Sunscreen compositions containing a combination of linear ultraviolet radiation absorbing polyethers and other ultraviolet screening compounds

Abstract

The present invention relates to a sunscreen composition comprising a combination of a linear UV radiation absorbing polyether comprising covalently bound UV chromophores and at least one non-polymeric UV screening compound.

Description

Technical Field

[0001] This invention relates to locally acceptable sunscreen compositions comprising linear UV-absorbing polyethers and other additional UV-blocking compounds, sunscreen products prepared from such sunscreen compositions, and methods for protecting the stratum corneum. Background Technology

[0002] Skin aging is not simply a matter of time; it is also caused by exposure to various environmental stresses, such as ultraviolet (UV) radiation, which lead to the formation of free radicals in the skin. Prolonged exposure to various environmental stresses, such as ultraviolet (UV) radiation from the sun, can lead to the formation of free radicals in the skin, resulting in skin diseases and erythema, as well as increasing the risk of skin cancers such as melanoma, and accelerating skin aging, such as causing the skin to lose elasticity and wrinkles.

[0003] Depending on the wavelength, UV radiation causes different types of skin damage. UV-B radiation (approximately 290 to 320 nm) is responsible for sunburn and can cause skin cancer. UV-A radiation (approximately 320 to 400 nm) causes sunburn and can induce skin cancer, while also producing tanning. Furthermore, the harmful effects of UV-B radiation can be exacerbated by UV-A radiation. Therefore, effective sunscreens preferably contain at least one UV-A and UV-B filter, as well as a broadband UV filter covering the entire range from approximately 290 nm to approximately 400 nm, to protect human skin from sun damage.

[0004] The level of UV protection provided by a sunscreen composition is directly related to the amount and type of UV-blocking compounds present therein. The more UV-blocking compounds present, the greater the level of UV protection.

[0005] There are numerous commercially available sunscreen compositions, each with varying abilities to shield the body from ultraviolet (UV) radiation. However, providing sunscreen compositions that offer strong UV protection remains a significant challenge. Adding further constraints to the sunscreen composition (e.g., gentleness) further complicates the process of obtaining sunscreen agents with diverse properties.

[0006] The present invention provides a mild and aesthetically pleasing sun protection composition comprising a combination of linear UV-absorbing polyethers and other additional UV-blocking compounds. Summary of the Invention

[0007] This invention includes sunscreen compositions comprising a combination of polymer compositions including a linear ultraviolet-absorbing polyether (which contains covalently bonded UV chromophores) and at least one additional UV-blocking compound. Such sunscreen compositions provide unexpected synergistic protection against ultraviolet radiation. Detailed Implementation

[0008] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. As used herein, unless otherwise specified, all hydrocarbon groups (e.g., alkyl, alkenyl) may be straight-chain or branched groups. As used herein, unless otherwise specified, the term "molecular weight" refers to weight-average molecular weight (Mw).

[0009] Unless otherwise defined, all concentrations refer to concentrations based on the weight of the composition. Similarly, unless otherwise specifically defined, the term "substantially free" with respect to a class of ingredients means that the particular ingredient is present at a concentration below that required for the particular ingredient to effectively deliver its beneficial effects or properties, for example, about 1% or less, or about 0.5% or less.

[0010] As used herein, “UV absorption” refers to a material or compound, such as a polymeric or nonpolymeric sunscreen or chemical component, that absorbs radiation in a portion of the ultraviolet spectrum (290 nm to 400 nm), such as having at least about 1000 mol of light at least one wavelength within the ultraviolet spectrum defined above. -1 cm -1 Those with extinction coefficients. The SPF values ​​disclosed herein and protected by the claims are determined using the in vitro methods described below.

[0011] Linear UV-absorbing polyether

[0012] Embodiments of the present invention relate to compositions comprising linear ultraviolet radiation-absorbing polyethers (i.e., "UV-absorbing polyethers"). A UV-absorbing polyether is defined as a polyether that absorbs radiation in a portion of the ultraviolet spectrum (wavelengths between 290 and 400 nm). Linear UV-absorbing polyethers have a weight-average molecular weight (Mw) suitable for reducing or preventing the absorption of chromophores through the skin. According to one embodiment, a suitable molecular weight for a UV-absorbing polyether is a Mw greater than 500. In one embodiment, M is in the range of about 500 to about 50,000. In another embodiment, M is in the range of about 1,000 to about 20,000, such as about 1,000 to about 10,000.

[0013] This document describes compositions comprising linear UV-absorbing polyethers. Those skilled in the art will recognize that "polyether" indicates that the UV-absorbing polymer contains multiple ether functional groups covalently bonded to each other. The "main chain" of a linear UV-absorbing polyether refers to the longest continuous sequence of covalently bonded ether functional groups. Other smaller groups of covalently bonded atoms are considered as side groups branching from the main chain.

[0014] According to certain embodiments, linear UV-absorbing polyethers contain glycerol repeating units and are therefore characterized as polyglycerol. The term "glycerol repeating unit" (also referred to herein as "glycerol residual unit") means a glycerol unit that does not include a nucleophilic group (such as a hydroxyl group). Glycerol residual units include ether functional groups and, for both linear and dendritic residual units, are typically represented as C3H5O (Green Chemistry, Rokicki et al., 2005, 7, 52). Suitable glycerol residual units include the dehydrated form of the following glycerol unit (i.e., removing 1 mole of water): linear-1,4(L... 1,4 ) Glyceryl group; linear-1,3(L 1,3 ) Glyceryl repeating unit; dendritic (D) glyceryl unit; terminal -1,2(T 1,2 ) unit; and end -1,3(T 1,3 Examples of the linear glycerol residual unit and terminal unit are shown below (to the right of the arrow). The corresponding glycerol unit before dehydration is also shown (to the left of the arrow; containing the hydroxyl group): Straight chain - 1,4(L 1,4 ) Glyceryl repeating unit

[0015] Straight chain - 1,3(L 1,3 ) Glyceryl repeating unit

[0016] terminal -1,2(T) 1,2 )unit

[0017] and terminal -1,3(T 1,3 )unit

[0018] The composition comprises a linear UV-absorbing polyether containing covalently bonded ultraviolet radiation absorbing chromophores (“UV chromophores”). The term “linear” means that the UV-absorbing polyether has an unbranched main chain.

[0019] According to certain embodiments, the linear UV-absorbing polyether comprises any or both of the repeating units shown in Formula IA and Formula IIB below:

[0020] Formula IA: Repeating unit of linear UV-absorbing polyether

[0021] Formula IIB: Repeating unit of linear UV-absorbing polyether

[0022] In formulas IA and IIB, Y represents the UV chromophore, as described below.

[0023] Exemplary examples of linear UV-absorbing polyethers containing covalently bonded UV chromophores are shown in Formula IIIC.

[0024]

[0025] Formula IIIC: Linear UV-absorbing polyether

[0026] In the structure shown in Formula IIIC, X is a terminal functional group or part of the polymer backbone; R is a side group attached to the polymer backbone, and X is a terminal group.

[0027] X and R may be the same or different. X and R may be independently selected from, for example, hydrogen, straight-chain alkyl, alkenyl or alkynyl hydrocarbon chains, straight-chain siloxanes, etc. In one embodiment, group X represents octadecane. Y represents a UV chromophore, and the group represented by Y is described below. The proportion of ether repeating units with substituent Y is a real number expressed by Formula 1.

[0028] Formula 1

[0029] Where both m and n represent real numbers between 0 and 1, and the sum of n and m equals 1. In one embodiment, m = 1 and n = 0 (the linear UV-absorbing polyether is a homopolymer and contains repeating units of formula IA). In another embodiment, m < 1 (the polymer is a copolymer with R and Y side groups). For copolymers containing R and Y side groups, the distribution of side groups R and Y along the polymer chain can be varied to obtain optimal polymer properties. In one embodiment, the polymer is a random copolymer, and the groups R and Y are statistically distributed along the polymer chain. In another embodiment, the linear UV-absorbing polyether is a block copolymer consisting of alternating segments of a polymer backbone functionalized with a larger proportion of R or Y. In another embodiment, the distribution of side groups R and Y along the polymer backbone is somewhere between the boundary conditions of block copolymers and statistically random copolymers. In formula IIIC, the integers o and p represent the number of CH2 groups in the repeating units with Y and R.

[0030] Different R-side groups can be introduced by using other comonomers during the polymerization process. The size, chemical composition, weight percentage, and position in the main chain of these comonomers can be varied to alter the physical and chemical properties of the final UV-absorbing linear polyether. Examples of comonomers that can be incorporated into UV-absorbing polyethers include, but are not limited to, ethylene oxide, propylene oxide, and glycidyl ethers (such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether).

[0031] It will be apparent to those skilled in the art that polyethers of the types shown in Formulas IA, IIB, and IIIC can be obtained via various synthetic routes. These routes involve ring-opening polymerization of cyclic ether monomers and, optionally, comonomers. The size of the ring in the cyclic ether monomer determines the value of o or p, and the resulting main chain structure of the linear UV-absorbing polyether. For monomers or comonomers that are epoxides (three-membered rings containing two carbon atoms and one oxygen atom), the value of o or p in the resulting linear UV-absorbing polyether is 1. Repeating units obtained by using epoxide comonomers are shown in structure A of Formula IV. For (co)monomers that are oxetanes (four-membered rings containing three carbon atoms and one oxygen atom), the value of o or p in the resulting linear UV-absorbing polyether is 2. Repeating units obtained by using oxetane comonomers are shown in structure B of Formula IV. The length of the alkyl chain within each monomer type can be selected to change the properties of the linear UV-absorbing polyether. In one embodiment, both o and p are equal to 1. An example of this is when the repeating units with both Y and R are derived from either an epoxide monomer (o=p=1) or an oxetane monomer (o=p=2). In another embodiment, o and p are not equal. An example of this is when the repeating unit with the UV chromophore Y is based on an epoxide monomer (o=1), and the repeating unit with the group R is based on an oxetane monomer (p=2).

[0032]

[0033] Formula IV: Optional repeating unit

[0034] Suitable UV chromophores that can be covalently incorporated into the linear UV-absorbing polyether of the present invention include UV-absorbing triazoles (comprising a portion of a five-membered heterocyclic ring having two carbon atoms and three nitrogen atoms), such as benzotriazole. In another embodiment, the structure represented by Y comprises or has a side-UV-absorbing triazine (comprising a six-membered heterocyclic ring having three nitrogen atoms and three carbon atoms). Suitable UV chromophores include those with UVA radiation absorbance. Other suitable UV chromophores are those with absorbance in the UVB region. In one embodiment, the UV chromophore absorbs in both the UVA and UVB regions. In one embodiment, when the linear UV-absorbing polyether is cast into a film, at least about 1000 mol of light can be produced for at least one wavelength in this wavelength range. -1 cm -1 Preferably at least about 2000 mol -1 cm -1 More preferably at least about 4000 mol -1 cm -1The molar extinction coefficient. In one embodiment, the molar extinction coefficient is at least about 1000 mol in at least 40% of the wavelengths in this portion of the spectrum. -1 cm -1 Examples of UV chromophores that absorb UVA include triazoles such as benzotriazole, such as hydroxyphenylbenzotriazole; camphor, such as benzylidene camphor and its derivatives (such as dicamphor sulfonic acid terephthalate); and dibenzoylmethane and its derivatives.

[0035] In one embodiment, the UV chromophore is a benzotriazole having the structure represented in Formula V, providing photostability and strong UVA absorbance.

[0036]

[0037] Formula V: Benzotriazole UV-absorbing chromophore

[0038] Each R 14 Independently selectable from hydrogen, C1-C 20 The group consisting of alkyl, alkoxy, acyl, alkyloxy, alkylamino, and halogen; R 15 Independently selectable from hydrogen, C1-C 20 The group consisting of alkyl, alkoxy, acyl, alkyloxy, alkylamino, and halogen groups, R21 is selected from C1-C. 20 The group consisting of alkyl, alkoxy, acyl, alkyloxy, and alkylamino groups. R 15 Or R 21 The groups may include functional groups that allow attachment to the polymer. Compounds with structures similar to those in Formula V are described in U.S. Patent 5,869,030 and include, but are not limited to, methylenebis-benzotriazolyltetramethylbutylphenol (a compound sold by BASF Corporation, Wyandotte, Michigan under the trade name TINSORB M). In one embodiment, the UV-absorbing triazole is derived from a transesterification product of 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionic acid and polyethylene glycol 300 (also available from BASF as TINUVIN 213). In another embodiment, the UV-absorbing triazole is 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-C 7-9- Branched and straight-chain alkyl esters (available commercially from BASF as TINUVIN 99). In another embodiment, the UV-absorbing group comprises a triazine moiety. An exemplary triazine is 6-octyl-2-(4-(4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-3-hydroxyphenoxy)propionate (a compound marketed by BASF Corporation, Wyandotte, Michigan under the trade name TINUVIN 479).

[0039] In another embodiment, the UV chromophore is the UVB absorption portion. A UVB absorbing chromophore means that the UV chromophore has absorbance in the UVB portion (290 to 320 nm) of the ultraviolet spectrum. In one embodiment, the criteria considered for a UVB absorbing chromophore are similar to those described above for UVA absorbing chromophores, except that the wavelength range is 290 nm to 320 nm. Examples of suitable UV-B absorbing chromophores include 4-aminobenzoic acid and its alkyl esters; anthranilic acid and its alkyl esters; salicylic acid and its alkyl esters; hydroxycinnamic acid and its alkyl esters; dihydroxy-, dicarboxy-, and hydroxycarboxybenzophenone and their alkyl esters or acyl halide derivatives; dihydroxy-, dicarboxy-, and hydroxycarboxychalcone and their alkyl esters or acyl halide derivatives; dihydroxy-, dicarboxy-, and hydroxycarboxycoumarin and their alkyl esters or acyl halide derivatives; benzoyl malonate (benzyl malonate); benzimidazole derivatives (such as phenylbenzimidazole sulfonate PBSA), benzoxazole derivatives, and other suitable functionalizing agents capable of copolymerizing in the polymer chain. In another embodiment, the UV-absorbing polyether contains more than one UV chromophore or more than one class of UV chromophores.

[0040] According to some embodiments, the linear UV-absorbing polyethers available in this invention can be synthesized by ring-opening polymerization of a suitable cyclic ether monomer to form a polyether, followed by covalently attaching a UV chromophore to a side functional group (“post-polymerization attachment”). According to some other embodiments, the linear UV-absorbing polyethers can be synthesized by polymerizing a cyclic ether monomer, wherein the monomer itself contains a covalently attached UV chromophore (i.e., “direct polymerization”).

[0041] Furthermore, as those skilled in the art will recognize, linear UV-absorbing polyethers that can be used in the topical compositions of the present invention are prepared via polymer synthesis. The synthesis of UV-absorbing polyethers typically yields a reaction product (hereinafter referred to as the "polymer composition") that is a mixture of linear UV-absorbing polyethers of various molecular weights. In some other embodiments, the reaction product may additionally contain a small amount of unpolymerized material (in addition to the linear UV-absorbing polyether), which can be removed using techniques known in the art. According to some embodiments, unpolymerized material (e.g., partially reacted or unreacted monomers or other reactants) can be partially or completely removed prior to inclusion in the topical compositions of the present invention using, for example, solvent extraction or supercritical CO2 purification.

[0042] According to some embodiments, the polymer composition to be incorporated into a local composition of the present invention comprises about 50% or more of a linear UV-absorbing polyether containing covalently bonded UV chromophores. According to some other embodiments, the polymer composition comprises about 75% or more of a linear UV-absorbing polyether containing covalently bonded UV chromophores. According to some other embodiments, the polymer composition comprises about 90% or more of a linear UV-absorbing polyether, such as about 95% or more.

[0043] According to certain embodiments, the sunscreen composition has low polydispersity. For example, the polydispersity index of the polymer composition may be about 1.5 or less, such as about 1.2 or less. The polydispersity index is defined as Mw / M N (That is, weight-average molecular weight Mw and number-average molecular weight Mw) N (ratio). According to certain other embodiments, the polymer composition contains 50% by weight or more of a specific linear UV-absorbing polyether molecule.

[0044] The polydispersity of the polymer composition can be kept low, for example, by specific synthetic processes such as ring-opening polymerization and deprotection of cyclic ether monomers (described below). Alternatively, techniques known in the art, such as supercritical CO2, can be used to treat the polymer composition to purify it (e.g., before or after the attachment of UV chromophores).

[0045] Synthesizing linear UV-absorbing polyethers by post-polymerization and attachment of UV chromophores may include the steps of ring-opening polymerization of cyclic ether monomers to form a polyether having protected groups; deprotecting the polyether to remove at least some of the protecting groups; and attaching UV chromophores to the deprotected linear UV-absorbing polyether to form a linear UV-absorbing polyether having covalently bonded linear UV chromophores.

[0046] An example of post-polymerization attachment of a linear UV-absorbing polyether is schematically shown in Formula VI. Initiator I is used to induce the polymerization of the cyclic ether monomer M, thereby producing polymer P0, wherein the side hydroxyl functional groups are protected by protecting groups (P). Polymer P0 is subjected to conditions that remove the protecting groups P, thereby providing deprotected polymer P. d Finally, the UV chromophore Y is attached to the polymer P. d The side hydroxyl groups provide the desired final polymer P. f .

[0047]

[0048] Formula VI: Synthesis of UV-absorbing chromophores via post-polymerization functionalization

[0049] Ring-opening polymers of cyclic ethers, such as monomer M in Formula VI, can be achieved using various methods, including cationic and anionic ring-opening polymerization. In one embodiment, the polymerization is performed by anionic ring-opening polymerization. Monomer M in Formula VI is in the form of glycidyl, wherein the primary hydroxyl group is masked by a protecting group P. Polymerization of unprotected glycidyl leads to the formation of highly branched polymers (US7988953B2, Tokar, R. et al., *Macromolecules*, 1994, 27, 320-322; Sunder, A. et al., *Macromolecules*, 1999, 4240-4246; Rokicki, G. et al., *Green Chemistry*). Green chemistry 2005, 7 Conversely, anionic polymerization of glycidyl derivatives with protected primary hydroxyl groups can produce linear polyethers, as shown by structure P0 in formula VI (Taton, D. et al., *Macromolecular Chemistry and Physics*, 1994, p. 529). 195 Period, 139-148: Erberich, M. et al., "Macromolecules" Macromolecules ) 2007 40 Issues, 3070-3079: Haouet, A. et al., *European Journal of Polymers* European Polymer Journal ( )》1983, Issue 19, pp. 1089-1098: Obermeier, B. et al., *Bioconjugated Chemistry*, 2011, 22 , 436-444: Lee, BF et al., in the Journal of Polymer Science (Journal of Polymer Science.)(See Part A of *Polymer Chemistry*, 2011, 49, 4498-4504). The protected cyclic ether monomers are not limited to epoxide derivatives, but include functionalized cyclic ethers containing 3 to 6 adjacent atoms. In another embodiment, monomer M is an oxobutane derivative containing a protected primary hydroxyl group.

[0050] The term "protection" refers to the selective derivatization of functional groups in multifunctional moleculees by a portion that prevents covalent modification at those functional groups. The portion used as a protecting group typically attaches to the desired functional group with excellent chemical yield and can be selectively removed with good yield as needed, thereby exposing the original functional group. Hydroxyl protecting groups include, but are not limited to, ethers, such as methyl, methoxymethyl (MOM), methylthiomethyl (MTM), tert-butylthiomethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), p-methoxybenzyloxymethyl (PMBM), (4-methoxyphenoxy)methyl (p-AOM), tert-butoxymethyl, 4-pentenyloxymethyl (POM), siloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, and 2-(trimethylsilyl)ethoxy Methyl (SEMOR), Tetrahydropyranyl (THP), Allyl, 3-Bromotetrahydropyranyl, Tetrahydrothiopyranyl, 1-Methoxycyclohexyl, Benzyloxy-2-fluoroethyl, 2,2,2-Trichloroethyl, 2-Trimethylsilylethyl, 2-(Phenylselenoethyl)ethyl, Tert-butyl, Allyl, p-Chlorophenyl, p-Methoxyphenyl, 2,4-Dinitrophenyl, Benzyl, p-Methoxybenzyl, 3,4-Dimethoxybenzyl, o-Nitrobenzyl, p-Nitrobenzyl, p-Halobenzyl, 2,6-Dichlorobenzyl, Trimethylsilyl (TMS), Triethylsilyl (TES), Triisopropylsilane TIPS, tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), tribenzylsilyl; esters, such as formate, benzoylformate, acetate, chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, methoxyacetate, triphenylmethoxyacetate, phenoxyacetate, p-chlorophenoxyacetate, 3-phenylpropionate, 4-oxovalerate (levulinoyldithioacetal), 4,4-(ethylidene dithio)valerate (levulinoyldithioacetal), neopentyl The esters include esters such as adamantide, crotonate, 4-methoxycrotonate, benzoate, p-phenylbenzoate, 2,4,6-trimethylbenzoate (mesitoate), and carbonates such as alkylmethyl carbonate, 9-fluorenylmethyl carbonate (Fmoc), alkylethyl carbonate, 2,2,2-trichloroethylalkyl carbonate (Troc), 2-(trimethylsilyl)ethyl carbonate (TMSEC), 2-(benzenesulfonyl)ethyl carbonate (Psec), 2-(triphenylphosphine)ethyl carbonate (Peoc), and alkyl isobutyl carbonate. In one embodiment, the protecting group is ethoxyethyl ether; in another embodiment, the protecting group is allyl ether.

[0051] Removing the protecting groups from the protected linear polyether P0 to produce the deprotected polymer P d This is achieved using a method complementary to the selection of the protecting group P; such methods are well known to those skilled in the art. In one embodiment, the primary hydroxyl group of the cyclic ether monomer is protected to 1-ethoxyethyl ether; dissociation of this protecting group to produce a deprotected polymer is achieved using aqueous acidic conditions such as aqueous acetic acid, aqueous hydrochloric acid, or an acidic ion exchange resin. In another embodiment, the primary hydroxyl group of the cyclic ether monomer is protected to allyl ether; dissociation of this protecting group to produce a deprotected polymer is achieved by isomerizing the allyl ether to a vinyl ether by treatment with a potassium alkoxide followed by treatment with an aqueous acid, isomerization using a transition metal catalyst followed by acidic hydrolysis, or direct removal using a palladium(O) catalyst and a nucleophilic scavenger.

[0052] The anionic ring-opening polymerization of monomer M shown in Formula VI is induced by alkoxide I. Examples of alkoxides suitable for inducing the ring-opening polymerization of cyclic ether monomers include, but are not limited to, linear C3 to C4 chains. 30 Potassium salts of hydrocarbon alcohols, polyethylene glycol methyl ethers, and methanol-terminated polysiloxanes. In one embodiment, the initiator for anionic ring-opening polymerization is a potassium salt of octadecyl alcohol. Another embodiment of the invention uses multifunctional initiators, including but not limited to polyoxyethylene, such as polyethylene glycol, polypropylene glycol, or poly(tetramethylene ether) glycol; polyesters, such as poly(ethylene adipate), poly(vinyl succinate); copolymers having oxyethylene and ester functional groups in the main chain, such as poly[di(ethylene glycol) adipate]; and lower molecular weight alcohols, such as 1,4-butanediol, 1,6-hexanediol, or neopentyl glycol.

[0053] Depending on the functional groups on the polyether side, various methods known to those skilled in the art can be used to attach chromophores to the polymer backbone. The following methods are exemplary and do not represent an exhaustive list of possible ways to attach UV chromophores to the polymer backbone. In polymers having free hydroxyl groups (such as those with structure P in formula VI) dIn the case described, various methods well known to those skilled in the art can be used to covalently attach a UV chromophore containing a carboxylate group to a polymer. A condensation agent can be used to form a covalent bond between the UV chromophore and the carboxylic acid and hydroxyl group on the polymer that generates the ester bond. In one embodiment, the condensation agent is N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride. A transition metal catalyst can also be used to attach the carboxylic acid of the UV chromophore to the hydroxyl group on the polymer via an ester bond; in one embodiment, the catalyst is tin(II) isooctanoic acid. The UV chromophore can also be attached to the polymer by converting the carboxylic acid of the UV chromophore to the corresponding acyl chloride. The acyl chloride reacts with the hydroxyl group on the functionalized polymer to form an ester bond; in one embodiment, a thionyl chloride is used to perform this conversion to the acyl chloride. The UV chromophore carboxylic acid can also be converted to an isocyanate via the Curtius rearrangement of the intermediate acid azide. The chromophore isocyanate reacts with the hydroxyl group on the functionalized polymer to form an angiocarbamate bond. In another embodiment, the carboxylic acid on the UV chromophore can be converted to an ester and attached to a hydroxyl group on the main chain via transesterification. This can be achieved by converting the carboxylic acid to an ester using a low-boiling alcohol such as methanol. Transesterification is performed by reacting the chromophore ester with a polymer containing side-chain hydroxyl groups using an acid catalyst (e.g., p-toluenesulfonic acid).

[0054] In the case of polymers containing free hydroxyl groups, various methods well known to those skilled in the art can be used to covalently attach hydroxyl-containing UV chromophores to polyethers. In one embodiment, the hydroxyl groups on the UV chromophore can be activated by nucleophilic substitution using reagents such as methanesulfonyl chloride or p-toluenesulfonyl chloride. Then, under alkaline conditions, the hydroxyl groups on the main chain can replace the resulting methanesulfonic acid or toluenesulfonate to form an ether bond between the polymer and the UV chromophore. In another embodiment, the hydroxyl groups on the UV chromophore can be converted to chloroformates using reagents such as phosgene, diphosgene, or triphosgene. The resulting UV chromophore chloroformate can react with the hydroxyl groups on the polymer main chain to form a carbonate bond between the polymer and the UV chromophore. In polymers containing free hydroxyl groups (such as those with structure P in formula VI), d In the case described above, various methods well known to those skilled in the art can be used to covalently attach an amine-containing UV chromophore to the polymer. In one embodiment, the hydroxyl groups on the polymer can be converted into the corresponding chloroformate using reagents such as phosgene, diphosgene, or triphosgene; then, the amine-functionalized UV chromophore can react with the polymer chloroformate to form a urethane bond between the UV chromophore and the polyether.

[0055] In another embodiment, after attaching an acid, acyl chloride, or isocyanate-functionalized UV chromophore, some of the hydroxyl groups on the linear polymer backbone are retained. These unreacted hydroxyl groups can be used to attach other monofunctional side groups to improve the physical and chemical properties of the polymer. Examples of hydroxyl-reactive functional groups include, but are not limited to, acyl chlorides and isocyanates. Specific examples of hydroxyl-reactive side groups include palmitoyl chloride and octadecyl isocyanate. Other examples of groups that may be on the polymer side and are sites for covalently attaching UV chromophores include, but are not limited to, conjugated alkenes, amines, and carboxylic acids.

[0056] In another embodiment, the polyether backbone is polyglycerol having side hydroxyl groups or hydrophobic groups, such as polyglycerol esters, for example, decaglyceryl monostearate sold by Lonza in Allendale, NJ under the trade name POLYALDO 10-1-S, or tetradecyl monostearate sold by Lonza in Allendale, NJ under the trade name POLYALDO 14-1-S. The side hydroxyl groups can react with UV chromophores containing complementary functional groups as described above to obtain a linear UV-absorbing polyether. In this embodiment, the polymer composition will be, for example, a reaction product of a polyglycerol ester and a UV chromophore having functional groups suitable for covalent attachment to the polyglycerol ester. In addition to the aforementioned functional groups, suitable functional groups on the UV chromophore also include carboxylic esters and isocyanates. The resulting polymer composition may comprise a linear UV-absorbing polyether having repeating units shown in Formula IIB. Depending on the percentage of linear material present in the polyglycerol, the resulting polymer composition may also contain some non-linear (e.g., cyclic) components.

[0057] As described above, the synthesis of suitable polymer compositions comprising linear UV-absorbing polyethers can also be achieved by polymerizing UV chromophores covalently modified with cyclic ether groups (direct polymerization). This is shown in Formula VII, where Y represents the UV chromophore and o represents the ring size characteristic of the cyclic ether monomer.

[0058]

[0059] Formula VII: Direct polymerization of UV chromophores covalently attached to cyclic ethers

[0060] Additional UV shielding compounds

[0061] The sunscreen composition of the present invention further comprises at least one additional UV-blocking compound. The additional UV-blocking compounds can be classified as UV-absorbing compounds or UV-blocking compounds according to the type of protection they provide.

[0062] A type of additional UV-blocking compound that may be included in a sunscreen composition may include a UV-absorbing compound. Such UV-absorbing compounds included in a sunscreen composition can be characterized as “organic” sunlight filters. This “organic” UV-absorbing compound (often referred to as a “monomeric, organic UV absorber”) is typically an aromatic compound conjugated with a carbonyl moiety substituted at the ortho or para position of an aromatic ring.

[0063] Traditional organic daylight filters are small aromatic molecules with a molecular weight of <900 g / mol. Examples of organic nonpolymeric UV-absorbing compounds include, but are not limited to: methoxycinnamate derivatives, such as octyl methoxycinnamate and isoamyl methoxycinnamate; camphor derivatives, such as 4-methylbenzyl camphor, camphor benzalkonium methyl sulfate, and terephthalimide dicamphor sulfonic acid; salicylate derivatives, such as octyl salicylate, triethanolamine salicylate, and homosalate; sulfonic acid derivatives, such as phenylbenzimidazole sulfonic acid; benzoin derivatives, such as dihydroxybenzone, sulphone, and oxybenzone; benzoic acid derivatives, such as aminobenzoic acid and octyldimethyl-p-aminobenzoic acid; octocrylene and other β,β-diphenylacrylates; dioctylbutyrylaminotriazinone; octyltriazinone; butyl methoxydibenzoylmethane; cresoltrazolium trisiloxane; and menthyl anthranilate.

[0064] Preferably, "organic" UV-absorbing compounds include avobenzone, oxybenzone, octocrylene, salicylate derivatives (homosalate and ethylhexyl salicylate), cinnamon derivatives (octyl methoxycinnamate [OMC]), triazolone derivatives (Uvinul T150 [ethylhexyl triazine]; UVASorb HEB [diethylhexylbutyramide triazine]; Tinosorb S [bisethylhexyloxyphenol methoxyphenyl triazine]), benzoate derivatives (Uvinul A Plus [diethylaminohydroxybenzoylhexyl benzoate]), benzotriazole derivatives (Mexoryl XL [cresoltrazol trisiloxane]), and camphor derivatives (Mexoryl SX [Etzschul]); p-phenylenemethylene dicamphor sulfonic acid). Aminoanionate derivatives (such as meladyl) are generally not commonly used filters due to their low efficacy.

[0065] Avobenzone (a dibenzoylmethane derivative) is one of the most effective UVA absorbing filters globally, and it is the only UVA absorbing organic daylight filter approved in the United States. However, avobenzone is prone to photostability due to its enol-keto tautomerism (Kokler et al. 2012). The enol form of avobenzone absorbs in UVA (315 to 400 nm), while the diketo form absorbs in UVC (200 to 280 nm) and is readily degraded (Kockler et al. 2012). Other photostabilizing ingredients must be used in combination with avobenzone to prevent photo-induced degradation (Cole et al. 2009). To achieve photostability of avobenzone, it must be combined with ingredients that are effective in both triple and single quenching. Examples of triple quenchers include UV filters such as octocrylene, 4-methylbenzyl camphor (pre-US), Tinosorb S (pre-US), or emollients such as diethylhexyl 2,6-naphthalenedicarboxylate (Cole et al. 2009). Furthermore, higher levels of oxybenzone are known to stabilize avobenzone via a single quenching mechanism (Cole et al. 2009). The combination of single and triple quenchers is most effective in stabilizing avobenzone.

[0066] Cinnamic acid is a very effective UVB absorber, but it also has issues related to photostability. OMC is a member of the cinnamic family known to react with avobenzone to prepare non-UV light-absorbing products. Therefore, the combination of avobenzone and OMC is unfavorable and should be avoided due to increased light instability (Cole et al. 2009; Ou-Yang et al. 2010).

[0067] Salicylate derivatives are photostable UVB absorber filters with long lifespans. They are excellent solubilizing agents for crystalline UV filters, including oxybenzone and avobenzone. However, these filters have relatively low absorption efficiency.

[0068] Oxybenzone (a benzophenone derivative) is used in many US sunscreen formulations, exhibiting absorbance in the UVB (290–320 nm) and UVA II (320–340 nm) regions. Padimate O is a derivative of para-aminobenzoic acid, which is liquid and oil-soluble. It is a very effective UVB filter with one of the highest molar extinction coefficients among approved filters. Due to concerns about the parent molecule para-aminobenzoic acid's association with allergic reactions, it is not widely used in products. Octocrylene is another oil-soluble UVB filter that has been widely used to provide enhanced Sun Protection Factor (SPF) values ​​and is also used to improve the photostability of avobenzone when used in combination. Ensolazole (phenylbenzimidazole sulfonic acid) is a water-soluble filter and is used to formulate lighter, less oily products, such as daily-use cosmetic moisturizers. Currently, in the US, it is not permitted to combine with avobenzone, and broad-spectrum protection must rely on other UVA absorbers such as zinc oxide.

[0069] Additional examples of “organic” UV-absorbing compounds include, but are not limited to: bis(ethylhexyloxyphenol)methoxyphenyltriazine; butylmethoxydibenzoylmethanediethylhexylbutyramidetriazine ketone; ethylhexyltriazine ketonediethylaminohydroxybenzoylhexylbenzoate; ethylhexyl methoxycinnamate; ethylhexyl salicylate; homosalate; octocrylene; methylenebisbenzotriazolyltetramethylbutylphenol; phenylbenzimidazole sulfonic acid; (2-{4-[2-(4-diethylamino-2-hydroxybenzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methyl ketone; BBDAPT; 4, 4'-[[6-[[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxyl]propyl]amino]-1,3,5-triazine-2,4-diyl]diimino]dibutyl bisbenzoate; benzyl malonate; and anthocyanin derivatives; bis(butylbenzoate)diaminotriazineaminopropylsiloxane; bis-ethylhexyloxyphenol methoxyphenyl triazine encapsulated in a polymer matrix); 2-(2H-benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4-methylphenol; 3-(4-methoxyphenyl)-2-acrylate-2-methylphenyl ester.

[0070] Other examples of “organic” UV-absorbing compounds include, but are not limited to: bis(ethylhexyloxyphenol)methoxyphenyltriazolylmethoxydibenzoylmethane; bis(ethylhexyl)butamide triazine; ethylhexyltriazine diethylaminohydroxybenzoyl benzoate; ethylhexyl methoxycinnamate; ethylhexyl salicylate; homosalate; octocrylene; methylenebisbenzotriazolyltetramethylbutylphenol; phenylbenzimidazole sulfonic acid; terphenyltriazine; (2-{4-[2-(4-diethylamino-2-hydroxybenzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methyl ketone; benzoin derivatives; bis(butylbenzoate)diaminotriazine aminopropylsiloxane; and bis(ethylhexyloxyphenol)methoxyphenyltriazine encapsulated in a polymer matrix.

[0071] In some embodiments of the present invention, the "organic" UV-absorbing compounds are selected from Table 1. (From a chapter in the Daly book)

[0072] ASEAN, Association of Southeast Asian Nations; EU, European Union; MBC, Methylbenzyl camphor; MERCOSUR, Southern Common Market, composed of Argentina, Brazil, Paraguay, Uruguay, and Venezuela; OMC, Octyl methoxycinnamate; PABA, Para-aminobenzoic acid; US, United States; UVA, Ultraviolet A; UVB, Ultraviolet B.

[0073] Another type of organic UV-absorbing compound is a polymer prepared from organic chromophore polymers attached to polysiloxane chains approved for use outside North America. With an average molecular weight >6000 Daltons, the molecule is envisioned to be large enough to reduce penetration through the skin, making it ideal for gentle applications. The polysiloxane backbone not only links the chromophores together but also provides a pleasing aesthetic effect on the skin or hair. Examples of polysiloxane UV-absorbing compounds include, without limitation, Parsol SLX and Polysilicone 15. These types of polysiloxane UV-absorbing compounds absorb in the UVB spectrum (λmax = 312) and are typically combined with UVA filters for broad-spectrum protection.

[0074] Another type of additional UV-shielding compound can include UV-blocking compounds. UV-blocking compounds reflect, absorb, or scatter UV radiation, and if present in sunscreen formulations, they reflect all ultraviolet, visible, and infrared light, thus enhancing sun protection. UV blockers are inorganic metal oxides, including titanium dioxide, zinc oxide, and certain other transition metal oxides. These inorganic compounds are typically solid particles with a diameter of about 0.1 micrometers to about 10 micrometers in their micronized and nano-sized form.

[0075] The following UV filters are preferred: Diethylaminohydroxybenzoyl benzoate (DH2O) Ethylhexyltriazinone, bis-ethylhexyloxyphenol methoxyphenyl triazine, Methylenebisbenzotriazolyltetramethylbutylphenol, Bis-ethylhexyloxyphenol methoxyphenyl triazine encapsulated in a polymer matrix Triphenyltriazine Ethylhexyl methoxycinnamate, Octocrylin, 1,1'-(1,4-piperazindiyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methyl ketone Titanium dioxide, Phenylenic acid, Zinc oxide, Ethylhexyl salicylate, Humosalt, Diethylhexylbutyramide triazinone, Isoamyl p-methoxycinnamate, Polysilicon 15, The preferred option is: Diethylaminohydroxybenzoyl benzoate (DH2O) Ethylhexyltriazinone, bis-ethylhexyloxyphenol methoxyphenyl triazine, Methylenebisbenzotriazolyltetramethylbutylphenol, Bis-ethylhexyloxyphenol methoxyphenyl triazine encapsulated in a polymer matrix Triphenyltriazine Ethylhexyl methoxycinnamate, Occrylonitrile, and 1,1'-(1,4-piperazindiyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl] ketone.

[0076] In one embodiment of the invention, the additional UV-absorbing compound is avobenzone.

[0077] Topical sunscreen compositions

[0078] The sunscreen compounds described herein can be used in applications requiring UV absorption. For example, sunscreen compositions can be combined with suitable cosmetically acceptable carriers for cosmetic applications, or combined with other materials to reduce UV degradation of the materials (i.e., melt-blending the materials with a polymer composition, or coating the materials with a polymer composition). Incorporating linear UV-absorbing polyethers into such compositions of the present invention can provide enhanced SPF (primarily UVB absorbance), enhanced PFA (primarily UVA absorbance), or enhanced both. Cosmetically acceptable topical carriers are suitable for topical application to human skin and may include one or more of, for example, carriers (such as water, ethanol, isopropanol, emollients, humectants), and / or one or more of surfactants / emulsifiers, fragrances, preservatives, waterproof polymers, and similar ingredients commonly used in cosmetic formulations. Thus, sunscreen compositions can be formulated into sprays, lotions, gels, sticks, or other product forms using ingredients known in the art. Similarly, according to certain embodiments, human skin can be protected from UV radiation by topical application of a composition comprising a combination of linear UV-absorbing polyethers and other additional UV-shielding compounds.

[0079] According to certain other embodiments, the sunscreen composition may include additional UV-absorbing polymers and / or non-UV-absorbing, light-scattering particles that are different from the linear UV-absorbing polyethers defined herein. The additional UV-absorbing polymer is a molecule that may be represented as having one or more structural units that are periodically repeated (e.g., at least twice) to generate a molecule, and may be a UV-absorbing polyether different from those defined in this specification and protected by the claims.

[0080] The additional UV-absorbing polymer may have a molecular weight greater than about 1500. Examples of suitable additional UV-absorbing polymers include benzyl malonide silicones, including those described in U.S. Patent 6,193,959 to Bernasconi et al. Particularly suitable benzyl malonide includes "Parsol SLX", commercially available from DSM (Royal DSM NV) of Heerlen, Netherlands. Other suitable additional UV-absorbing polymers are disclosed in U.S. Patents 6,962,692; 6,899,866; and / or 6,800,274; including polymers of adipic acid with 2,2-dimethyl-1,3-propanediol and 3-[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]-2,2-dimethylpropyl 2-octyl dodecyl ester; sold under the trade name “POLYCRYLENE” and available from HallStar Company of Chicago, Illinois. When used, such additional UV-absorbing polymers may be used at concentrations of about 1% or more (e.g., about 3% or more).

[0081] Non-UV absorbing light-scattering particles are particles that do not absorb UV radiation but can enhance SPF by scattering incident UV radiation. Examples of non-UV absorbing light-scattering particles include solid particles having dimensions, such as an average diameter, of about 0.1 micrometers to about 10 micrometers. In some embodiments, non-UV absorbing light-scattering particles are hollow particles comprising an organic polymer or glass, or substantially composed of an organic polymer or glass. Suitable organic polymers include acrylic polymers, including acrylic / styrene copolymers, such as those known as SUNSPHERES, available from Dow Chemical of Midland, Michigan. Suitable glasses include borosilicate glasses, such as those described in published U.S. Patent Application US20050036961A1 entitled “AESTHETICALLY AND SPF IMPROVED UV-SUNSCREENS COMPRISING GLASS MICROSPHERES”.

[0082] In one embodiment, a composition suitable for application to the human body (e.g., keratinized surfaces such as skin, hair, lips, or fingernails / toenails), particularly the skin, for topical / cosmetic purposes is provided. The sunscreen composition comprises a combination of a polymer composition and at least one additional UV-blocking compound, the polymer composition comprising one or more linear UV-absorbing polyethers containing covalently bonded UV chromophores.

[0083] The concentration of the UV-absorbing polymer may be from about 1% to about 30% of the local sunscreen composition, such as from about 2% to about 20%, such as from about 5% to about 15%. In some embodiments, the concentration of the UV-absorbing polyether is about 2% or more of the sunscreen composition, such as about 5% or more, such as about 15% or more.

[0084] The concentration of the additional UV-blocking compound in the topical sunscreen composition may be from about 1% to about 40% of the topical composition, such as from about 2% to about 30%, such as from about 5% to about 20%. In some embodiments, the concentration of the additional UV-absorbing compound is about 2% or more of the composition, such as about 10% or more, such as about 15% or more, such as about 25% or more.

[0085] The concentration of UV-absorbing light-scattering particles (if present) may be about 1% or more, such as about 1% to about 10%, such as about 2% to about 5%. In some embodiments where the UV sunscreen further comprises the amount of UV-absorbing sunscreen as discussed above, the composition of the present invention may have an SPF of about 20 or greater.

[0086] The compositions of this invention can be used for a variety of cosmetic applications, particularly for protecting the skin from UV radiation. The compositions can therefore be formulated into a variety of delivery forms. These forms include, but are not limited to, suspensions, dispersions, solutions, or coatings on water-soluble or water-insoluble substrates (e.g., substrates such as organic or inorganic powders, fibers, or membranes). Suitable product forms include lotions, creams, gels, sticks, sprays, ointments, mousses, and powder / cassette products. The compositions can be used for a variety of end uses, such as recreational or daily sunscreens, moisturizers, cosmetics / makeup, cleansers / toners, anti-aging products, or combinations thereof. The compositions of this invention can be prepared using methods well known to those skilled in the art of cosmetic formulation.

[0087] For a UV sunscreen agent to be effective in a sunscreen composition, it must be dissolved in at least a portion of the composition. The compositions of the present invention comprise a continuous aqueous phase, wherein a discontinuous oil phase is uniformly distributed, the discontinuous oil phase comprising a linear UV-absorbing polyether and additional UV-shielding compounds. In some embodiments, rather than dispersion or suspension, the linear UV-absorbing polyether and additional UV-shielding compounds are dissolved within the oil phase. The oil phase may then be stabilized within the aqueous phase. The oil phase may exist as discrete droplets or units having an average diameter of about one micrometer to about 1000 micrometers, such as about one micrometer to about 100 micrometers.

[0088] The relative concentrations of the aqueous and oil phases can vary. In some embodiments, the aqueous phase comprises about 10% to about 90% by weight, such as about 40% to about 80%, or 50% to about 80%; the balance being the oil phase. The oil phase is in equilibrium.

[0089] The percentage of water contained in the composition can range from about 20% to about 90%, such as about 20% to about 80%, such as about 30% to about 70%, such as about 51% to about 80%, such as about 51% to about 70%, such as about 51% to about 60%.

[0090] Local carrier

[0091] One or more linear UV-absorbing polyethers in the composition can be combined with a "cosmetically acceptable topical carrier" (i.e., a topical carrier that disperses or dissolves other ingredients therein and has acceptable properties that allow for safe topical application). Therefore, the composition may additionally contain any of the various functional ingredients known in the field of cosmetic chemistry, such as emollients (including oils and waxes) and other functional ingredients commonly used in personal care compositions, such as humectants, thickeners, sunscreens, fragrances, dyes, and solvents for the linear UV-absorbing polyethers. Suitable examples of solvents for UV-absorbing polyethers include dioctyl carbonate, available from Cognis Corporation of Ambler, Pennsylvania, as CETIOL CC. To provide pleasing aesthetic properties, in some embodiments of the invention, the composition is substantially free of volatile solvents; and specifically free of C1-C4 alcohols, such as ethanol and isopropanol.

[0092] Furthermore, the composition may be substantially free of ingredients that would render it unsuitable for topical application. Thus, the composition may be substantially free of solvents, such as volatile solvents, and specifically, free of volatile organic solvents, such as ketones, xylene, toluene, etc.

[0093] emulsifier

[0094] The inventors have surprisingly discovered that sunscreens with mild UV protection can be prepared by forming an oil-in-water (O / W) emulsion comprising a polymer composition containing a linear UV-absorbing polyether and a specific emulsifier within a specific weight range. Therefore, the compositions of the present invention comprise an O / W emulsifier component containing one or more O / W emulsifiers. The term "O / W emulsifier" refers to any molecule of a variety of molecules suitable for emulsifying discrete oil-phase droplets in a continuous aqueous phase. The term "low molecular weight emulsifier" refers to an emulsifier having a molecular weight of 2000 Daltons or less, such as about 1000 Daltons or less. When an O / W emulsifier concentration of 0.5% or less is added to pure deionized water at room temperature, the O / W emulsifier is able to reduce the surface tension of the pure deionized water to 45 dynes / cm. O / W emulsifiers are sometimes characterized as having a hydrophilic-lipophilic balance (HLB) value of about 8 or higher (such as about 10 or higher).

[0095] The O / W emulsifier component comprises one or more anionic emulsifiers, such that the total concentration of the anionic emulsifiers in the composition is about 3% or less. Examples of suitable chemical classes of anionic emulsifiers are alkyl, aryl, or alkylaryl or acyl modified forms of the following portions: sulfates, ether sulfates, monoglyceride sulfates, sulfonates, sulfosuccinates, ether sulfosuccinates, sulfosuccinamides, amide sulfosuccinates, carboxylates, amide ether carboxylates, succinates, sarcosine salts, amino acids, taurines, sulfoacetates, and phosphates. Notable anionic emulsifiers are phosphate esters, such as potassium hexadecyl phosphate. In some embodiments, the concentration of one or more anionic emulsifiers is from about 0.5% by weight to about 3% by weight of the composition, such as from about 0.6% by weight to about 3% by weight, such as from about 0.6% by weight to about 2.5% by weight. According to some embodiments, the O / W emulsifier component consists essentially of one or more anionic emulsifiers.

[0096] According to certain embodiments, the O / W emulsifier component is substantially free of nonionic emulsifiers with alcohol functional groups having hydrocarbon chain lengths of 14 to 22 carbon atoms. Chemical classes of nonionic emulsifiers with alcohol functional groups may include fatty alcohols, such as various saturated or unsaturated, straight-chain or branched C7-C... 22 Unethoxylated aliphatic alcohols, such as those having a single -OH group. These aliphatic alcohols may be derived from vegetable or animal oils and fats having at least one hydrocarbon side chain. The aliphatic alcohol may have 14 to about 22 carbon atoms, such as about 16 to about 18 carbon atoms. Examples of unbranched aliphatic alcohols include cetyl alcohol and stearyl alcohol.

[0097] According to certain other embodiments, the O / W emulsifier component is substantially free of cationic emulsifiers, such as alkyl quaternary ammonium, benzyl quaternization, ester quaternization, ethoxylated quaternary ammonium, and alkylamine.

[0098] According to certain embodiments, in addition to the above-described (one or more) anionic oil-in-water emulsifiers, the O / W emulsifier component contains additional emulsifiers, such as nonionic emulsifiers lacking alcohol functional groups, amphoteric emulsifiers, and / or polymeric emulsifiers. Examples of suitable chemical classes of nonionic emulsifiers include ethoxylated amides; polyoxyethylene derivatives of polyol esters; non-crosslinked silicone copolymers, such as alkoxy or alkyl dimethylsiloxane copolyols; silicones having hydrophilic side chains, such as linear silicones having polyether or polyglycerol side chains; and crosslinked elastomeric solid organopolysiloxanes containing at least one hydrophilic portion.

[0099] Examples of suitable chemical classes for amphoteric emulsifiers include alkyl betaines, amide alkyl betaines, alkyl amphoteric formates; amide alkyl sulfobetaines; amphoteric phosphates; phosphorylated imidazolines; carboxyalkylalkyl polyamines; alkyl imino dipropionates; alkyl amphoteric glycinates (mono or di); alkyl amphoteric propionates; N-alkyl β-aminopropionic acid; and alkyl polyaminocarboxylates. Examples of suitable chemical classes for polymeric emulsifiers include copolymers based on acrylamide alkyl sulfonic acids, such as Aristoflex from Clariant Corporation. ® AVC and Aristoflex ® HMB; and Grant Industries, Inc.'s Granthix APP.

[0100] Film-forming polymers

[0101] Sunscreen compositions are typically formulated to enhance the water resistance of film-forming agents. In some embodiments of the invention, the compositions comprise a film-forming polymer. A "film-forming polymer" is defined as a polymer that, when dissolved, emulsified, or dispersed in one or more diluents, can form a continuous or semi-continuous film when spread onto a smooth glass surface with a liquid solvent and allowed to evaporate. Therefore, the polymer should be dried on the glass in such a way that it is primarily continuous over the area where it is spread, rather than forming multiple discrete island-like structures. Generally, the film formed by applying the composition to the skin according to embodiments of the invention described herein has an average thickness of less than about 100 micrometers, such as less than about 50 micrometers.

[0102] Compared to polymeric UV-absorbing polymers, film-forming polymers typically do not absorb ultraviolet radiation and therefore do not meet the requirements of UV-absorbing polymers. Film-forming polymers may be useful in the compositions of the present invention because they can enhance the UV protection (UV-A, UV-B, or both) and / or enhance the water resistance or water-resistance of the composition.

[0103] Suitable film-forming polymers include natural polymers, such as polysaccharides or proteins, and synthetic polymers, such as polyesters, polyacrylates, polyurethanes, vinyl polymers, polysulfonates, polyureas, polyoxazolines, etc. Specific examples of film-forming polymers include, for example, hydrogenated dimer dihydroindole / dimethyl carbonate copolymers available from Cognis Corporation of Ambler, Pennsylvania, under COSMEDIA DC; copolymers of vinylpyrrolidone and long-chain α-olefins, such as those available under GANEX V220 from Specialty Chemicals, Wayne, New Jersey; vinylpyrrolidone / tricontanyl copolymers also available under GANEX WP660 from ISP; and water-dispersible polyesters, including sulfonated polyesters, such as those commercially available under EASTMAN AQ 38S from Eastman Chemical. The amount of the film-forming polymer in the composition may be from about 0.1% to about 5%, or from about 0.1% to about 3%, or from about 0.1% to about 2%.

[0104] In some embodiments, the composition comprises an emollient for preventing or alleviating dryness and protecting the skin, as well as for dissolving the linear UV-absorbing polyether. Suitable emollients include mineral oils, petrolatum, vegetable oils (e.g., triglycerides such as caprylic / capric triglycerides), waxes, and other mixtures of fatty esters (including, but not limited to, esters of glycerol such as isopropyl palmitate and isopropyl myristate), and silicone oils such as polydimethylsiloxane. In some embodiments, a mixture of triglycerides (e.g., caprylic / capric triglycerides) and esters of glycerol (e.g., isopropyl myristate) may be used to dissolve the linear UV-absorbing polyether.

[0105] In some embodiments, the composition comprises a pigment suitable for providing color or coverage. The pigment may be suitable for colored cosmetic products, including compositions applied to hair, nails, and / or skin, particularly the face. Colored cosmetic compositions include, but are not limited to, foundations, concealers, primers, blushes, mascaras, eyeshadows, eyeliners, lipsticks, nail polishes, and color-correcting moisturizers.

[0106] Pigments suitable for providing color or hiding power may consist of iron oxide (including red and yellow iron oxide), titanium dioxide, ultramarine pigment, and chromium or chromium hydroxide particles, as well as mixtures thereof. Pigments may be colored pigments, such as organic dyes precipitated onto an inert binder (such as insoluble salts), such as azo, indigo, triphenylmethane, anthraquinone, and xanthine dyes designated as D&C and FD&C blue, brown, green, orange, red, yellow, etc. Examples of lake pigments include Red #6, Red #7, Yellow #5, and Blue #1. Pigments may be interference pigments. Examples of interference pigments include those containing mica substrates, bismuth oxychloride substrates, and silica substrates, such as mica / bismuth oxychloride / iron oxide pigments commercially available from CHROMALITE pigments (BASF); titanium dioxide and / or iron oxide coated onto mica, such as commercially available FLAMENCO pigments (BASF); mica / titanium dioxide / iron oxide pigments, including commercially available KTZ pigments (Kobo Products) and CELLINI pearl pigments (BASF); and borosilicate pigments, such as REFLECKS pigments (BASF).

[0107] The compositions of the present invention may also contain one or more other cosmetic active agents. A "cosmetic active agent" is a compound that has cosmetic or therapeutic effects on the skin, such as an agent for treating wrinkles, acne, or brightening the skin. Cosmetic active agents are typically present in the compositions of the present invention in an amount from about 0.001% to about 20% by weight of the composition, for example, from about 0.01% to about 10% by weight of the composition, such as from about 0.1% to about 5%.

[0108] In some embodiments, the pH of the composition is from about 4.0 to about 8.0, such as from about 5.5 to about 7.0.

[0109] Sun protection factor (SPF) can be tested using the following in vitro SPF testing method. The baseline transmittance of a PMMA plate (substrate) to which no test material is applied is determined. The test sample is prepared by providing a polymer sample. Blends can also be tested using this method. One or more polymers can be tested without any additional additives; they can be tested in a solvent system or as part of a personal care composition, which may contain solvents and / or additional ingredients.

[0110] Place each sample at 25cm 2The substrate (available from Helioscience, Marseille, France) was applied individually to PMMA plates using an application density of approximately 32 micrograms, rubbed into a uniform thin layer by the operator's fingers, and allowed to dry. This was done using a calibrated Labsphere... ® UV-1000S UV Transmission Analyzer or Labsphere ® Before measuring absorbance using the UV-2000S UV transmission analyzer (Labsphere, North Sutton, NH, USA), allow the sample to dry for 15 minutes. Calculate the SPF and PFA indices (UVA-based biological protection factors) using the absorbance measurements.

[0111] SPF and PFA are calculated using methods known in the art – for the calculation of SPF, see Formula (1) below:

[0112] in: E(λ) = Erythema-related spectrum I(λ) = Spectral irradiance received from the UV source A0(λ) = Before UV exposure The average monochromatic absorbance of the test product layer dλ = wavelength step (1nm).

[0113] The compositions of the present invention have a low tendency to cause irritation. Irritation can be measured using, for example, the modified TEP test shown below. A lower modified TEP value in a composition tends to indicate less irritation compared to a composition with a higher modified TEP value, which tends to result in a higher level of eye irritation.

[0114] The applicant has recognized that the compositions of the present invention have surprisingly low modified TEP values ​​and associated low irritation. For example, in some embodiments, the compositions have modified TEP values ​​of 0.3 or less, or about 0.25 or less, or about 0.20 or less as determined by the modified TEP test described below.

[0115] The compositions of the present invention can be prepared using mixing and blending methods well known to those skilled in the art. In one embodiment of the invention, a method for preparing the compositions of the present invention includes preparing an oil phase by mixing at least a linear UV-absorbing polyether with an optional oil-soluble or oil-miscible component; and preparing an aqueous phase by mixing water with an optional water-soluble or water-miscible component. The oil phase and the aqueous phase can then be mixed in a manner sufficient to uniformly disperse the oil phase in the aqueous phase such that the aqueous phase is continuous while the oil phase is discontinuous.

[0116] The compositions of the present invention can be used by topical application to mammals, for example by directly spreading, applying or spreading the composition on human skin or hair.

[0117] The modified TEP test was used in this method and the following examples. In particular, as described above, the modified TEP test was used to determine when the composition exhibits the reduced irritation according to the invention.

[0118] Modified TEP test : The modified TEP assay was designed to assess the ability of the test material to disrupt the permeability barrier formed by the confluence of canine kidney (MDCK) cells. MDCK cells grown to the confluence on a porous filter were used to assess transepithelial permeability, determined by the leakage of fluorescein dye through the monolayer. The MDCK permeability barrier is a model of the outermost layer of the corneal epithelium, and therefore this system can be considered to reflect early changes in ocular stimulation in vivo.

[0119] The following equipment is suitable for modified TEP testing: Packard multi-probe 104 liquid handling system; BioTek washer, model ELx405; and BioTek Powerwave XS microplate reader with a 490 nm filter. Disposable laboratory equipment includes: Corning Support Transwell 24-well cell culture plates with microporous membranes (catalog number 29445-100 or 29444-580, MFG number 3397); Corning receiver 24-well tissue culture plates (catalog number 29444-100, MFG number 3527); disposable 200 µL tips (catalog number 82003-196); Eppendorf 5 mL combination tips (catalog number 21516-152); 0.9% (w / v) sodium chloride aqueous solution (catalog number RC72105); and sterile 15 mL polypropylene centrifuge tubes. (Produced by Life Sciences, Inc.) The reagents supplied by Technologies include: phenol red-free Hank balanced salt solution (10x) (catalog number 14065056) and 7.5% sodium bicarbonate solution (catalog number 25080094), minimal basal medium (MEM) (1x) (catalog number 11095072), fetal bovine serum HI (catalog number 10082147), 100x antibiotic antimalarial drug (catalog number 15240096), L-glutamine 200mM (100x) (catalog number 25030081), and Sigma's fluorescein sodium Sig (catalog number F-6377, supplied by Sigma / Aldrich).

[0120] The cell line ATCC CCL 34 MDCK (NBL-2) (kidney: canine) was maintained according to ATCC (Manassas, Virginia) recommendations. Cell cultures were harvested via trypsin and kept at 5 × 10⁻⁶. 5 Cells were seeded into complete MEMSupport Transwell 24 plates 48 hours before testing at a concentration per milliliter. Preparation of reagents: (1) Prepare 1X HBSS buffer by mixing 200 mL of phenol red-free Hank balanced salt solution (HBSS) (10x) with 9.3 mL of sodium bicarbonate and increasing the volume to 2000 mL with distilled water. The pH should be in the range of 6.8 to 7.2 and the solution should be warmed to 37°C; (2) 200 μg / mL stock solution of sodium fluorescein in HBSS buffer; (3) Prepare complete minimum basal medium (MEM) by mixing 100 mL of fetal bovine serum, 10 mL of antibiotic antimicrobial agent (100x) and 10 mL of L-glutamine 200 nM (100x) with 1000 mL of MEM (1x).

[0121] The permeability of the membrane was confirmed using a cell-free control, including daily testing. The sunscreen test composition was evaluated over its entire length.

[0122] Wash the insert to remove cell culture medium. Remove the 24-well cell culture plate (Corning catalog number 29445-100) containing a confluent monolayer of MDCK cells from the incubator. Each 24-well plate includes an insert that holds the inner wells, with the microporous membrane cell growth surface suspended in the lower wells. Wash the insert containing cell culture 5 times with warm HBSS (BioTek washer) to remove culture medium and serum. Wash the bottom portion of the 24-well plate 3 times with warm HBSS, dispensing 1 mL of HBSS into each bottom well on the final wash.

[0123] Each sunscreen test composition was used in four wells of a 24-well plate, so a maximum of six sunscreen test compositions could be tested on a single 24-well plate. The sunscreen test compositions were added directly to the insert wells (pure (100%), 200 µL per insert well). The 24-well cell culture plate was then returned to the incubator for a 1-hour latency period.

[0124] After completing the first incubation step, remove the 24-well plate from the incubator and wash manually to remove the test composition. Add approximately 200 µL of HBSS to each inner well and allow it to soak for approximately 1 minute. Then decant the test composition and HBSS from each well. Remove any residual sample by carefully overflowing the insert with HBSS and decanting. When the insert is free of residual test composition, complete 10 washes with warm HBSS (Bio Tek washer). Wash the bottom wells 3 times with warm HBSS, and on the last wash, dispense 1 mL of HBSS (receiver buffer) into each bottom well.

[0125] Place the insert back into the base plate containing 1 mL of HBSS (receiver buffer), add sodium fluorescein to each well (200 µL per well), and return the plate to the incubator for a 45-minute cycle.

[0126] After incubation for 45 minutes, the first plate containing sodium fluorescein was removed from the incubator, the upper insert was removed, and the amount of dye that had leaked into the receiver buffer in the lower wells was determined using a Powerwave XS microplate reader. Fluorescence was read spectrophotometrically at 490 nm. The data were printed and recorded.

[0127] The insert is then placed on an empty, temporary 24-well plate on a Bio Tek washing machine for 10 washes. Ensure that the sodium fluorescein has been washed away and that there is no residual fluorescein in the top (inner) or bottom wells.

[0128] Place the washed inserts into new 24-well receiver cell culture plates (Corning catalog number 29445-100). Insert two inner wells into the receiver plate with minimal essential medium (MEM), Life Sciences, Cat No. 11095072. Approximately 1 mL of complete memory is added to the bottom of 200 µL of the inner well. The 24-well culture plate is then incubated three times.

[0129] After 3 hours of incubation, remove the 24-well plate from the incubator. Insert warm HBSS containing cell culture wash 5X (BioTek washer) to remove culture medium and serum. Wash the bottom plate 3 times with warm HBSS, and on the last wash, dispense 1 mL of HBSS into each bottom well (receiver buffer).

[0130] Add sodium fluorescein to each inner insertion well (200 µL per well), and reassemble the plate and place it back in the incubator for a 45-minute cycle.

[0131] After a 45-minute incubation, the plate containing sodium fluorescein was removed from the incubator, the insert was removed and discarded, and the amount of dye leaked into the lower wells was determined using a Powerwave XS microplate reader. Fluorescence was read spectrophotometrically at 490 nm. The data was printed and recorded.

[0132] Spectrophotometric measurements (fluorescein leakage) for each of the four repeat sequences of a given sunscreen test composition were used to calculate the average fluorescein leakage value of the sunscreen test composition. The average fluorescein leakage values ​​for four “cell-free controls” were also calculated. The modified TEP score was calculated by dividing the average fluorescence value of the sunscreen test composition by the average fluorescence value of the cell-free controls.

[0133] Further details of the TEP test are described in the following publications: Tchao, R (1988) In vitro fluorescein trans-epithelial permeability as an analysis for determining ocular irritation. Alternative methods in toxicology, Advances in in vitro toxicology (AM Goldberg edition), p. 271.

[0134] The values ​​for SPF (in computer) and UVA-PF (in computer) given in the following examples were calculated according to the methods described in Pure Applied Chemistry 87 (2015) 937 to 951.

[0135] The following examples are intended to illustrate the principles and implementation of the invention, and not to limit it. Many other embodiments within the scope and spirit of the invention will become apparent to those skilled in the art with the aid of this disclosure.

[0136] Example

[0137] Examples 1 to 11: Synthesis and SPF testing of polymer compositions containing linear UV-absorbing polyethers

[0138] Example 1: Synthesis of glycidol in its protected form.

[0139]

[0140] Formula VIII: Synthesis of protected epoxide monomers

[0141] The synthesis of the protected epoxide monomer 1 was performed using a variation of the procedure described in the literature (Fitton, A. et al., *Synthesis*, 1987 edition, pp. 1140–1142), as shown in Formula VIII. Glycidyl ether (53 mL, 0.80 mol) and ethyl vinyl ether (230 mL, 2.40 mol; distilled immediately before reaction) were added to a 500 mL two-necked round-bottom flask equipped with a magnetic stir bar. The flask was fitted with a diaphragm and a thermometer connector. The thermometer was inserted into the connector and positioned such that the bulb was immersed in the liquid. The flask was placed in an ice bath. The mixture was magnetically stirred. While the internal temperature was 0 °C, p-toluenesulfonic acid hydrate (pTSA·H₂O, 1.43 g, 7.5 mmol) was added in small portions while stirring vigorously. The temperature of the solution was rapidly increased with each addition of pTSA; the rate of addition was slow enough to prevent the solution temperature from rising above 20 °C. The final portion of pTSA was added 5 hours after the initial addition, and no exothermic reaction was observed; thin-layer chromatography of the reaction mixture after the final addition of pTSA showed no residual glycidyl. The reaction mixture was transferred to a separatory funnel; a saturated aqueous solution of NaHCO3 (230 mL) was slowly poured into the funnel. The mixture was shaken to allow the layers to separate, the organic layer was removed, dried with sodium sulfate, and filtered through filter paper. The solution was concentrated by rotary evaporation, followed by vacuum distillation (distillate at 60 °C under 8 Torr) to provide a clear, oily, protected epoxide monomer 1 (79.38 g). NMR analysis was performed on a Varian Unity Inova 400 MHz spectrometer. 1 H) Spectroscopy was performed at 30 °C on a spectrometer; chemical shifts were reported in parts per million (ppm) on the δ scale, with reference to residual protonated solvent peaks or tetramethylsilane. Spectral reference δ obtained in DMSO-d6 H (C at 2.50) H D2)(CD3)SO. 1 HNMR (400MHz, CDCl3) δ ppm 4.76 (quin, J=5.2Hz, 1 H), 3.81 (dd, J=11.5, 3.3Hz, 1H), 3.60-3.74 (m, 3H), 3.38-3.60 (m, 4H), 3.10-3.20 (m, 2H), 2.81 (dd d, J=5.1, 4.0, 1.3Hz, 2H), 2.63 (ddd, J=14.6, 5.1, 2.7Hz, 2H), 1.33 (dd, J=6.2, 5.4Hz, 6 H), 1.21 (td, J=7.1, 1.3Hz, 6H).

[0142] Example 2A: Synthesis of linear polyglycerol

[0143] Formula IX: Synthesis of linear polyether polymers

[0144] The polymerization of the protected epoxide monomer 1 was achieved as shown in Formula IX. 1-Octadecanol (27.76 g, 102.6 mmol) was added to a 250 mL two-necked round-bottom flask, oven-dried and equipped with a magnetic stir bar. The flask was fitted with a nitrogen inlet and a rubber septum. Potassium methoxide (25 wt% in methanol (MeOH), 6.06 mL, 20.52 mmol) was added to the flask via a syringe inserted through the septum. The round-bottom flask was immersed in an oil bath preheated to 90 °C. The septum was inserted with an 18-meter measuring needle, and the material in the flask was stirred for 1 hour under a constant nitrogen flow, during which the alcohol melted and the methanol evaporated from the flask. The septum was replaced with a uniformly pressurized feeding funnel containing monomer 1 (151 g, 1.04 mol). This funnel was sealed with a rubber septum. Monomer 1 was added dropwise to the stirred mixture; the reaction mixture was stirred at 90 °C for 15 hours. When cooled, it is provided as a light brown, slightly viscous, oily crude polyether 2, which is used in subsequent reactions without further purification. 1 ¹H NMR (400MHz, chloroform-d) δppm 4.48–4.80 (m, 10H), 3.25–3.97 (m, 70H), 1.41–1.64 (m, 2H), 1.23–1.40 (m, 60H), 1.09–1.23 (m, 30H), 0.88 (t, J = 7.0Hz, 3H).

[0145] Gel permeation chromatography for molecular weight determination was performed at 35°C on a Waters Alliance 2695 Separations Module (Waters, Milford, MA) at a flow rate of 0.5 mL / min THF (stable w / 0.025% BHT). The 2695 was equipped with two tandem GPC columns (Waters Corp HR 0.5 and HR3) with a particle size of 7.8 × 300 mm and a 5 µm particle size, and a Waters 410 refractive index detector. The molecular weight of the samples was determined by comparison with polystyrene standards. Standards were prepared by weighing 1 to 2 mg of each polystyrene (PS) polymer into 2 mL vials containing THF solvent (two standards per vial); the samples were filtered (0.22 µm) prior to analysis. Polystyrene standards ranged from 70,000 to 600 Daltons and were manufactured by three suppliers (Polymer Standards Service-USA, Phenomenex, and Shodex). The resulting calibration curves provide r 2=0.9999. Prior to analysis, the experimental samples were dissolved in THF at a concentration of 3–5 mg / mL and filtered (0.22 µm). GPC (THF) analysis of polymer 2: Mw1724.

[0146] Crude polyether 2 was transferred together with tetrahydrofuran (THF, approximately 500 mL) into a 1 L round-bottom flask containing a magnetic stir bar. A concentrated aqueous HCl solution (37%, 20 mL) was added to the stirred reaction mixture via a glass pipette. After 16 hours, the reaction mixture was concentrated to an oil by rotary evaporation, which was then diluted with methanol to ~500 mL. Solid NaHCO3 was partially added to the vigorously stirred solution, resulting in significant foaming. When the addition of NaHCO3 did not produce additional foaming (total NaHCO3 added was 107 g), the mixture was filtered through filter paper to remove the solid NaHCO3. The filtrate was concentrated by rotary evaporation to provide brown, foamy linear polyglycerol 3. 11 ¹H NMR (400 MHz, DMSO-d6) δ ppm 4.43 (br.s, 11H), 3.20–3.70 (m, 52H), 1.38–1.55 (m, 2H), 1.23 (s, 30H), 0.85 (t, J = 7.0 Hz, 3H).

[0147] Example 2B: Synthesis of linear polyglycerol.

[0148] Different batches of the protected crude polymer 2 (260 g) and methanol (ACS grade, 1.25 L) were transferred to a 2 L round-bottom flask with a two-necked neck. The dried H₂ was then... + An acidic ion exchange resin (Dowex DR-2030, 446483; 100.3 g from Aldrich) was added to a flask. The flask had a central neck fitting for mechanical stirring and a paddle fitting; the side neck fitting had a water-cooled distillation fitting. The reaction flask was immersed in an oil bath. The reaction mixture was heated to boiling (85°C oil bath temperature) with vigorous mechanical stirring. Methanol (and dimethyl ether resulting from the removal of protecting groups) was distilled from the flask. After collecting 750 mL of methanol, an additional 750 mL of methanol was added to the reaction mixture. Another 750 mL of methanol was distilled from the flask. Decolorized charcoal was added to the hot reaction mixture. The mixture was briefly stirred and then filtered through filter paper. The filtrate was concentrated by rotary evaporation. Residual solvent was removed under vacuum, yielding a pale yellow, foamy linear polyglycerol (107 g).

[0149] Example 3A: Synthesis of benzotriazole chromophore carboxylic ester .

[0150]

[0151] Formula X: Benzotriazole carboxylic acid ester.

[0152] Polyethylene glycol 3-[3-(2H-1,2,3-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (chromophore sold by BASF Corporation, Wyandotte, Michigan under the trade name TINUVIN 213) (81.0 g) was added to a 2 L round-bottom flask containing a magnetic stir bar. EtOH (600 mL) was added to the flask via a funnel, and the mixture was stirred until homogeneous. Sodium hydroxide (NaOH, 30.8 g) was dissolved in water (400 mL); the alkaline solution was transferred to a feeding funnel above the 2 L flask. The NaOH solution was slowly added to the stirred mixture; the pale amber turbid solution immediately turned clear and deep orange. When the addition was complete, the mixture was stirred overnight at room temperature. The solution was concentrated by rotary evaporation to remove most of the EtOH. The resulting orange solution was diluted with 1400 mL of H2O. The mixture was mechanically stirred and acidified to approximately pH 1 by adding 1M aqueous solution. Acidification to ~ pH 1 was achieved with an aqueous HCl solution (~700 mL). The resulting white precipitate was filtered and pressed to remove water, then recrystallized from EtOH. The first batch of crystals consisted of long, thin, colorless needles. The supernatant was removed and concentrated by rotary evaporation. The second batch of material was separated into a white solid. The two batches were combined and dried overnight in a vacuum oven to provide a UV chromophore with a carboxylate group as a white solid, specifically benzotriazole carboxylate 4,3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionic acid (37.2 g); the structure is shown in Formula X. 1 H NMR (400MHz, DMSO-d6) δ ppm11.25 (br.s, 1 H), 8.00-8.20 (m, 2H), 7.95 (d, J=2.1Hz, 1H), 7.50-7.67 (m, 2H), 7.28 (d, J=2.1Hz, 1H), 2.87 (t, J=7.5Hz, 2H), 2.56 (t, J=7.5Hz, 2H), 1.45 (s, 9H).

[0153] Example 3B: Synthesis of benzotriazole chromophore carboxylic ester .

[0154]

[0155] 120 g (265.7 mmol) of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7-9-branched and straight-chain alkyl phenylpropionic acid (available from BASF) was added to a 3 L single-necked round-bottom flask equipped with a magnetic stir bar. Isopropanol (900 mL, ACS grade) was added to the flask, and the resulting mixture was stirred until completely dissolved. Sodium hydroxide (36 g, 900 mmol) was dissolved in 600 mL of distilled water, and this solution was added to the reaction mixture. The resulting opaque mixture (which turned into a clear orange solution within 40 minutes) was stirred at room temperature for 24 hours, and then slowly added to a vigorously stirred mixture (1800 mL, ACS grade) of isopropanol and 1N HCl (1200 mL), and cooled to 10 to 15 °C. The precipitated white solid was filtered, washed with 1.2 L of a 1:1 isopropanol-1N HCl mixture, suspended in 2.0 L of 0.25N HCl, stirred for 1 hour, filtered, and dried overnight in a vacuum oven at 90 °C. The resulting UV chromophore (85 g, 94.5%), a pale yellow solid containing a carboxylate group, was obtained, specifically benzotriazole carboxylate 4 (37.2 g).

[0156] Example 4A: Esterification of polyether backbone with benzotriazole carboxylate .

[0157]

[0158] Formula XI: Esterification of polyglycerol with benzotriazole carboxylate

[0159] Formula XI illustrates the esterification of polyglycerol 3 with benzotriazole carboxylate 4 using catalytic tin. Linear polyglycerol 3 (5.52 g, 60.1 hydroxy mequivalents) from Example 2A was dissolved in methanol and transferred to a 500 mL two-necked round-bottom flask. Methanol was removed by rotary evaporation; benzotriazole carboxylate 4 (20.38 g, 60.1 mmol) was added to the flask with a magnetic stir bar. The flask was fitted with a nitrogen inlet and a vacuum distillation fitting with a 100 mL receiving flask. The flask was placed under vacuum (< 1 Torr) for 1 hour, then backfilled with nitrogen. The inlet fitting was removed from the 500 mL flask; tin(II) ethylhexanoate (49 µL, 0.15 µL) was added to the flask via a syringe under a nitrogen flow. The apparatus was reassembled and immersed in an oil bath preheated to 200 °C. When most of the solids had melted, the oil bath was cooled to 190 °C. The reaction was stirred under a nitrogen stream for 16 hours. While maintaining the temperature and stirring, the reaction flask was then placed under vacuum (< 1 Torr) for 24 hours. The apparatus was then backfilled with nitrogen and cooled to room temperature. The material was frozen and cut, and ground into powder using a mortar and pestle. The powder was dissolved in a minimal amount of THF. Methanol (900 mL) and a magnetic stir bar were added to the conical flask; the flask was then immersed in an ice bath. The THF solution was added to the methanol under vigorous stirring; the resulting precipitate was separated by vacuum filtration. The residual solvent was removed overnight under vacuum, yielding linear polyglycerol 5 (18.7 g) as a grayish-white solid. 1 H NMR (400MHz, CDCl3) δ ppm11.71 (br.s, 9H), 8.03 (br.s, 9H), 7.80 (br.s, 18H), 7.28-7.48 (m, 18H), 7.12 (br.s, 9H), 5.19 (br.s, 1H), 3.98-4.46 (br.m, 20H), 3.21-3.61 (br.m, 32H), 2.91 (br.s, 18H), 2.67 (br.s, 18H), 1.38-1.51 (m, 85H), 1.13-1.35 (m, 28H), 0.87 (t, J=6.6Hz, 3H). GPC(THF): M w 3299; M n 2913.

[0160] Example 4B: Synthesis of linear UV-absorbing polyether (actual process)

[0161] Example 5: Benzotriazole carboxylate to acyl chloride (3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-) Transformation of butyl(4-hydroxyphenyl)propionyl chloride .

[0162]

[0163] Formula XII: Conversion from benzotriazole carboxylate to benzotriazole acyl chloride

[0164] The conversion of benzotriazole carboxylic acid 4 to the corresponding benzotriazole acyl chloride 6 is shown in Formula XII. Benzotriazole carboxylic acid ester 4 (50 g, 147 mmol) synthesized as described in Example 3 was added to a 1000 mL three-necked flask equipped with a magnetic stir bar; the flask was fitted with a reflux condenser, a nitrogen inlet, and a rubber septum. Anhydrous toluene (~500 mL) was transferred to the flask through a tube inserted through the septum. Thionyl chloride (16.1 mL, 221 mmol) was transferred to the flask using a syringe; dimethylformamide (2.7 mL) was added to the flask using a syringe. The flask was immersed in an oil bath set at 80 °C; the suspension was stirred; the solids began to disperse, eventually producing a clear solution. After ~4 hours, the reaction mixture was cooled, transferred to a round-bottom flask, and concentrated by rotary evaporation. The resulting oil was ground with hexane to provide a pale yellow solid. The suspension of the material was recrystallized by adding additional hexane and heating to reflux, filtering through filter paper, and slowly cooling to room temperature with stirring. The resulting pale yellow crystals were filtered and dried under vacuum at 50°C. The filtrate was concentrated and recrystallized twice to obtain a second batch of crystals. The combined batch of benzotriazole chloride 6 weighed 44.7 grams. 1 H NMR (400MHz, CDCl3) δ 11.88 (s, 1H), 8.16 (d, J=2.2Hz, 1H), 7.91-7.98 (m, 3H), 7.47-7.54 (m, 2H), 7.21 ( d, J=2.2Hz, 1H), 3.29 (t, J=7.5Hz, 2H), 3.07 (t, J=7.5Hz, 2H), 1.50-1.53 ​​(s, 9H).

[0165] Example 6: Conversion of benzotriazole acyl chloride to isocyanate (2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(tert-butyl)-4-(2-isocyanate ethyl)phenol).

[0166]

[0167] Formula XIII: Conversion from acyl chloride to isocyanate

[0168] The synthesis of benzotriazole isocyanate 7, suitable for coupling to a side functional group, is shown in Formula XIII. Sodium azide (NaN3, 2.5 g, 38 mmol: Caution! NaN3 is highly toxic) was carefully transferred to a single-necked 500 mL round-bottom flask equipped with a magnetic stir bar. Methanol (500 mL) was added to the flask; the NaN3 was dissolved by mixing, thus providing a clear solution. The flask was immersed in an ice bath. Acyl chloride 6 (7.0 g, 20 mmol) and anhydrous acetone (45 mL) were transferred to a uniform feeding funnel in a positive-pressure N2 atmosphere glove box. The acyl chloride was dissolved in the acetone using a gentle vortex, thus providing a clear yellow solution. The feeding funnel containing benzotriazole acyl chloride 6 was fitted into a flask containing an aqueous solution of NaN3; the top of the feeding funnel was equipped with an N2 connector connected to a vacuum gas manifold. The solution of benzotriazole acyl chloride 6 was added dropwise to the NaN3 solution. After adding a few drops, a white precipitate begins to appear, suspended in the aqueous solution. The addition of benzotriazole chloride 6 is completed within 30 minutes. Mixing continues for 20 minutes in an ice bath. Water (30 mL) is added to the resulting white slurry; the solid is collected by filtration through a sintered glass funnel under vacuum. The white solid is transferred to a separatory funnel, followed by CHCl3 (185 mL). The flask is shaken to allow layer separation. The lower organic phase is removed from the small aqueous layer and dried with Na2SO4. The solution is filtered; the filtrate is placed in a single-necked 500 mL round-bottom flask equipped with a magnetic stir bar. The flask is fitted with a reflux condenser with a nitrogen inlet connector and immersed in an oil bath. The solution is slowly heated to reflux over 30 minutes. The final oil bath temperature is 65 °C. When the oil bath temperature exceeds 55 °C, bubbles are noticeable in the solution. Reflux is permitted at a total temperature of 90 °C. CHCl3 was then removed by rotary evaporation; the resulting oil was allowed to stand overnight to crystallize, thus providing benzotriazole isocyanate 7 (5.8 g) as a slightly gray solid. 1 H NMR (400MHz, CDCl3) δ 11.91 (s, 1H), 8.18 (d, J =1.9Hz, 1H), 7.92-7.98 (m, 2H), 7.47-7.53 (m, 2H), 7.23 (d, J =2.1Hz, 1H), 3.59 (t, J =6.9Hz, 2H), 2.96 (t, J =6.9Hz, 2H), 1.52 (s, 9H).

[0169] Example 7: Coupling of isocyanate to polyglycerol .

[0170]

[0171] Formula XIV: Reaction of polyglycerol with isocyanate

[0172] The reaction of linear polyglycerol 3 with benzotriazole isocyanate 7 is shown in formula XIV.

[0173] Formula XIV : The solution of polyglycerol 3 in methanol was concentrated by rotary evaporation. Residual solvent was removed by drying in a vacuum oven overnight at 75°C. The polymer (2.22 g, 24.1 mEq of hydroxyl groups) was added to a 100 mL two-necked round-bottom flask equipped with a magnetic stir bar. Isocyanate 7 (7.65 g, 22.7 mmol), bismuth catalyst (25 mg; a bismuth carboxylate complex sold by Shepherd Chemical, Norwood, OH, under the trade name BICAT 8210), and THF (17.4 mL, dried on a 3 Å molecular sieve) were added to the flask. The flask was placed in a heated oil bath at 65°C with a gas inlet. The reaction mixture was stirred under a nitrogen atmosphere for 5 hours and then cooled to room temperature. The concentration of the polymer was determined by FTIR at 2250 cm⁻¹. -1 The strong isocyanate peak disappeared. The reaction mixture was poured into 160 mL of methanol, resulting in a brown precipitate. The methanol was decanted, and the product was washed with methanol (2 × 75 mL) in a flask. Residual solvent removal was carried out overnight in a vacuum oven at 60 °C; the material was ground into a fine powder.

[0174] Example 8: Synthesis of epoxide chromophores for direct polymerization methods .

[0175]

[0176] Formula XV: Synthesis of epoxide chromophore monomers

[0177] The synthesis of epoxide monomer 9 containing a benzotriazole chromophore is shown in Formula XV. A solution of lithium aluminum hydride (LAH) in THF (1M, 250 mL) was transferred via tube under a nitrogen atmosphere to an oven-dried 500 mL two-necked round-bottom flask containing a magnetic stir bar and equipped with a rubber septum and a pressure-equalizing feeding funnel. The reaction flask was immersed in an oil bath. Stirring was initiated. Phenylacetic acid, 3-(2-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy, C7-C9 branched and straight-chain alkyl ester, comprising 5% by weight 1-methoxy-2-propyl ester (50.06 g; marketed under the trade name TINUVIN 99-2 by BASF Corporation, Wyandotte, Michigan). The benzotriazole UV absorber product, sold in Michigan, was transferred to a feeding funnel and dissolved in anhydrous THF (30 mL). The THF solution containing benzotriazole was added dropwise to the solution containing LAH; this resulted in slow bubbling. After the addition was complete, an additional portion of the LAH solution (100 mL) was introduced into the reaction flask through a tube. The reaction was allowed to rise to room temperature with stirring. After 2 hours, the reaction mixture was poured into a 1 L Erlenmeyer flask immersed in an ice bath. The solution was mechanically stirred while water (approximately 60 mL) was slowly added to quench any residual LAH (Note: Quenching LAH with water is exothermic and releases a large amount of highly flammable H2 gas). When the LAH was quenched (using additional water does not release additional gas), the gray suspension was diluted to 1 L with 1 M HCl aqueous solution. This solution was transferred to a 2 L separatory funnel and extracted with ethyl acetate (1 × 400 mL, then 2 × 400 mL). 50 mL). The combined ethyl acetate layer was washed with brine (1 × 400 mL), dried with Na2SO4, and then filtered through filter paper. The solvent was first removed by rotary evaporation and then dried overnight in a vacuum oven, thus providing benzotriazol 8 (42.16 g) as a pale yellow solid with a strong, unpleasant odor. 1 H NMR (400MHz, CDCl3) δ ppm11.75 (s, 1H), 8.15 (d, J =2.1Hz, 1H), 7.88-7.99 (m, 2H), 7.43-7.52 (m, 2H), 7.22 (d, J =2.1Hz, 1H), 3.75 (m, 2H), 3.62 (br.s, 1H), 2.77 (t, J =7.7Hz, 2H), 1.91-2.06 (m, 2H), 1.52 (s, 9H).

[0178] Sodium hydride (6.0 g, 250 mmol) was added to an oven-dried, three-necked round-bottom flask equipped with a magnetic stir bar. The flask was fitted with a pressure-equalizing feed funnel, a nitrogen inlet connector, and a rubber septum. Anhydrous THF (300 mL) was added to the flask under nitrogen by inserting a syringe plunger. The reaction flask was immersed in an ice bath and stirring was initiated. Benzotriazol 8 (20.0 g, 61.5 mmol) and a small magnetic stir bar were added to the feed funnel; THF was inserted into the addition funnel, and the stir bar was agitated to promote solvent dissolution of the alcohol in the THF. The final volume of the alcohol / THF solution was 65 mL. This solution was added dropwise to a cold, stirred sodium hydride suspension. The cold reaction mixture was stirred for 1 hour, and then epichlorohydrin (20 mL, 256 mmol) was added through a syringe inserted through the septum. The feed funnel was replaced with a reflux condenser with a nitrogen inlet, and the round-bottom flask was immersed in a 70°C oil bath. The mixture was stirred for 19 hours, then transferred to a separatory funnel containing 750 mL of 1 M HCl aqueous solution and 500 mL of ethyl acetate. After shaking, the aqueous layer was discarded. The organic layer was washed with water (2 × 250 mL) and brine (1 × 250 mL), then dried over Na₂SO₄. The solution was concentrated by rotary evaporation. The crude product was purified by chromatography on silica gel (6:1 hexane / ethyl acetate). The fraction containing the desired product was collected and concentrated by rotary evaporation; residual solvent was removed overnight under vacuum to give epoxide monomer 9 as a beige solid containing a benzotriazole chromophore (7.35 g). 1 H NMR (400MHz, CDCl3) δ ppm11.77 (s, 1H), 8.14 (d, J =1.9Hz, 1H), 7.85-8.00 (m, 2H), 7.41-7.53 (m, 2H), 7.21 (d, J =1.9Hz, 1H), 3.74 (dd, J =11.5, 3.1Hz, 1H), 3.57 (ddt, J =19.8, 9.3, 6.4Hz, 2H), 3.43 (dd, J =11.5, 5.8Hz, 1H), 3.19 (ddt, J =5.8, 4.0, 2.9Hz, 1H), 2.82 (br.t, J =4.7Hz, 1H), 2.76 (br.t, J =7.7Hz, 2H), 2.64 (dd, J =5.1, 2.6Hz, 1H), 1.93-2.04 (m, 2H), 1.52 (s, 9H).

[0179] Example 9: Esterification of alternating polyglycerols using benzotriazole acid.

[0180] Partially esterified polyglycerol (2.5 g, 19.8 hydroxy milliequivalents) from stearic acid (polyglycerol monostearate sold by Lonza in Allendale, NJ under the trade name POLYALDO 14-1-S) and benzotriazole carboxylate 4 (8.8 g, 23.8 mmol) were transferred to a two-necked 100 mL round-bottom flask equipped with a magnetic stir bar. The flask was fitted with a nitrogen inlet connector and a distillation connector with a 100 mL receiving flask. The apparatus was placed under vacuum for 1 hour, then backfilled with nitrogen. The distillation head was removed, and tin(II) ethylhexanoate (50 µL) was added to the reaction flask via a syringe under a nitrogen flow. The apparatus was reassembled, then purified under vacuum and backfilled with nitrogen three times. The reaction flask was immersed in an oil bath heated to 180 °C, with a constant nitrogen flow entering the two-necked flask through the distillation connector and exiting through the vacuum connector to room atmosphere. The reaction was stirred under a nitrogen stream for 3 hours and then cooled to room temperature to provide a yellow solid product, UV-absorbing polyglycerol. 1 H NMR (400MHz, CDCl3) δ ppm11.81 (br.s., 2H), 8.15 (br.s., 2H), 7.75-8.02 (br.s, 4H), 7.34-7.58 (br.s, 4H), 7.21 (br.s., 2H), 4.93-5.32 (br, 1H), 3.17-4.50 (b r.m, 38H), 2.86-3.11 (br.m, 4H), 2.54-2.84 (br.m, 4H), 2.31 (br.s., 2H), 1.61 (br.s., 2H) 1.50 (br.s., 18H), 1.26 (br.s., 28H), 0.89 (t, J =6.3Hz, 3H). GPC(THF): M w 1700; M n 950.

[0181] Example 10: Synthesis of methyl benzotriazole .

[0182]

[0183] Formula XVI: Synthesis of Methyl Ester 11

[0184] The synthesis of benzotriazole methyl ester 11, intended for transesterification with polymers having hydroxyl functional groups, is shown in Formula XVI. Poly(ethylene glycol) 300 β-[3-(2-H-benzotriazole-2-yl)-4-hydroxy-5-tert-butylphenyl]propionate (50.1 g; a UV-absorbing product sold by BASF Corporation, Wyandotte, Michigan as TINUVIN1130) was added to the two-necked 1-liter round-bottom flask containing a magnetic stir bar. Methanol (500 mL) was added to the flask. The flask was immersed in an ice bath. The solution was stirred. p-TSA·H₂O (0.63 g) was added to the solution. The two-necked flask was equipped with a reflux condenser and a rubber septum; the stirred reaction mixture was refluxed by heating an oil bath. Reflux was maintained for 17 hours. The flask was then removed from the oil bath and allowed to cool to room temperature, at which point the product precipitated as a white solid. The precipitate was separated by vacuum filtration and then recrystallized from methanol; the solid was separated by vacuum filtration and dried under vacuum at 80°C to obtain benzotriazole methyl ester 11 (18.27 g) as a white solid. 1 H NMR (400MHz, CDCl3) δ ppm11.81 (s, 1H), 8.16 (d, J =2.1Hz, 1H), 7.90-7.98 (m, 2H), 7.45-7.53 (m, 2H), 7.22 (d, J =2.2Hz, 1H), 3.71 (s, 3H), 3.01 (t, J =7.8Hz, 2H), 2.71 (t, J =7.8Hz, 2H), 1.51 (s, 9H).

[0185] Example 11: Transesterification of benzotriazole methyl ester with polyglycerol polymer .

[0186]

[0187] Formula XVII: Transesterification of polyglycerol

[0188] The transesterification of benzotriazole methyl ester 11 with polyglycerol 3 is shown in Formula XVII. The solution of polyglycerol 3 in MeOH was concentrated by rotary evaporation. Residual solvent was removed overnight under vacuum at 75°C. Polyglycerol 3 (1.36 g, 14.9 milliequivalents of hydroxyl groups) was added to a 100 mL two-necked round-bottom flask equipped with a magnetic stir bar. Benzotriazole methyl ester 11 (4.24 g, 12 mmol) and pTSA·H₂O (7.1 mg) were added to the flask. The flask was equipped with a nitrogen inlet connector and a distillation connector with a 100 mL receiving flask. The reaction flask was immersed in an oil bath, and the oil bath was heated to 175°C. All reactants were melted within 20 minutes. The reaction mixture was stirred vigorously overnight under a nitrogen stream. The next morning, the flask was placed under vacuum; residual UV chromophores were sublimated and collected in the distillation connector. Heating under vacuum continued overnight. The reaction mixture was then cooled to room temperature to obtain a UV-absorbing polyglycerol product that was a yellow, glassy solid. 1 H NMR (400MHz, CDCl3) δ ppm11.71 (br.s., 8H), 8.05 (br.s., 8H), 7.81 (br.s., 16H), 7.36 (br.s., 16H), 7.14 (br.s., 8H), 5.06-5.32 (br.s., 1H), 3. 86-4.57 (m, 16H), 3.15-3.82 (m, 30H), 2.92 (br.s., 16H), 2.68 (br.s., 16H), 1.45 (br.s., 76H), 1.24 (br.s., 28H), 0.88 (t, J =6.6Hz, 3H).

[0189] As can be seen from Examples 1 to 11, the analytical characterization of the obtained linear UV-absorbing polyethers is consistent with the expected structure. HPLC analysis of the polymers described in the examples provides evidence that the polymerization method produces low concentrations of residual UV-absorbing monomers.

[0190] Example 12: Preparation of a combination containing linear ultraviolet radiation absorbing polyether and other ultraviolet shielding compounds. Sunscreen Composition

[0191] Composition Examples 1 to 8 illustrate the formulation of linear UV-absorbing polyethers using avobenzone. The UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A.

[0192] Examples 1 to 8 were prepared using a standard sunscreen emulsion containing 3% or 1% avobenzone, 20% or 10% linear UV-absorbing polyether, or a combination of avobenzone and linear UV-absorbing polyether, with concentrations shown in Tables 2 and 3 below.

[0193] Table 2

[0194] Table 3

[0195] Composition Examples 9 to 11 Examples 9 to 11 illustrate linear UV-absorbing polyethers that can be formulated with other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A. Examples 9 to 11 were prepared using standard sunscreen emulsions by heating phases a and B to 80°C, then adding phase A to phase B to homogenize, followed by cooling to room temperature and continuous stirring (pH 6.00 to 6.40), as shown in Table 4 below. Table 4

[0196] Composition Examples 12 to 14 Examples 12 to 14 illustrate linear UV-absorbing polyethers that can be formulated with other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3A and 4A. Examples 12 to 14 were prepared using standard sunscreen emulsions as shown in Table 5 below, after heating phase A to 75°C and then heating phase B with stirring without allowing Amphisol K to reach 75°C with stirring. At 75°C, zwitterionic K was added to phase B, and stirring continued. Phase B was added to phase A and homogenized with stirring. Cooling to 40°C with stirring. The components of phases C and D were added with stirring. Cooling to room temperature with stirring. pH 6.0.

[0197] Table 5

[0198] Composition Examples 15 to 16. Examples 15 to 16 illustrate linear UV-absorbing polyethers that can be formulated with other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A. Examples 15 to 16b were prepared using the standard sunscreen emulsions shown in Table 6 below by heating phases A and B (phase B without Tinovis GTC, added with stirring) to 75°C under stirring (to resolve all crystalline components). Phase A was added to B under a homogenizer (Ultra Turrax, at 9500 rpm for 90 seconds). Cooling to room temperature with continuous stirring (using a paddle stirrer). Simultaneously, phase C was mixed at room temperature, phase C was added, and the pH was adjusted to approximately 6.5. Finally, the pH was adjusted to 6.5 to 7.0.

[0199] Table 6

[0200] Composition Examples 17 to 21. Examples 17 to 21 illustrate linear UV-absorbing polyethers that can be formulated with other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A. Examples 17 to 21 were prepared using standard sunscreen emulsions as shown in Table 7 below, by heating phase A to 75°C with stirring, followed by heating phase B with stirring without allowing Amphisol K to reach 75°C. At 75°C, zwitterionic K was added to phase B, and stirring continued. Phase B was added to phase A with stirring and homogenized. After cooling to room temperature, phase C was added. The pH was 6.1 to 6.5.

[0201] Table 7

[0202] Composition Examples 22 to 23: Examples 22 to 23 demonstrate the formulation of linear UV-absorbing polyethers using other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A. Examples 22 to 23 were prepared using the standard sunscreen emulsions shown in Table 8 below by heating phase A to 75°C with stirring, followed by heating phase B to 75°C with stirring. Homogenization was achieved by adding phase A to B with stirring. The mixture was cooled to below 40°C with stirring, and phase C was added. Stirring continued. The pH was maintained at 5.6 to 6.5.

[0203] Table 8

[0204] Composition Examples 24 to 25: Examples 24 to 25 demonstrate the formulation of linear UV-absorbing polyethers using other UV-absorbing compounds. The linear UV-absorbing polyethers were prepared in accordance with the methods described in Examples 3B and 4A. Examples 24 to 25 were prepared using standard sunscreen emulsions as shown in Table 9 below, by heating phases A and B to 75°C. Phase B was added with rapid stirring at 75°C. Phase C was added at 40°C. After cooling to room temperature, phase D was added in the given order.

[0205] Table 9

[0206] Table 10

[0207] Table 11

[0208] Table 12

[0209] Table 13

[0210] Table 14

[0211] Table 15

[0212] The embodiments of the present invention include, but are not limited to, the following: 1. A sunscreen composition comprising: A polymer composition comprising a linear ultraviolet radiation absorbing polyether, the linear ultraviolet radiation absorbing polyether comprising covalently bonded UV chromophores; and At least one additional UV-shielding compound.

[0213] 2. The composition according to embodiment 1, wherein the additional UV shielding compound is avobenzone.

[0214] 3. The composition according to Embodiment 1, wherein the covalently bonded UV chromophore is benzotriazole.

[0215] 4. The composition according to Embodiment 1, wherein the additional UV shielding compound is a UV blocking compound.

[0216] 5. The composition according to embodiment 4, wherein the UV blocking compound is titanium dioxide or zinc oxide.

[0217] 6. The composition according to embodiment 1, wherein the additional UV shielding compound is an organic UV absorbing compound.

[0218] 7. The composition according to Embodiment 6, wherein the organic UV-absorbing compound is selected from the following: diethylaminohydroxybenzoyl benzoate, ethylhexyl triazine, bis(ethylhexyloxyphenol) methoxyphenyl triazine, methylenebis(benzotriazolyl)tetramethylbutylphenol, bis(ethylhexyloxyphenol) methoxyphenyl triazine, terphenyl triazine, ethylhexyl methoxycinnamate, octocrylene, 1,1'-(1,4-piperazindiyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methyl ketone, phenylbenzimidazole sulfonic acid, ethylhexyl salicylate, holomethasone salicylate, diethylhexylbutyramide triazine, isoamyl p-methoxycinnamate, and polysilicon-15.

[0219] 8. The composition according to Embodiment 6, wherein the organic UV-absorbing compound is selected from the following: diethylaminohydroxybenzoyl benzoate, ethylhexyl triazine, bis(ethylhexyloxyphenol)methoxyphenyl triazine, methylenebisbenzotriazolyltetramethylbutylphenol, bis(ethylhexyloxyphenol)methoxyphenyl triazine, terphenyl triazine, ethylhexyl methoxycinnamate, octocrylene, and 1,1'-(1,4-piperazindiyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl] ketone.

[0220] 9. The composition according to Embodiment 1, wherein the additional UV shielding compound is a mixture of ethylhexyl triazine ketone, diethylaminohydroxybenzoylhexylbenzoate, and bis(ethylhexyloxyphenol)methoxyphenyltriazine.

[0221] 10. The composition according to Embodiment 1, wherein the additional UV shielding compound is a mixture of ethylhexyl triazine ketone, butyl methoxydibenzoylmethane, bisethylhexyloxyphenol methoxyphenyl triazine, and methylene bisbenzotriazolyl tetramethylbutylphenol.

[0222] 11. The composition according to embodiment 1, wherein the additional UV shielding compound is methylenebisbenzotriazolyltetramethylbutylphenol and octocrylene.

[0223] 12. The composition according to embodiment 1, wherein the additional UV shielding compound is octocrylene.

[0224] 13. The composition according to embodiment 1 further comprises an acrylic acid / styrene copolymer.

[0225] 14. The composition according to embodiment 1 further comprises a film-forming polymer selected from natural polymers and synthetic polymers.

[0226] 15. The composition according to embodiment 14, wherein the film-forming polymer is a copolymer of vinylpyrrolidone and long-chain α-olefin.

[0227] 16. The composition according to embodiment 1 further comprises silicon dioxide.

[0228] It should be understood that although the present invention has been described in conjunction with specific embodiments thereof, the foregoing description is intended to be illustrative and not to limit the scope of the invention.

Claims

1. A sunscreen composition comprising: A polymer composition comprising a linear ultraviolet radiation absorbing polyether, the linear ultraviolet radiation absorbing polyether comprising covalently bonded UV chromophores; and At least one additional UV-shielding compound.

2. The composition according to claim 1, wherein the additional UV-shielding compound is avobenzone.

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