests.

[0109] Sunscreen formulations typically contain 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 generally described by their ability to act as UV active agents and their performance in different spectral regions, described as UV-A, UV-B, or UV-A / UV-B. Inclusion of an active agent in a formulation intended for human use generally requires regulatory approval. Active agents approved or currently approved for sunscreen use in the United States include organic and inorganic substances including, but not limited to, para-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digalloyl trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, lawsone with dihydroxyacetone, red petrolatum. Examples of additional sunscreen actives not yet approved in the United States but acceptable in formulations sold outside the United States include ethylhexyl triazone, dioctyl butamido triazone, benzylidene malonate polysiloxane, terephthalylidene dicamphorsulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexyl benzoate, bisdiethylamino hydroxybenzoyl benzoate, bisbenzoxazoylphenyl ethylhexyl imino triazine, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethylbutylphenol, and bis-ethylhexyloxyphenol methoxyphenyl triazine, 4-methylbenzylidene camphor, and isopentyl 4-methoxycinnamate.However, those skilled in the art will recognize that the list of approved sunscreens is currently expanding, and therefore the present invention is not limited to sunscreen actives currently approved for human use, but can readily be applied to sunscreen actives that may become acceptable in the future.

[0110] Sunscreen actives that have been approved in Europe and are therefore useful in accordance with the present disclosure include, again without limitation, benzophenones, such as benzophenone-3 (BP3) and benzophenone-4 (BP4); salicylates, such as homosalate (HMS) and 2-ethylhexyl salicylate (EHS); p-aminobenzoic acid and derivatives, such as ethylhexyl dimethyl PABA (OD-PABA) and 4-p-aminobenzoic acid (PABA); benzimidazole derivatives, such as phenylbenzimidazole sulfonic acid (PMDSA) and disodium phenyldibenzimidazole tetrasulfonate (bisdisulizole disodium); triazines, such as ethylhexyl triazone (OT), diethylhexylbutamido triazone (DBT), and bis-ethylhexyloxyphenol methoxyphenyl triazine. (EMT); benzotriazoles such as drometrizole trisiloxane (DRT) and methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, Biscotrazole); dibenzoylmethane derivatives such as 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM, Avobenzone); cinnamic acid esters such as ethylhexyl methoxycinnamate (OMC) and isoamyl p-methoxycinnamate (IMC, Amiloxate); and camphor derivatives such as terephthalylidene dicamphorsulfonic acid (PDSA), 3-benzylidene camphor (3BC), benzylidene camphorsulfonic acid (BCSA), 4-methylbenzylidene camphor (4-MBC), polyacrylamidomethyl benzylidene camphor (PBC) and camphor benzalkonium methosulfate (CBM).

[0111] In one embodiment of the present disclosure, the sunscreen active comprises a photoprotectively effective amount of at least one inorganic pigment or nanopigment particulate, non-limiting examples of which include titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, or mixtures thereof.

[0112] Generally, sunscreen actives are present in sunscreen formulations in amounts known in the art to be effective in protecting a user who is about to be exposed to or has already been exposed to the sun from the damaging effects of sun exposure. Typically, these amounts range from 1 to 25% by weight, preferably 3 to 25% by weight, based on the total weight of the sunscreen formulation.

[0113] The disclosed sunscreen formulations, referred to herein as "cosmetic components," can optionally contain a wide variety of additional components, which can also include components commonly known as pharmaceutically active agents. The CTFA Cosmetic Ingredient Handbook, Seventh Edition, 1997 and the Eighth Edition, 2000, each of which is incorporated herein by reference in its entirety, describe a wide variety of cosmetic and pharmaceutical ingredients commonly used in skin care compositions that are suitable for use in the compositions of the present disclosure. Examples of these functional classes disclosed in this reference include absorbents, abrasives, anti-caking agents, anti-foaming 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 components, moisturizers, opacifiers, pH adjusters, plasticizers, reducing agents, skin whitening agents, skin conditioning agents (emollients, moisturizers, miscellaneous, and occlusive), skin protectants, solvents, foam boosters, hydrotropes, solubilizers, suspending agents (non-surfactant), sunscreens, UV absorbers, SPF boosters, waterproofing agents, and thickeners (aqueous and non-aqueous).

[0114] In one embodiment, the present disclosure relates to a water-in-oil sunscreen formulation comprising the following individual components: (a) at least one sunscreen active, and (b) at least one waterproofing polymer disclosed herein, and (c) at least one water-in-oil emulsifier.

[0115] Suitable water-in-oil emulsifiers are all well known in the art.The materials and amounts of these materials described in US Patent Application Publication No. 2011 / 0091397, the entire contents of which are incorporated herein by reference, are particularly preferred.Effective water-in-oil emulsifiers typically have low water solubility, and include, for example, hydrogenated tri(polyglyceryl-3 / lauryl)trilinoleate, polyglyceryl-4 isostearate, cetyl PEG / PPG-10 / 1 dimethicone, hexyl laurate, cetyl PEG / PPG-10 / 1 dimethicone, cetyl PEG / PPG-10 / 1 dimethicone (and) hexyl laurate (and) polyglyceryl-4 isostearate, PEG-30 dipolyhydroxystearate and polyglyceryl-3 polyricinoleate.

[0116] The disclosed sunscreen formulations are applied as liquids by rubbing into the skin, but can also be applied as a spray. However, the disclosed water-in-oil formulations can take other forms, such as lipsticks, makeup, lip balms, eye shadows, hair dyes and conditioners, or any application where sun protection may be beneficial.

[0117] The present disclosure will now be described in more detail with reference to the following non-limiting examples. [Example]

[0118] Compound Examples A. General Procedures As described in the co-pending application, the inventors prefer to use a reaction in which all monomers are added in a single addition, with or without any acid or base catalyst, with the reaction vessel under vacuum or nitrogen sparge, or a combination of vacuum and nitrogen sparge. The reaction mixture is heated with stirring either in a constant or stepwise ramp to a temperature of 160°C to 250°C over a period of 10 minutes to 10 hours, and then held at a temperature of 160°C to 250°C for 2 to 10 hours.

[0119] The present inventors consider it more preferable to ramp the temperature to 200°C linearly or stepwise over 20 minutes to 8 hours, and then maintain the temperature at 180°C to 210°C for 2 to 6 hours.

[0120] The inventors find it most preferable to ramp the temperature to 200°C over 2 to 5 hours, either linearly or stepwise, and then hold the temperature at 195 to 205°C for 3 to 5 hours.

[0121] For example, a useful waterproofing polymer was prepared as follows: A mixture of 24.0 g of polyglycerol-3, 28.2 g of dimer acid, 28.4 g of isostearic acid (CAS#30399-84-9), and 0.24 g of sodium hydroxide was added to a reaction vessel using a downward distillation setting. The mixture was stirred and heated to 180°C and held at 180°C for 30 minutes. The temperature of the mixture was then increased to 190°C for 30 minutes and continued to 200°C. The mixture was held at 200°C-205°C for approximately 2-4 hours until the final acid value reached less than 3.0 meq (KOH) / ml by titration. The distillation setting removed condensation during the reaction. The final product was cooled to approximately 100°C-120°C and then decanted at 100% active material.

[0122] B.Water-resistant polymer Following the general procedures outlined above, the polymers in the table below were produced.

[0123] [Table 1]

[0124] In the above table, PG-3 "Type A" is a proprietary polyglycerol composed of 17.62 wt% glycerol, 25.4 wt% diglycerol, 18.46 wt% triglycerol, 12.15 wt% tetraglycerol, 8.09 wt% pentaglycerol, 5.48 wt% hexaglycerol, 3.69 wt% heptaglycerol, 2.43 wt% octaglycerol, 1.46 wt% nonaglycerol, 0.83 wt% decaglycerol, 0.37 wt% undecaglycerol, and 0.16 wt% dodecaglycerol.

[0125] PG-3 "Type B," available from Inovyn, has a narrower oligoglycerol distribution, consisting of 30.6 wt% diglycerol, 49.41 wt% triglycerol, 14.78 wt% tetraglycerol, 3.86 wt% pentaglycerol, 1.10 wt% hexaglycerol, 0.28 wt% heptaglycerol, and 0.07 wt% octaglycerol.

[0126] C. Comparison with industry standards (SPF WR) The water-resistant SPF of the prepared polymers was compared to controls and certain industry standards as shown in the table below.

[0127] [Table 2]

[0128] Ganex™ V216 is a vinylpyrrolidone and hexadecene copolymer (INCI: VP / Hexadecene) available from Ashland Corporation. It is a synthetic polymer that provides waterproofing but not biodegradable properties in sunscreen formulations and is a liquid at 25° C.

[0129] Ganex™ V220 is a blend of polyvinylpyrrolidone (PVP) and copolymers of vinylpyrrolidone and eicosane (INCI: PVP (and) VP / eicosane) available from Ashland Corporation. It is a synthetic polymer that provides waterproofing properties in sunscreen formulations but is not biodegradable and is a solid at 25° C.

[0130] Schercemol™ PDD is a different non-performing polymer made up of PG-3, DA, and ISA available from Lubrizol.

[0131] Isolan™ PDI is a non-performing, distinct polymer made from PG-3, DA, and ISA available from Evonik Corporation.

[0132] As is standard in the art, UV absorption through a plastic film coated with a UV-absorbing suncare formulation used to simulate human skin is measured using a spectrophotometer to obtain a measurement of Sun Protection Factor (SPF). 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 UV light being transmitted through the skin.

[0133] In each case, 100cm 2 A UV-absorbing film with a surface area of ​​1000 nm is coated with 20 × 5 mg droplets of emulsion containing the test polymer and exposed to UV light in the range of 290-400 nm to obtain a so-called "static" SPF measurement.

[0134] SPF Water Resistance (SPF WR) measurements are performed on the same membrane after placing it in a water bath heated to 40° C. and gently agitating it. After removal, the sample is gently dried and measured again for light transmission, at which point the SPF WR data is obtained.

[0135] Data is provided in the co-pending application showing that the polymers of the present disclosure provide SPF WR in oil-in-water sunscreen formulations that are at least as good as, and in many cases better than, some industry standards. Furthermore, when the waterproofing polymer is prepared from a hydrogenated dimer, the SPF WR is even better than the gold standard in the industry.

[0136] Among the waterproof polymers of the present disclosure, the effect of hydrogenation and the difference in polymer weight average molecular weight are illustrated in Figure 1. The use of hydrogenated dimer acid can clearly significantly increase the SPF WR. Further benefits can be realized by producing waterproof polymers with higher weight average molecular weights.

[0137] D. Exemplary Water-in-Oil Formulations Example 13 was a water-in-oil formulation prepared by preparing an oil phase and emulsifying it in an aqueous phase. The oil phase was prepared in a 1000 mL beaker equipped with an overhead stirrer, and the following ingredients were added and dissolved at 75-80° C.: 90 g dicaprylyl ether (Cetiol OE, Cognis Corp), 90 g zinc oxide (Super Zinc Natural, Vizor LLC), 30 g C13-15 alkane, 15 g sunflower oil (Statfold Oil Ltd), 20 g hydrogenated tri(polyglyceryl-3 / lauryl) trilinoleate (Cithrol™ PGTL), and 8.3 g Example 28 (consisting of 60% polymer Example 10 and 40% caprylic-capric triglyceride). In a separate 500 mL beaker, the following aqueous solution was mixed and heated to 60°C: 218 g of deionized water, 5 g of phenoxyethanol (and) ethylhexylglycerin (Euxyl PE 9010, Schulke & Mayr GmbH), 3.5 g of magnesium sulfate (USP grade, Textile Chemical Co), and 20 g of barley (Hordeum Vulgare) seed flour (Amaze™ Nordic Barley, Nouryon). The aqueous phase was slowly added to the oil phase in a high-shear mixer (Silverson) at 1200 rpm, increased to 4000 rpm, and emulsified at 75-80°C for 10 minutes. The resulting W / O emulsion was slowly cooled to 65°C, final homogenization was performed, and cooled to 45°C for slow mixing and adjustment.

[0138] In vitro testing was performed using the W / O emulsion of Example 13. In vitro SPF and WR SPF were measured using the described method with artificial skin (partially hydrophilic acrylic polymer material). In vitro SPF results showed SPF 36 and WR SPF 37, both of which exceeded the SPF target of 30 for this formulation based on UV absorbing and scattering components. This example demonstrates that the polymer of the present disclosure provided waterproof benefits in W / O formulations.

[0139] Other waterproofing polymers disclosed, as well as other waterproofing polymers produced according to the methods described, can also be made into W / O sunscreen formulations that should provide similar benefits.

[0140] While the present disclosure has been described in conjunction with the foregoing specific embodiments, many alternatives, modifications and other variations thereof will be apparent to those skilled in the art, and all such alternatives, modifications and variations are intended to be within the spirit and scope of the present disclosure. The present specification includes the following aspects. Section 1. 1. A water-in-oil formulation comprising a waterproofing polymer, wherein the waterproofing polymer is a reaction product of the following components: (i) at least one polyglycerol, (ii) at least one dimer acid, and (iii) at least one fatty acid having from 8 to 30 carbon atoms, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 2. Item 1, wherein the waterproof polymer is a completely non-sequential reaction product. Section 3. Item 3. The formulation of item 1 or 2, wherein the waterproof polymer is produced from a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40% by weight based on the total weight of the polyglycerol. Section 4. 4. The formulation of any one of paragraphs 1 to 3, wherein the waterproof polymer is produced from at least one hydrogenated dimer acid. Section 5. Item 5. The formulation of item 4, wherein the waterproof polymer is produced from a hydrogenated dimer acid obtained by dimerization and subsequent hydrogenation of an unsaturated C18 fatty acid. Section 6. Item 6. The composition according to item 5, containing a trimer acid content in the range of about 5 to 25 wt% based on the total weight of the hydrogenated dimer acid. Section 7. Item 7. The formulation of any one of items 1 to 6, wherein the waterproofing polymer is produced from at least one fatty acid selected from the group consisting of caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecylic acid (C11), lauric acid (C12), tridecylic acid (C13), myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), margaric acid (C17), stearic acid (C18), isostearic acid (C18), nonadecylic acid (C19), arachidic acid (C20), behenic acid (C22), and lignoceric acid (C24). Section 8. Item 8. The formulation of item 7, wherein the waterproof polymer is produced from isostearic acid. Section 9. Item 10. The formulation of any one of items 1 to 8, wherein the waterproofing polymer is produced from (i) a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40 wt.% based on the total weight of the polyglycerol, (ii) a C18 hydrogenated dimer acid having a trimer acid content in the range of about 5 to 25 wt.% based on the total weight of the hydrogenated dimer acid, and (iii) isostearic acid, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 10. 10. The formulation of any one of paragraphs 1 to 9, wherein the waterproofing polymer exhibits a combination of Mw >2500 Da and <1,000,000 Da as measured using standard linear polystyrene by GPC, and a viscosity of the neat polymer of >50,000 cP and <5,000,000 cP at 25°C. Section 11. 1. A water-in-oil sunscreen formulation comprising the following individual components: (a) at least one sunscreen active, and (b) at least one waterproofing polymer, wherein the at least one waterproofing polymer is a reaction product of the following components: (i) at least one polyglycerol, (ii) at least one dimer acid, and (iii) at least one fatty acid having from 8 to 30 carbon atoms, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 12. Item 12. The formulation of item 11, wherein the waterproof polymer is a completely non-sequential reaction product. Section 13. Item 13. The formulation of item 11 or 12, wherein the waterproof polymer is produced from a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40% by weight based on the total weight of the polyglycerol. Section 14. Item 14. The formulation of any one of items 11 to 13, wherein the waterproof polymer is produced from at least one hydrogenated dimer acid. Section 15. Item 15. The formulation of item 14, wherein the waterproof polymer is produced from hydrogenated dimer acid obtained by dimerization of unsaturated C18 fatty acid and subsequent hydrogenation. Section 16. Item 16. The formulation according to item 15, containing a trimer acid content in the range of about 5 to 25 wt% based on the total weight of the hydrogenated dimer acid. Section 17. Item 17. The formulation of any of items 11 to 16, wherein the waterproofing polymer is produced from at least one fatty acid selected from the group consisting of caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecylic acid (C11), lauric acid (C12), tridecylic acid (C13), myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), margaric acid (C17), stearic acid (C18), isostearic acid (C18), nonadecylic acid (C19), arachidic acid (C20), behenic acid (C22), and lignoceric acid (C24). Section 18. Item 18. The formulation of item 17, wherein the waterproof polymer is produced from isostearic acid. Section 19. Item 19. The formulation of any one of items 11 to 18, wherein the waterproofing polymer is produced from (i) a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40 wt.% based on the total weight of the polyglycerol, (ii) a C18 hydrogenated dimer acid having a trimer acid content in the range of about 5 to 25 wt.% based on the total weight of the hydrogenated dimer acid, and (iii) isostearic acid, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 20. 20. The sunscreen formulation of any one of paragraphs 11 to 19, further comprising at least one water-in-oil emulsifier. Section 21. The sunscreen active agent is para-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digalloyl trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, lawsone with dihydroxyacetone, red petrolatum, ethylhexyl triazone, dioctyl palmitate. Rubutamide triazone, benzylidene malonate polysiloxane, terephthalidene dicamphorsulfonic acid, phenyl dibenzimidazole tetrasulfonate disodium, diethylamino hydroxybenzoyl hexyl benzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazoyl phenyl ethylhexyl imino triazine, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethyl butyl phenol, bis-ethylhexyloxyphenol methoxyphenyl triazine, 4-methyl Benzylidene camphor, homosalate, butyl methoxydibenzoylmethane, octocrylene, octyl salicylate, bemotrizinol and isopentyl 4-methoxycinnamate, benzophenone-3 (BP3), benzophenone-4 (BP4), homosalate (HMS), 2-ethylhexyl salicylate (EHS), ethylhexyl dimethyl PABA (OD-PABA), 4-p-aminobenzoic acid (PABA), phenylbenzimidazole sulfonic acid (PMDSA), phenyldibenzimidazole tetrasulfonic acid disodium (bisdisulfonate) Lysole disodium), ethylhexyl triazone (OT), diethylhexyl butamido triazone (DBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT), drometrizole trisiloxane (DRT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, Biscotrimazole), 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM, Avobenzone), ethylhexyl methoxycinnamate (OMC), isoamyl p-methoxycinnamate (IMC, Amiloxate),21. The sunscreen formulation of any one of paragraphs 11 to 20, wherein the at least one member is selected from the group consisting of terephthalylidene dicamphorsulfonic acid (PDSA), 3-benzylidene camphor (3BC), benzylidene camphorsulfonic acid (BCSA), 4-methylbenzylidene camphor (4-MBC), polyacrylamidomethyl benzylidene camphor (PBC), camphor benzalkonium methosulfate (CBM), titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and mixtures thereof. Section 22. 22. The sunscreen formulation of any one of paragraphs 11 to 21, wherein the waterproof polymer exhibits a combination of Mw >2500 Da and <1,000,000 Da as measured by GPC using standard linear polystyrene, and a viscosity of the neat polymer of >50,000 cP and <5,000,000 cP at 25°C. Section 23. 23. A method for protecting a user who is about to be exposed to or has already been exposed to sunlight from the damaging effects of exposure to sunlight, comprising the step of applying to the skin of the user an effective amount thereof of the sunscreen formulation according to any one of paragraphs 11 to 22. Section 24. 1. A method for waterproofing a sunscreen formulation containing at least one sunscreen active, comprising incorporating into the sunscreen formulation a waterproofing amount of at least one waterproofing polymer, wherein the at least one waterproofing polymer is a reaction product of the following components: (i) at least one polyglycerol, (ii) at least one dimer acid, and (iii) at least one fatty acid having from 8 to 30 carbon atoms, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 25. Item 25. The method of claim 24, wherein the waterproof polymer is a completely non-sequential reaction product. Section 26. Item 26. The method of claim 24 or 25, wherein the waterproof polymer is produced from a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40% by weight based on the total weight of the polyglycerol. Section 27. 27. The method of any one of paragraphs 24 to 26, wherein the waterproof polymer is produced from at least one hydrogenated dimer acid. Section 28. Item 28. The method according to item 27, wherein the waterproof polymer is produced from a hydrogenated dimer acid obtained by dimerization of an unsaturated C18 fatty acid and subsequent hydrogenation. Section 29. Item 29. The method according to Item 28, wherein the trimer acid content is in the range of about 5 to 25 wt % based on the total weight of the hydrogenated dimer acid. Section 30. 30. The method of any of items 24 to 29, wherein the waterproofing polymer is produced from at least one fatty acid selected from the group consisting of caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecylic acid (C11), lauric acid (C12), tridecylic acid (C13), myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), margaric acid (C17), stearic acid (C18), isostearic acid (C18), nonadecylic acid (C19), arachidic acid (C20), behenic acid (C22), and lignoceric acid (C24). Section 31. Item 31. The method according to item 30, wherein the waterproof polymer is produced from isostearic acid. Section 32. Item 32. The method of any one of items 24 to 31, wherein the waterproof polymer is produced from (i) a polyglycerol composed of a combination of diglycerol and triglycerol in an amount of at least 40 wt. % based on the total weight of the polyglycerol, (ii) a C18 hydrogenated dimer acid having a trimer acid content in the range of about 5 to 25 wt. % based on the total weight of the hydrogenated dimer acid, and (iii) isostearic acid, wherein (iii) and (i) are in a molar ratio of less than 2:1. Section 33. 33. The method of any one of paragraphs 24 to 32, wherein the waterproofing polymer exhibits a combination of Mw >2500 Da and <1,000,000 Da as measured by GPC using standard linear polystyrene, and a viscosity of the neat polymer of >50,000 cP and <5,000,000 cP at 25°C.

Claims

1. 1. A water-in-oil formulation comprising 1 to 5 weight percent, based on the total weight of the formulation, of a waterproofing polymer, said waterproofing polymer being a completely non-sequential reaction product of the following components: (i) polyglycerols, including combinations of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, and octaglycerol; (ii) hydrogenated C36 dimer acid, and (iii) isostearic acid, A water-in-oil formulation wherein (i), (ii) and (iii) are in a molar ratio of 1:0.5:

1.

2. 10. The water-in-oil formulation of claim 1, wherein the waterproofing polymer is produced from a polyglycerol comprising at least 40% by weight of a combination of diglycerol and triglycerol, based on the total weight of the polyglycerol.

3. 3. The water-in-oil blend of claim 1 or 2, wherein the waterproofing polymer exhibits a combination of Mw >2500 Da and <1,000,000 Da as measured using standard linear polystyrene by GPC, and a viscosity of the neat polymer of >50,000 cP and <5,000,000 cP at 25°C.

4. 1. A water-in-oil sunscreen formulation comprising the following individual components: (a) at least one sunscreen active, and (b) 1-5 wt. % of a waterproofing polymer, based on the total weight of the formulation, wherein the waterproofing polymer is a completely non-sequential reaction product of the following components: (i) polyglycerols, including combinations of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, and octaglycerol; (ii) hydrogenated C36 dimer acid, and (iii) isostearic acid, A water-in-oil sunscreen formulation wherein (i), (ii) and (iii) are in a molar ratio of 1:0.5:

1.

5. 5. The water-in-oil sunscreen formulation of claim 4, wherein the waterproofing polymer is formed from a polyglycerol comprising at least 40% by weight of a combination of diglycerol and triglycerol, based on the total weight of the polyglycerol.

6. 6. The water-in-oil sunscreen formulation of claim 4 or 5, further comprising at least one water-in-oil emulsifier.

7. The sunscreen active agent is para-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digalloyl trioleate, ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, lawsone with dihydroxyacetone, red petrolatum, ethylhexyl triazone, dioctyl benzoate. Benzylbutamide triazone, benzylidene malonate polysiloxane, terephthalidene dicamphorsulfonic acid, phenyl dibenzimidazole tetrasulfonate disodium, diethylamino hydroxybenzoyl hexyl benzoate, bis-diethylamino hydroxybenzoyl benzoate, bis-benzoxazoyl phenyl ethylhexyl imino triazine, drometrizole trisiloxane, methylene bis-benzotriazolyl tetramethyl butyl phenol, bis-ethylhexyloxyphenol methoxyphenyl triazine, 4-methyl Benzylidene camphor, homosalate, butyl methoxydibenzoylmethane, octocrylene, octyl salicylate, bemotrizinol and isopentyl 4-methoxycinnamate, benzophenone-3 (BP3), benzophenone-4 (BP4), homosalate (HMS), 2-ethylhexyl salicylate (EHS), ethylhexyl dimethyl PABA (OD-PABA), 4-p-aminobenzoic acid (PABA), phenylbenzimidazole sulfonic acid (PMDSA), disodium phenyldibenzimidazole tetrasulfonate (bisdisulfonate) Lysole disodium), ethylhexyl triazone (OT), diethylhexyl butamido triazone (DBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT), drometrizole trisiloxane (DRT), methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, Biscotrimazole), 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM, Avobenzone), ethylhexyl methoxycinnamate (OMC), isoamyl p-methoxycinnamate (IMC, Amiloxate),7. The water-in-oil sunscreen formulation of any one of claims 4 to 6, wherein the at least one member is selected from the group consisting of terephthalylidene dicamphorsulfonic acid (PDSA), 3-benzylidene camphor (3BC), benzylidene camphorsulfonic acid (BCSA), 4-methylbenzylidene camphor (4-MBC), polyacrylamidomethylbenzylidene camphor (PBC), camphor benzalkonium methosulfate (CBM), titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and mixtures thereof.

8. 8. A water-in-oil sunscreen formulation according to any one of claims 4 to 7, wherein the waterproofing polymer exhibits a combination of Mw >2500 Da and <1,000,000 Da as measured using linear polystyrene standards by GPC, and a viscosity of the neat polymer of >50,000 cP and <5,000,000 cP at 25°C.

9. 10. A method of protecting a user who is about to be exposed to or has already been exposed to the sun from the damaging effects of exposure to the sun, comprising the step of applying to the skin of said user an effective amount thereof of a water-in-oil sunscreen formulation according to any one of claims 4 to 8.

10. 1. A method for waterproofing a sunscreen formulation containing at least one sunscreen active, comprising incorporating into said sunscreen formulation 1 to 5 wt. % of a waterproofing polymer, based on the total weight of the formulation, wherein said waterproofing polymer is a fully non-sequential reaction product of the following components: (i) polyglycerols, including combinations of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, and octaglycerol; (ii) hydrogenated C36 dimer acid, and (iii) isostearic acid, wherein (i), (ii) and (iii) are in a molar ratio of 1:0.5:

1.

11. 11. The method of claim 10, wherein the waterproofing polymer is produced from a polyglycerol comprising at least 40% by weight of a combination of diglycerol and triglycerol, based on the total weight of the polyglycerol.

12. 12. The method of claim 10 or 11, wherein the waterproofing polymer exhibits a combination of Mw > 2500 Da and < 1,000,000 Da as measured by GPC using linear polystyrene standards, and a viscosity of the neat polymer of > 50,000 cP and < 5,000,000 cP at 25°C.

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