Low-penetration sunscreen composition

Abstract

The present invention provides a sunscreen composition comprising (a) diethylamino hydroxybenzoylhexyl benzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylene bis-benzotriazolyltetramethylbutylphenol, and substantially free of UV absorbers having a molecular weight of 380 daltons or less.

Description

[Technical Field]

[0001] This application claims the interests of U.S. Provisional Patent Application No. 63 / 471362, filed June 6, 2023, the full disclosure of which is incorporated herein by reference for all purposes. [Background technology]

[0002] It is well known that prolonged exposure to ultraviolet (UV) radiation from sunlight and other sources can lead to photo-induced skin diseases and the formation of erythema, and may increase the risk of skin cancers such as melanoma. UV exposure also accelerates skin aging, including loss of skin elasticity and the development of wrinkles.

[0003] For these reasons, sunscreen compositions are commonly used to provide protection from the sun, and a variety of sunscreen compositions are commercially available. Many contain low molecular weight organic UV absorbers such as octocrylene, homosalate, avobenzone, oxybenzone, octyl salicylate, and cinnamic acid. While these UV filters are effective in absorbing ultraviolet rays, large quantities are often required to provide a high SPF sunscreen composition. Because they are low molecular weight compounds, consumers may have concerns about their potential to penetrate the skin, especially when used in large quantities.

[0004] HIRUDO Derm Sun Protect Krem dlya Ditei Sontsezakhysnyi SPF 75 Solar Protect Kids contains a combination of UV absorbers and UV blockers, specifically titanium dioxide. The UV absorber combination is a combination of diethylamino hydroxybenzoylhexyl benzoate, ethylhexyl triazone, methylene bis-benzotriazolyltetramethylbutylphenol, tris-biphenyl triazine, and bis-ethylhexyloxyphenol methoxyphenyl triazine, along with the low molecular weight UV absorber ethylhexyl methoxycinnamate.

[0005] LUPIN Propiacne Day Local Sunscreen with Solar Protection SPF 35 also contains a combination of UV absorbers and titanium dioxide. The UV absorbers are diethylaminohydroxybenzoylhexylbenzoate, tris-biphenyltriazine, bis-ethylhexyloxyphenol methoxyphenyltriazine, methylenebis-benzotriazolyltetramethylbutylphenol, and ethylhexyltriazone. However, this product also contains the low molecular weight UV absorber octocrylene. [Overview of the project] [Problems that the invention aims to solve]

[0006] A sunscreen composition substantially free of low molecular weight UV absorbers such as ethylhexyl methoxycinnamate and octocrylene, and therefore substantially non-penetrating to the skin, has been discovered. Such a composition would instead contain a specific combination of high molecular weight UV absorbers in specific amounts, but still be desirable to provide a high SPF product. [Means for solving the problem]

[0007] The present invention provides a sunscreen composition comprising (a) diethylamino hydroxybenzoylhexyl benzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylene bis-benzotriazolyltetramethylbutylphenol, and substantially free of UV absorbers having a molecular weight of 380 daltons or less.

[0008] The composition may optionally further contain up to about 3% by weight of tris-biphenyltriazine.

[0009] The composition may optionally further contain up to about 2% by weight of a UV-blocking agent, such as titanium dioxide or zinc oxide.

[0010] The composition may optionally further contain a polymeric UV absorber, such as a linear UV-absorbing polyether containing a covalently bonded benzotriazole chromophore.

[0011] The composition may optionally further contain one or more cosmetically acceptable surfactants, such as niacinamide, glycerin, acetylglucosamine, and sodium hyaluronate. [Modes for carrying out the invention]

[0012] Unless otherwise specified, all scientific and technical terms used herein have the same meanings as those generally understood by those skilled in the art in the field to which this invention pertains. All publications, patent applications, patents, and other references referenced herein are incorporated herein by reference.

[0013] As used herein, “topical application” means applying or massaging directly onto the skin or scalp, for example, by hand or using an applicator such as a wipe, roller, or spray.

[0014] As used herein, “cosmetics” specifically refers to beautifying substances or preparations that maintain, restore, give, adorn, or enhance a physically beautiful appearance, or that make a person appear more beautiful or youthful, in the case of the appearance of tissues, skin, or hair.

[0015] As used herein, “effective amount for cosmetic use” means an amount of physiologically active compound or composition that is sufficient to treat one or more conditions, but in a quantity that is small enough to avoid severe side effects. The effective amount for cosmetic use of a compound or composition varies depending on the condition being treated, the age and health status of the end user, the severity of the condition being treated / prevented, the duration of treatment, the nature of other treatments, the specific compound or product / composition used, the cosmetically acceptable carrier used, and similar factors.

[0016] As used herein, “cosmetic-grade” means that the ingredient described by this term is suitable for use in contact with tissue (e.g., skin or hair) without excessive toxicity, incompatibility, instability, irritation, allergic reactions, etc.

[0017] As used herein, “cosmetic-grade surfactant” means a compound (synthetic or natural) that has a cosmetic or therapeutic effect on the skin or hair.

[0018] As used herein, “treat or treat” means to alleviate, reduce, prevent, improve or eliminate the presence or signs of a condition or disorder.

[0019] As used herein, "phase-stable" means that the aqueous and oil phases of the emulsion do not separate to a detectable extent for at least two weeks at room temperature.

[0020] As used herein, “substantially absent” means not intentionally or willfully added. For example, if a composition contains an ingredient in less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, it may be substantially absent from such an ingredient. A composition may contain no such ingredient at all, i.e., 0% by weight, and may be completely absent from such an ingredient.

[0021] As used herein, "UV absorber" refers to a compound that absorbs radiation in a portion of the ultraviolet spectrum (290 nm to 400 nm), for example, at least about 1000 mol for at least one wavelength in the ultraviolet spectrum as defined above. -1 cm -1 This refers to something that has an absorption coefficient of [value].

[0022] Unless otherwise specified, percentages or concentrations refer to weight percentages or weight concentrations (i.e., %(W / W)). Unless otherwise specified, all ranges include both endpoints; for example, "4-9" includes both endpoints 4 and 9.

[0023] UV absorber The sunscreen composition of the present invention contains a combination of UV absorbers each having a molecular weight exceeding 380 Daltons. In particular, the sunscreen composition contains (a) diethylamino hydroxybenzoyl hexyl benzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylene bis-benzotriazolyl tetramethylbutyl phenol.

[0024] The combination of UV absorbers in the sunscreen composition may consist essentially of, or consist of, (a) diethylamino hydroxybenzoyl hexyl benzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylene bis-benzotriazolyl tetramethylbutyl phenol.

[0025] The sunscreen composition of the present invention may contain a UV absorber, a UV blocker, and a topically acceptable carrier for cosmetic use, and the UV absorber and the UV blocker consist essentially of, or consist of, (a) about 2 to about 6 weight percent of diethylamino hydroxybenzoyl hexyl benzoate, (b) tris-biphenyl triazine at 3 weight percent or less, (c) about 0.5 to about 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyl triazine, (d) about 1.64 to about 4.55 weight percent of ethylhexyl triazone, (e) about 2 to about 6 weight percent of methylene bis-benzotriazolyl tetramethylbutyl phenol, and (f) titanium dioxide at 2 weight percent or less.

[0026] The sunscreen composition substantially does not contain a UV absorber having a molecular weight of 380 Daltons or less. Preferably, the sunscreen composition completely does not contain a UV absorber having a molecular weight of 380 Daltons or less.

[0027] Therefore, the sunscreen composition contains only UV absorbers having a molecular weight greater than 380 daltons. This sunscreen composition may optionally also contain one or more UV blockers or polymer UV absorbers, as described below. However, it substantially does not contain UV absorbers having a molecular weight of 380 daltons or less. In this way, the sunscreen composition is advantageously low-penetration or substantially non-penetrating to the skin or hair.

[0028] Optionally, all UV absorbers in the sunscreen composition have a melting point above 50°C.

[0029] The total amount of UV absorbers in the sunscreen composition is in the range of about 9 to about 20 weight percent of the total weight of the sunscreen composition, preferably about 9.5 to about 17.5 weight percent. The total amount of UV absorbers in the sunscreen composition may be less than about 18 weight percent of the total weight of the sunscreen composition. More preferably, the total amount of UV absorbers in the sunscreen composition is less than about 15 weight percent of the total weight of the sunscreen composition.

[0030] Despite the low total amount of UV absorbers in the sunscreen composition, the composition provides a high SPF value.

[0031] Diethylamino hydroxybenzoyl hexyl benzoate ("DHHB") The first UV absorber in the sunscreen composition is diethylamino hydroxybenzoyl hexyl benzoate ("DHHB"). Diethylamino hydroxybenzoyl hexyl benzoate is also chemically known as benzoic acid, 2-[-4-(diethylamino)-2-hydroxybenzoyl]-hexyl ester. For example, it is marketed by BASF as UVINUL® A-PLUS or by DSM as PARSOL® DHHB. The molecular weight of diethylamino hydroxybenzoyl hexyl benzoate is 398 daltons.

[0032] The sunscreen composition preferably contains about 2 to about 6 weight percent of diethylaminohydroxybenzoylhexylbenzoate, based on the total weight of the sunscreen composition.

[0033] More preferably, the sunscreen composition contains about 3 to about 5.5 weight percent of diethylaminohydroxybenzoylhexylbenzoate, based on the total weight of the sunscreen composition.

[0034] Bis-ethylhexyloxyphenol methoxyphenyl triazine ("BEMT") The second UV absorber in the sunscreen composition is bis-ethylhexyloxyphenol methoxyphenyl triazine ("BEMT"). Bis-ethylhexyloxyphenol methoxyphenyl triazine is also chemically known as phenol, 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis(5-((2-ethylhexyl)oxy,(1,3,5)-triazine-2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl), anisotriazine, and bemotidinol. For example, it is commercially available from BASF as Tinosorb® S. The molecular weight of bis-ethylhexyloxyphenol methoxyphenyl triazine is 627 daltons.

[0035] The sunscreen composition preferably contains about 0.5 to about 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyl triazine, based on the total weight of the sunscreen composition.

[0036] More preferably, the sunscreen composition contains about 1.5 to about 2.3 weight percent of bis-ethylhexyloxyphenol methoxyphenyl triazine, based on the total weight of the sunscreen composition.

[0037] Ethylhexyl triazone (EHT) The third UV absorber in the sunscreen composition is ethylhexyl triazone ("EHT"). Ethylhexyl triazone is also chemically known as 4-[[4,6-bis[[4-(2-ethylhexoxy-oxomethyl)phenyl]amino]-1,3,5-triazine-2-yl]amino]benzoate 2-ethylhexyl ester and octyl triazone. For example, it is commercially available from BASF as UVINUL® T 150. The molecular weight of ethylhexyl triazone is 823 daltons.

[0038] The sunscreen composition preferably contains about 1.64 to about 4.55 weight percent of ethylhexyl triazone, based on the total weight of the sunscreen composition.

[0039] Methylenebis-benzotriazol tetramethylbutylphenol ("MBBT") The fourth UV absorber in the sunscreen composition is methylenebis-benzotriazoltetramethylbutylphenol ("MBBT"). Methylenebis-benzotriazoltetramethylbutylphenol is also chemically known as phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) and bisoctrizole. For example, it is commercially available from BASF as Tinosorb® M. The molecular weight of methylenebis-benzotriazoltetramethylbutylphenol is 659 daltons.

[0040] The sunscreen composition preferably contains about 2 to about 6 weight percent of methylenebis-benzotriazolyltetramethylbutylphenol, based on the total weight of the sunscreen composition.

[0041] More preferably, the sunscreen composition contains about 2 to about 5.5 weight percent of methylenebis-benzotriazolyltetramethylbutylphenol, based on the total weight of the sunscreen composition.

[0042] Tris-biphenyltriazine (TBT) The composition may optionally contain an additional UV absorber, tris-biphenyltriazine ("TBT"). Tris-biphenyltriazine is also chemically known as 1,3,5-triazine, 2,4,6-tris([1,1'-biphenyl]-4-yl)-, and 2,4,6-tri([1,1'-biphenyl]-4-yl)-1,3,5-triazine. It is commercially available from BASF as Tinosorb® A2B. The molecular weight of tris-biphenyltriazine is 537 daltons.

[0043] When used, the sunscreen composition preferably contains 3% by weight or less of tris-biphenyltriazine based on the total weight of the sunscreen composition.

[0044] More preferably, the sunscreen composition contains about 0.5 to about 1 weight percent of tris-biphenyltriazine based on the total weight of the sunscreen composition.

[0045] Low molecular weight UV absorber The sunscreen composition is substantially free, and preferably completely free, of UV absorbers having a molecular weight of 380 daltons or less.

[0046] Examples of UV absorbers having a molecular weight of 380 daltons or less include: octocrylene, homosalate, avobenzone, octyl salicylate, methoxycinnamic acid derivatives (e.g., octyl methoxycinnamate and isoamyl methoxycinnamate), camphor derivatives (e.g., 4-methylbenzylidene camphor, camphor or benzalkonium methosulfate, ecamsul (Mexoryl® SX)), terephthalylidenedicansulfonic acid, and other salicylic acid Salic acid derivatives (e.g., trolamine salicylate and ethylhexyl salicylate), sulfonic acid derivatives (e.g., phenylbenzimidazole sulfonic acid), benzone derivatives (e.g., dioxybenzone, surisobenzone, and oxybenzone), benzoic acid derivatives (e.g., aminobenzoic acid and octyldimethylparaaminobenzoic acid), octocrylene and other β,β-diphenyl acrylates, dioctylbutamide triazone, octyltriazone, drometrizole trisiloxane, and menthyl anthranylate.

[0047] Optionally, the sunscreen composition is substantially free of UV absorbers having a melting point below 30°C.

[0048] The sunscreen composition does not need to contain octocrylene.

[0049] The sunscreen composition does not need to contain homosalate.

[0050] The sunscreen composition does not need to contain avobenzone.

[0051] The sunscreen composition does not need to contain octyl salicylate.

[0052] The sunscreen composition does not need to contain ethylhexyl methoxycinnamate.

[0053] The sunscreen composition does not need to contain phenylbenzimidazole sulfonic acid.

[0054] UV blocking agent The sunscreen composition may optionally contain a UV blocker. As used herein, "UV blocker" means a compound that reflects or scatters ultraviolet light. UV blockers are typically inorganic metal oxides, examples of which include titanium dioxide, zinc oxide, and other transition metal oxides. UV blockers are typically solid particles in a fine or nanoparticle form having a diameter of about 0.01 μm to about 10 μm.

[0055] The sunscreen composition may contain 2% by weight or less of a UV-blocking agent based on the total weight of the sunscreen composition.

[0056] The UV blocking agent may be selected from the group consisting of titanium dioxide and zinc oxide.

[0057] The UV blocking agent may be titanium dioxide. An example of titanium dioxide that can be used is titanium dioxide (and) silica, which is commercially available from Merck as Eusolex® T AVO.

[0058] Polymer UV absorber The sunscreen composition may also optionally contain polymeric UV absorbers.

[0059] The polymer UV absorber may be a linear UV-absorbing polyether, that is, a polymer comprising a backbone of ether functional groups and UV-absorbing chromophores covalently bonded to the backbone.

[0060] As used herein, “linear UV-absorbing polyether” means a polyether that absorbs radiation in a portion of the ultraviolet spectrum (wavelengths from 290 to 400 nm). Linear UV-absorbing polyethers have a weight-average molecular weight (Mw) that may be suitable for reducing or preventing chromophores from being absorbed through the skin. According to one embodiment, a suitable molecular weight Mw for a linear UV-absorbing polyether is greater than 500. In one embodiment, Mw is in the range of about 500 to about 50,000. In another embodiment, Mw is in the range of about 1,000 to about 20,000, for example, in the range of about 1,000 to about 10,000.

[0061] Such linear UV-absorbing polyethers are typically contained in polymer compositions consisting of complex combinations of different molecules, i.e., complex reaction products. Typically, these polymer compositions contain at least about 50% linear UV-absorbing polyether. A polymer composition may contain at least about 75% linear UV-absorbing polyether. A polymer composition may contain at least about 90%, for example, about 95% or more linear UV-absorbing polyether.

[0062] Linear UV-absorbing polyethers contain multiple ether functional groups covalently bonded to each other. The "backbone" 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 can be considered pendant groups branching off from the backbone.

[0063] The linear UV-absorbing polyether preferably has a branchless skeleton.

[0064] Linear UV-absorbing polyethers may contain glyceryl repeating units and may therefore be characterized as polyglycerols. As used herein, “glyceryl repeating units” (also referred to herein as “glyceryl remnant units”) means glycerol units excluding nucleophiles such as hydroxyl groups. Glyceryl remnant units contain ether functional groups and can generally be represented as C3H5O for linear and dendritic remnants (Rokicki et al. Green Chemistry., 2005, 7, 52). Suitable glyceryl remnant units include the following dehydrated forms of glyceryl units (i.e., with 1 mole of water removed): linear-1,4(L1,4) glyceryl units, linear-1,3(L1,3) glyceryl repeating units, dendritic(D) glyceryl units, terminal-1,2(T1,2) units, and terminal-1,3(T1,3) units.

[0065] According to a particular embodiment, the linear UV-absorbing polyether comprises either or both of the repeating units shown in the following formulas IA and IB.

[0066] [ka]

[0067] In formulas IA and IB, X can be selected from, for example, hydrogen, a linear alkyl, alkenyl or alkynyl hydrocarbon chain, a linear siloxane, and the like. In one embodiment, the group X represents octadecane.

[0068] Y represents a UV chromophore as described below. The proportion of ether repeating units having substituent Y is a real number represented by Equation 1. m / (n+m) Equation 1 In the formula, m and n represent real numbers between 0 and 1, and the sum of n and m is equal to 1.

[0069] The linear UV-absorbing polyether may be, for example, a homopolymer or a copolymer optionally containing additional pendant groups other than UV-absorbing chromophores. The distribution of pendant groups along the polymer chain can be modified to obtain optimal polymer properties. In one embodiment, the linear UV-absorbing polyether is a random copolymer, and the pendant groups, including UV-absorbing chromophores, 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 pendant groups. In yet another embodiment, the distribution of pendant groups along the polymer backbone lies somewhere between the boundary conditions of a block copolymer and a statistically random copolymer.

[0070] A linear UV-absorbing polyether contains one or more covalently bonded UV chromophores. UV chromophores that absorb UVA or UVB radiation are preferred. UV chromophores can absorb in both the UVA and UVB regions.

[0071] Suitable UV chromophores include triazoles (a moiety containing a five-membered heterocycle having two carbon atoms and three nitrogen atoms), such as benzotriazoles including hydroxyphenyl-benzotriazole, and triazines (a six-membered heterocycle containing three nitrogen atoms and three carbon atoms). Other examples of UV chromophores include camphor, such as benzylidene camphor and its derivatives (e.g., terephthalylidene dicansulfonic acid), and dibenzoylmethane and its derivatives.

[0072] In one embodiment, the UV chromophore is a benzotriazole having a structure represented by formula II, which provides both photostability and strong UVA absorbance.

[0073] [ka] In the formula, each R 14R is independently selected from the group consisting of hydrogen, C1-C20 alkyl, alkoxy, acyl, alkyloxy, alkylamino, and halogen, 15 R is independently selected from the group consisting of hydrogen, C1-C20 alkyl, alkoxy, acyl, alkyloxy, and alkylamino, 21 R is selected from C1-C20 alkyl, alkoxy, acyl, alkyloxy, and alkylamino. 15 or R 21 One of the groups may contain a functional group that enables bonding to the polymer.

[0074] Compounds similar in structure to formula II are described in U.S. Patent No. 5,869,030 and include, but are not limited to, methylenebis-benzotriazolyltetramethylbutylphenol.

[0075] In one embodiment, the benzotriazole is derived from a transesterification product of 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoic acid and polyethylene glycol 300, which is commercially available from BASF as TINUVIN 213. In another embodiment, the benzotriazole is a benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, C7-9-branched and linear alkyl ester, which is commercially available from BASF as TINUVIN 99.

[0076] In another embodiment, the UV-absorbing group contains a triazine moiety. An exemplary triazine is 6-octyl-2-(4-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-3-hydroxyphenoxy)propanoate, which is commercially available from BASF as TINUVIN 479.

[0077] Examples of suitable UVB-absorbing chromophores include: 4-aminobenzoic acid and its alkanes; anthranilic acid and its alkanes; salicylic acid and its alkanes; their hydroxycinnamic acid alkanes; dihydroxy, dicarboxy, and hydroxycarboxybenzophenone, and their alkanes or acid halide derivatives; dihydroxy, dicarboxy, and hydroxycarboxychalcone, and their alkanes or acid halide derivatives; dihydroxy, dicarboxy, and hydroxycarboxycoumarin, and their alkanes or acid halide derivatives; benzalmalonate (benzylidenemalonate); benzimidazole derivatives (e.g., phenylbenzylimazole sulfonic acid, PBSA (phenyl benzilimazole sulfonic acid), benzoxazole derivatives, and other suitably functionalized species copolymerizable within the polymer chain).

[0078] A linear UV-absorbing polyether may contain two or more UV chromophores, or two or more types or chemical classes of UV chromophores.

[0079] Linear UV-absorbing polyethers preferably have low polydispersity. For example, the polydispersity index of a linear UV-absorbing polyether may be about 1.5 or less, for example, about 1.2 or less. The polydispersity index is defined as Mw / Mn (i.e., the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn).

[0080] Linear UV-absorbing polyethers can be manufactured as described in U.S. Patent No. 9,255,180 and No. 9,248,092 (these disclosures are incorporated herein by reference in their entirety).

[0081] A preferred linear UV-absorbing polyether is a linear UV-absorbing polyether containing a benzotriazole chromophore having the following formula.

[0082] [ka] In the formula, n and m are independent numbers between 0 and 20, and at least one of m or n is 1 or greater. For example, the sum of n and m is a number between 3 and 10.

[0083] For example, such a linear UV-absorbing polyether containing a benzotriazole chromophore may be based on a polyglycerol skeleton containing five glycerol units, as shown in Formula IV.

[0084] [ka]

[0085] The glycerol backbone in these preferred polyethers typically consists mainly of 3 to 10 glycerol units, thereby covalently bonding the hydroxyl groups of the glycerol backbone to the benzotriazole UV chromophore. It can be reasonably assumed that primary hydroxyl groups (terminal units) react faster than secondary hydroxyl groups, which are less reactive for derivatization. Therefore, some secondary hydroxyl groups remain unreacted. The glycerol backbone consists mainly of linear and unbranched structural units. Branched isomers and higher molecular weight fractions containing more than 10 glycerol units may exist.

[0086] A particularly preferred linear UV-absorbing polyether is polyglycerylbenzotriazolyl t-butylhydroxyphenylpropionate.

[0087] Polymer compositions containing these preferred linear UV-absorbing polyethers, including benzotriazole chromophores, may be further characterized as follows: 1. MW distribution: Mn over 500 Da, Mw over 1200 Da (GPC, calibrated on polystyrene) 2. Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-methyl ester: 1.0% or less (HPLC) 3. Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-: 1.0% or less (HPLC) 4. Total concentration of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-methyl ester and benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-: 1.0% or less (HPLC) 5. UV absorption: E 1% 1cm (344nm): over 310 6. Amount of binding chromophore: over 70% 7.Tg (℃): Over 50 (DSC) 8. The concentration of residual catalyst (tin-II-ethylhexanoate) in the transesterification reaction is less than 700 ppm, or substantially tin-free (IPC). 9. Solubility in cethiol B: over 30% 10. Solubility in cethiol AB: over 30%

[0088] These preferred linear UV-absorbing polyethers containing benzotriazole chromophores can be prepared by esterification / transesterification reactions, including the step of reacting a polyglycerol intermediate with a benzotriazole UV chromophore containing complementary functional groups to form a polyether, as described in U.S. Patent No. 1,0596,087 (the disclosure thereof is incorporated herein in its entirety).

[0089] The sunscreen composition may contain, based on the total weight of the sunscreen composition, about 5 to about 20 weight percent, or about 10 to about 15 weight percent, of such linear UV-absorbing polyethers.

[0090] SPF The sun protection factor (SPF) of a composition can be tested using the following in vitro SPF test method. The baseline transmittance of the collagen matrix substrate (in vitro skin®-IMS-Florida Skincare Testing, Florida USA) is measured for UV absorbance using a calibrated transmission spectrophotometer with an integrating sphere (Labsphere® UV-1000S UV transmission analyzer, Labsphere® UV-2000S UV transmission analyzer (Labsphere, North Sutton, NH, USA) or equivalent). The test sample is then applied to the substrate at an application density of approximately 0.75 mg / cm² and subsequently rubbed with a metallic pointe to form a uniform thin layer. The sample is dried for 15 minutes and then measured for UV absorbance in the same manner. Using the absorbance measurements, the SPF is calculated as known in the art using the following equation:

[0091]

number

[0092] The sunscreen composition is advantageous in that it has a high SPF ratio to the total amount of UV absorbers and UV blockers. In particular, the ratio of the SPF of the composition to the total weight percentage of UV absorbers and UV blockers combined in the composition is at least about 4.1, preferably at least about 4.4.

[0093] The sunscreen composition has an SPF of at least about 30 when measured by, for example, an in vitro SPF test, and the ratio of the composition's SPF to the total weight percentage of UV absorbers and UV blockers combined in the composition is at least about 4.1.

[0094] Topical composition The sunscreen composition can be used by topical application to mammals, for example, by placing, wiping, or spreading the composition directly onto the skin, hair, or nails of mammals, particularly humans.

[0095] The sunscreen composition preferably contains a topical carrier acceptable for cosmetic use. Preferably, the composition is in the form of an oil-in-water emulsion containing a continuous aqueous phase and a discontinuous oil phase dispersed within the continuous aqueous phase. However, other product forms may be used, such as oil-in-water, oil-water-oil, water-oil-water, or PIT emulsions, microemulsions, anhydrous compositions, gels, oils, creams, milks, lotions, powders, lacquers, tablets, makeup or other color cosmetics, sticks, sprays and aerosols (with or without propellants), foams, pastes, hair treatment formulations such as shampoos and conditioners, hair care formulations, for example, pre-treatment formulations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair straightening formulations, liquid hair setting formulations, hair foams and hair sprays.

[0096] Sunscreen compositions can be prepared using mixing and blending methods well known in the fields of sunscreens and cosmetics. In one embodiment, the sunscreen composition is an oil-in-water emulsion produced by preparing an oil phase by mixing a UV absorber 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 to a degree sufficient to substantially uniformly disperse the oil phase in the aqueous phase, such that the aqueous phase is continuous and the oil phase is discontinuous.

[0097] In certain embodiments, the sunscreen composition is a phase-stable oil-in-water emulsion.

[0098] In certain embodiments, the UV absorber is dissolved in the oil phase, rather than dispersed or suspended within it. A suitable solvent for the UV absorber is dicaprylyl carbonate, available from BASF as CETIOL CC.

[0099] The oil phase may exist as individually separated droplets or units, for example, having an average diameter of approximately 1 μm to 1000 μm, such as approximately 1 μm to 100 μm.

[0100] The weight percentage of the aqueous phase in the composition may be in the range of approximately 45 to approximately 90%, for example, approximately 55 to approximately 80%, or for example, approximately 60 to approximately 80%. The weight percentage of water in the aqueous phase may be approximately 90% or more, for example, approximately 95% or more.

[0101] In certain embodiments, the weight percentage of the oil phase in the composition is about 10 to about 55%, for example, about 20 to about 45%, for example, about 20 to about 40%.

[0102] In certain embodiments, the oil phase essentially consists of a UV absorber. In certain embodiments, the oil phase includes more than about 60% by weight of a UV absorber, for example more than 75% by weight of a UV absorber, for example more than 90% by weight of a UV absorber, for example more than 97% by weight of a UV absorber, for example more than 99% by weight of a UV absorber.

[0103] The composition can be combined with a "cosmetic-grade topical carrier," that is, a carrier for topical use which may contain other components dispersed or dissolved therein and which has acceptable properties that make it safe for topical use.

[0104] The composition may optionally contain a wide variety of additional oil-soluble and / or water-soluble materials, at concentrations established in the art, that have been conventionally used in compositions for use on skin or hair. For example, it may contain emulsifiers, surfactants, pearlescent or opaque agents, thickeners, emollients, conditioners, humectants, chelating agents, scrubbing agents, and additives that improve the appearance, feel, or scent of the cleansing composition, such as colorants, fragrances, preservatives, and pH adjusters.

[0105] Water-soluble or water-dispersible polymers may be added to the composition. Water-dispersible polymers typically consist of water-insoluble polymers that are micronized and, if possible, dispersed in a water carrier using a surfactant dispersant. Water-dispersible polymers can form a film and improve the water resistance of the composition. An example of a water-soluble polymer is Polyaldo® 10-1-L (polyglyceryl-10 laurate), available from Lonza. Examples of water-dispersible polymers include water-dispersible polyurethanes such as Baycusan® C1000 (polyurethane-34), available from Bayer; Dow Corning® 2501 (bis-PEG-18 methyl ether dimethyl silane), available from Dow Corning; Eastman AQTM38S (polyester-5), available from Eastman Chemical; and Intelimer® 8600 (C8-22 alkyl acrylate / methacrylate crosspolymer), available from Air Products.

[0106] The sunscreen composition may also include a film-forming agent. The film-forming agent is typically a hydrophobic material that imparts film-forming and / or waterproof properties. One such agent is available from New Phase Technologies as Performalene® 400 (polyethylene with a molecular weight of 400). Another suitable film-forming agent is polyethylene 2000 (molecular weight 2000), available from New Phase Technologies as Performalene®. Another suitable film-forming agent is a synthetic wax available from New Phase Technologies as Performa® V-825. Other typical film-forming agents include acrylate / acrylamide copolymers, acrylate copolymers, acrylate / C12-C22 alkyl methacrylate copolymers, polyethylene, wax, VP / dimethiconyl acrylate / polycarbamyl polyglycol esters, butylated PVP, PVP / hexadecene copolymers, octadecene / MA copolymers, PVP / eicosene copolymers, tricontanyl PVP, rapeseed oil / tung oil copolymers, decamethylcyclopentasiloxane (and) trimethylsiloxysilicate, dimethicone; acrylate / dimethicone copolymers, hydrolyzed jojoba esters; jojoba esters and mixtures thereof. In some cases, the film-forming agent is acrylate / C12-C22 alkyl methacrylate copolymer, sold by Ashland under the trade name Allianz(trademark) OPT.

[0107] Preferably, the film-forming agent is selected from the group consisting of hydrolyzed jojoba esters, jojoba esters, triacontanyl PVP, acrylate / dimethicone copolymers, and mixtures thereof.

[0108] Suitable emollients include mineral oil, petrolatum, vegetable oils (e.g., triglycerides such as caprylic / capric triglyceride), waxes and mixtures of other fatty acid esters (including, but not limited to, isopropyl palmitate, isopropyl myristate, diisopropyl adipate, dicaprylyl carbonate, C12-15 alkyl benzoates, diisopropyl sebacate, and isononyl isononanoate), and silicone oils such as dimethicone. Preferably, the emollient is selected from the group consisting of C12-15 alkyl benzoates, diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, and isononyl isononanoate, and mixtures thereof.

[0109] In certain embodiments, a mixture of a triglyceride (e.g., caprylic / capric triglyceride) and a glycol ester may be used to solubilize the UV absorber. In other embodiments of the present invention, the composition is substantially free of or free of emollients.

[0110] Other examples of suitable solvents include propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, 1,2,4-butanetriol, sorbitol ester, 1,2,6-hexanetriol, ethanol, and mixtures thereof.

[0111] The composition may contain an emulsifier. Preferably, the emulsifier is selected from the group consisting of glyceryl stearate; PEG-100 stearate, cetyl alcohol; PEG-75 stearate; ceteth-20; steareth-20; potassium cetyl phosphate, and mixtures thereof.

[0112] In certain embodiments, the composition comprises a pigment suitable for providing color or opacity. The pigment may be suitable for use in color cosmetics, including compositions for application to hair, nails, and / or skin, particularly the face. Examples of color cosmetic compositions include, but are not limited to, foundations, concealers, primers, blushes, mascaras, eyeshadows, eyeliners, lipsticks, nail polishes, and colored moisturizers. Pigments suitable for providing color or opacity may consist of iron oxides (including red and yellow iron oxides), titanium dioxide, ultramarine, and chromium or chromium hydroxide pigments, as well as mixtures thereof. The pigment may be lake pigments precipitated on an inert binder such as an insoluble salt, and are organic dyes such as azo, indigoid, triphenylmethane, anthraquinone, and xanthine dyes, which are referred to as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc. Examples of lake pigments include Red #6, Red #7, Yellow #5, Violet #2, and Blue #1. The pigment may be an interference pigment. 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 as CHROMALITE pigment (BASF), titanium dioxide and / or iron oxide coated on mica such as FLAMENCO pigment (BASF), mica / titanium dioxide / iron oxide pigments including commercially available KTZ pigment (Kobo products), CELLINI pearl pigment (BASF), and borosilicate-containing pigments such as REFLECKS pigment (BASF).

[0113] In certain embodiments, the sunscreen composition may contain one or more compounds suitable for enhancing the photostability of UV absorbers of other components in the composition. Examples of photostabilizers include naphthalenedicarboxylic acid diesters or polyesters.

[0114] In one embodiment, the sunscreen composition includes a humectant. Examples of humectants include, but are not limited to, glycerin, pentylene glycol, and butylene glycol.

[0115] In one embodiment, the sunscreen composition includes a humectant selected from the group consisting of glycerin, pentylene glycol, and mixtures thereof.

[0116] The sunscreen composition may, advantageously, contain about 0.5 to about 2 weight percent of glycerin. For example, the sunscreen composition may contain about 1 weight percent of glycerin.

[0117] In another embodiment, the sunscreen composition has a pH of about 5 to about 6. The sunscreen composition may also have a pH of about 5.5.

[0118] The composition may contain one or more other cosmetically acceptable surfactants, such as anti-acne agents, oil control agents, antibacterial agents, anti-inflammatory agents, antifungal agents, antiparasitic agents, topical analgesics, sunscreens, photoprotective agents, antioxidants, keratolytic agents, surfactants, moisturizers, various nutrients, vitamins, energy boosters, antiperspirants, skin astringents, deodorants, stabilizers, skin hardening inhibitors, and skin or hair conditioning agents.

[0119] The amount of other cosmetic surfactants may range from about 0.001% to about 20% by weight of the composition, for example, from about 0.01% to about 5% by weight of the composition, or from about 0.005% to about 10% by weight of the composition.

[0120] Activating agents acceptable for cosmetic use include, for example, benzoyl peroxide, D-panthenol carotenoids, ceramides, polyunsaturated fatty acids, essential fatty acids, enzymes such as laccase, enzyme inhibitors, minerals, hormones such as estrogen, steroids such as hydrocortisone, copper salts such as 2-dimethylaminoethanol and copper chloride, peptides (such as argireline, Syn-Ake, those containing copper, and acetyl dipeptide-31 amide), amino acids such as coenzyme Q10 and proline, vitamins, lactobionic acid, acetylcoenzyme A, niacin, riboflavin, thiamine, ribose, electron transporters such as NADH and FADH2, and natural extracts (aloe vera, feverfew, oats, dill, blackberry, paulownia, Pichia anomala). The following may be selected: anomala (and chicory, etc.), resorcinols such as 4-hexylresorcinol, curcuminoids, sugar amines such as acetylglucosamine, glycosaminoglycans such as hyaluronic acid or its sodium salt (sodium hyaluronate), and derivatives and mixtures thereof.

[0121] The composition may advantageously contain about 0.5 to about 2 weight percent of feverfew extract, for example, about 1 weight percent of feverfew extract.

[0122] The composition may advantageously contain about 2 to about 6 weight percent of acetylglucosamine, for example, about 4 weight percent of acetylglucosamine.

[0123] The composition may preferably contain about 0.01 to about 0.1 weight percent of sodium hyaluronate, for example, about 0.05 weight percent of sodium hyaluronate.

[0124] Examples of vitamins include, but are not limited to, vitamin A, B vitamins (e.g., vitamin B3, vitamin B5, and vitamin B12), vitamin C, vitamin K, and different forms of vitamin E, such as α, β, γ, or δ tocopherols, or mixtures and derivatives thereof.

[0125] The composition may, advantageously, contain about 1 to about 5 weight percent of niacinamide, for example, about 2 weight percent of niacinamide.

[0126] Examples of antioxidants include, but are not limited to, water-soluble antioxidants such as sulfhydryl compounds and their derivatives (e.g., sodium metabisulfite and N-acetyl-cysteine), lipoic acid and dihydrolipoic acid, resveratrol, lactoferrin, and ascorbic acid and ascorbic acid derivatives (e.g., ascorbyl palmitate, ascorbyl polypeptide, and sodium ascorbyl phosphate). Suitable oil-soluble antioxidants for use in the compositions of the present invention include, but are not limited to, butylated hydroxytoluene, retinoids (e.g., retinol and retinyl palmitate), tocopherols (e.g., tocopherol acetate), tocotrienols, and ubiquinone. Suitable natural extracts containing antioxidants for use in the compositions of the present invention include, but are not limited to, extracts containing flavonoids and isoflavonoids and their derivatives (e.g., genistein and daidzein), resveratrol, rutin, and the like. Examples of such natural extracts include grape seeds, green tea, pine bark, and propolis.

[0127] The composition may contain about 0.1 to about 0.5 weight percent of tocopherol acetate, for example, about 0.2 weight percent of tocopherol acetate.

[0128] The composition may contain about 0.1 to about 0.5 weight percent of sodium ascorbyl phosphate, for example, about 0.2 weight percent of sodium ascorbyl phosphate.

[0129] Advantageously, the composition may also contain a cosmetically acceptable surfactant selected from the group consisting of niacinamide, tocopheryl acetate, sodium ascorbyl phosphate, acetylglucosamine, trehalose, feverfew extract, glycerin, sodium hyaluronate, and capryloyl glycine (and) sarcosine (and) cinnamon bark extract, and mixtures thereof.

[0130] For example, the composition may contain a cosmetic-grade surfactant selected from the group consisting of niacinamide, glycerin, sodium hyaluronate, and mixtures thereof.

[0131] The composition may also contain about 1 to about 5 weight percent of niacinamide, about 0.5 to about 2 weight percent of glycerin, and about 0.01 to about 0.1 weight percent of sodium hyaluronate.

[0132] The composition may also contain about 2 weight percent niacinamide, about 1 weight percent glycerin, and about 0.05 weight percent sodium hyaluronate.

[0133] Alternatively, the composition may contain a cosmetically acceptable surfactant selected from the group consisting of acetylglucosamine, niacinamide, and mixtures thereof.

[0134] For example, the composition may contain about 2 to about 6 weight percent of acetylglucosamine and about 1 to about 5 weight percent of niacinamide.

[0135] The composition may also contain about 4 weight percent of acetylglucosamine and about 4 weight percent of niacinamide.

[0136] The present invention will be further illustrated by the following non-limiting examples. The compositions described were prepared as follows.

[0137] For formulations without pigments, the lipid-soluble components were mixed together as an "oil phase" in the main tank / pot and heated to 75-85°C to ensure proper solubility of all components. After all components were dissolved, dispersing materials such as thickeners were added. The phase was stirred and homogenized to ensure proper dispersion of all materials, and then hot water (75-85°C) was poured into the main tank along with the oil phase under high shear and homogenization to promote emulsification. After the emulsion was formed, the mixture was cooled to below 60°C, and temperature-sensitive components such as MBBT were added while stirring. In the next step, the mixture was cooled to 35-40°C, and other temperature-sensitive components such as fragrances and antioxidants were added while stirring. Finally, the mixture was homogenized and cooled to 25°C for pH measurement and adjustment with sodium hydroxide if necessary.

[0138] For formulations containing pigments, hot water and pigments were heated to 75-85°C in a main tank containing a chelating agent and homogenized under high shear to promote pigment dispersion. Lipid-soluble components were mixed together as an "oil phase" in a second tank / pot and heated to 75-85°C to ensure proper solubility of all components. After all components were dissolved, dispersing materials such as thickeners were added. The phases were stirred and homogenized to ensure proper dispersion of all materials. Using both phases at 75-85°C, the oil phase was poured into water under high shear and homogenization to promote emulsification. After the emulsion was formed, the mixture was cooled to below 60°C, and temperature-sensitive components such as MBBT were added while stirring. In the next step, the mixture was cooled to 35-40°C, and other temperature-sensitive components such as fragrances and antioxidants were added while stirring. Finally, the mixture was homogenized and cooled to 25°C for pH measurement and adjustment with sodium hydroxide if necessary. [Examples]

[0139] A series of compositions were prepared and tested for SPF using the in vitro SPF test method. The compositions were formulated in the vehicles shown in Table 1 and contained the UV absorbers and UV blockers shown in Table 2. For each composition, the ratio of SPF to the total weight percentage of all UV absorbers and UV blockers was calculated. These results are also shown in Table 2.

[0140] [Table 1]

[0141] [Table 2]

[0142] All compositions contained high molecular weight UV absorbers BEMT, EHT, and MBBT. However, compositions 1-4 also contained one or more low molecular weight UV absorbers avobenzone, octocrylene, octisalate, and homosalate. Compositions 1-4 had relatively low SPF-to-total weight percent of the filter (UV absorber + UV blocker) ratios, the highest of which was 3.66 (Composition 2). This indicated low filter pack efficiency. Composition 5 did not contain any low molecular weight UV absorbers, but also did not contain DHHB, and provided an SPF of 64.77 and an SPF-to-total weight percent of the filter ratio of only 3.1. Composition 6 contained the low molecular weight UV absorber PBSA, resulting in an SPF-to-total weight percent of the filter ratio of 3.9. Composition 7 did not contain any low molecular weight UV absorbers, but also did not contain DHHB, and provided an SPF of only 20.87 and an SPF-to-total weight percent of the filter ratio of only 0.9. Composition 8 did not contain low molecular weight UV absorbers and contained BEMT, EHT, MBBT, DHHB, TiO2, and TBT, respectively. It provided a maximum SPF of 95.71 and a maximum SPF-to-total weight percent of the filter ratio of 6.6. [Examples]

[0143] A series of compositions were prepared and tested for SPF using the in vitro SPF test method. The compositions were formulated in the vehicles shown in Table 3 and contained the UV absorbers and UV blockers shown in Table 4. For each composition, the ratio of SPF to the total weight percentage of all UV absorbers and UV blockers was calculated. These results are also shown in Table 4.

[0144] [Table 3-1]

[0145] [Table 3-2]

[0146] [Table 4]

[0147] Compositions 9-16 and 18 each contained a combination of the UV absorbers DHHB, BEMT, EHT, and MBBT according to the present invention, and all provided high SPF values ​​of 52.23-103.26. Furthermore, all of these compositions provided high filter pack efficiency with an SPF-to-total weight percent ratio of 4.29-6.45. Composition 17 did not contain MBBT but provided an SPF of 52.63 and an SPF-to-total weight percent ratio of 4.38. This is thought to be because it contained high concentrations of EHT and BEMT, and these UV absorbers have higher UVB absorbance than MBBT. However, when composition 17 was tested in vivo for SPF, the result was 44, and the SPF-to-total weight percent ratio of the filter was only 3.66. In contrast, compositions 15 and 16 yielded in vivo SPF results of 72 and 74, respectively, with SPF ratios of 4.61 and 6.06 to the total weight percentage of the filter, which were significantly higher than those of composition 17. [Examples]

[0148] The series of compositions according to the present invention were prepared using the following amounts of UV absorbers and blockers: BEMT 0.5% by weight, EHT 2.5% by weight, MBBT 4% by weight, DHHB 2% by weight, and TiO2 0.5% by weight. The compositions also contained 0 to 20% by weight of the polymer UV absorber polyglycerylbenzotriazolyl t-butylhydroxyphenylpropionate. The compositions were formulated using the vehicles shown in Table 5.

[0149] [Table 5]

[0150] The SPF of each composition was measured using the in vitro SPF test method. The ratio of SPF to the total weight percentage of UV absorbers and UV blockers combined was calculated for each composition.

[0151] Table 6 shows the results along with the amounts of UV absorbers and UV blockers in each composition.

[0152] [Table 6]

[0153] Compositions 19-23 containing a combination of UV absorber and UV blocker according to the present invention provided excellent in vitro SPF results of 39.1-126.55. The addition of polyglycerylbenzotriazolyl t-butylhydroxyphenylpropionate to compositions 20-23 synergistically increased the SPF compared to composition 19. The best SPF results were obtained using 10 or 15 weight percent polyglycerylbenzotriazolyl t-butylhydroxyphenylpropionate in combination with BEMT, EHT, MBBT, DHHB, and TiO2. [Examples]

[0154] Compositions 27 to 31 according to the present invention were prepared using the components listed in Tables 7, 8, 9, and 10.

[0155] [Table 7]

[0156] [Table 8]

[0157] [Table 9]

[0158] [Table 10]

[0159] Compositions 27-31 were found to provide excellent moisturizing effects on the skin when applied topically. Furthermore, advantageously, the UV absorbers and UV blockers in the compositions remained substantially on the skin, i.e., did not penetrate the skin, and therefore provided excellent UV protection. On the other hand, cosmetic-grade surfactants such as niacinamide penetrated the skin. Thus, the effectiveness of both the UV absorbers and UV blockers and the cosmetic-grade surfactants was maintained.

[0160] [Implementation Method] (1) (a) diethylamino hydroxybenzoylhexyl benzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylene bis-benzotriazolyl tetramethylbutylphenol, comprising 6.31 × 10 -25 A sunscreen composition that is substantially free of UV absorbers having a molecular weight of 380 daltons or less per kg. (2) The composition according to Embodiment 1, further comprising a UV blocking agent selected from the group consisting of titanium dioxide and zinc oxide. (3) The composition according to Embodiment 2, wherein the UV blocking agent is titanium dioxide. (4) The composition according to Embodiment 1, further comprising tris-biphenyltriazine. (5) The composition according to Embodiment 1, further comprising a polymer UV absorber.

[0161] (6) The polymer UV absorber is of the following formula: [ka] The composition according to Embodiment 5, wherein the linear UV-absorbing polyether is a linear UV-absorbing polyether in which n and m are independently a number from 0 to 20, and at least one of m and n is 1 or more. (7) The composition according to Embodiment 1, having an SPF of at least about 30 when measured by an in vitro SPF test method, and the ratio of the SPF of the composition to the total weight percent of the UV absorber and UV blocker in the composition being at least about 4.1. (8) The composition according to Embodiment 1, further comprising a topical carrier acceptable for cosmetic use. (9) The composition according to Embodiment 8, further comprising niacinamide, tocopheryl acetate, ascorbic acid, acetylglucosamine, trehalose, feverfew extract, glycerin, sodium hyaluronate, and capryloyl glycine (and) sarcosine (and) cinnamon bark extract, and a cosmetic-grade surfactant selected from the group consisting of mixtures thereof. (10) The composition according to Embodiment 9, wherein the activator acceptable for cosmetic use is selected from the group consisting of niacinamide, glycerin, and sodium hyaluronate.

[0162] (11) The composition according to Embodiment 9, wherein the cosmetic-grade surfactant is selected from the group consisting of acetylglucosamine, niacinamide, and mixtures thereof. (12) (a) Approximately 2 to 6 weight percent of diethylaminohydroxybenzoylhexylbenzoate, (b) Tris-biphenyltriazine in a weight percentage of 3% or less, (c) About 0.5 to about 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyltriazine, and (d) About 1.64 to about 4.55 weight percent of ethylhexyltriazone, and (e) About 2 to about 6 weight percent of methylene bis-benzotriazolyltetramethylbutylphenol, and (f) Titanium dioxide of 2 weight percent or less, and comprising, substantially free of a UV absorber having a molecular weight of 6.31×10 -25 kg (380 daltons) or less, a sunscreen composition. (13) About 1 to about 5 weight percent of niacinamide, about 0.5 to about 2 weight percent of glycerin, and about 0.01 to about 0.1 weight percent of sodium hyaluronate, further comprising the composition according to embodiment 12. (14) About 2 to about 6 weight percent of acetylglucosamine and about 1 to about 5 weight percent of niacinamide, further comprising the composition according to embodiment 12. (15) A UV absorber, a UV blocker, and a cosmetically acceptable topical carrier, wherein the UV absorber and the UV blocker are (a) About 2 to about 6 weight percent of diethylamino hydroxybenzoyl hexyl benzoate, and (b) Tris-biphenyltriazine of 3 weight percent or less, and (c) About 0.5 to about 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyltriazine, and (d) About 1.64 to about 4.55 weight percent of ethylhexyltriazone, and (e) About 2 to about 6 weight percent of methylene bis-benzotriazolyltetramethylbutylphenol, and (f) Titanium dioxide of 2 weight percent or less, consisting of a sunscreen composition.

[0163] (16) The composition according to Embodiment 15, further comprising about 1 to about 5 weight percent of niacinamide, about 0.5 to about 2 weight percent of glycerin, and about 0.01 to about 0.1 weight percent of sodium hyaluronate. (17) The composition according to Embodiment 15, further comprising about 2 to about 6 weight percent of acetylglucosamine and about 1 to about 5 weight percent of niacinamide.

Claims

1. (a) diethylaminohydroxybenzoylhexylbenzoate, (b) bis-ethylhexyloxyphenol methoxyphenyl triazine, (c) ethylhexyl triazone, and (d) methylenebis-benzotriazolyltetramethylbutylphenol, comprising 6.31 × 10 －２５ A sunscreen composition that is substantially free of UV absorbers having a molecular weight of 380 daltons or less per kg.

2. The composition according to claim 1, further comprising a UV blocking agent selected from the group consisting of titanium dioxide and zinc oxide.

3. The composition according to claim 2, wherein the UV blocking agent is titanium dioxide.

4. The composition according to claim 1, further comprising tris-biphenyltriazine.

5. The composition according to claim 1, further comprising a polymer UV absorber.

6. The polymer UV absorber has the following formula: 【Chemistry 1】 The composition according to claim 5, wherein the linear UV-absorbing polyether is a linear UV-absorbing polyether in which n and m are independently a number from 0 to 20, and at least one of m and n is 1 or more.

7. The composition according to claim 1, wherein it has an SPF of at least about 30 when measured by an in vitro SPF test method, and the ratio of the SPF of the composition to the total weight percentage of the UV absorber and UV blocker in the composition is at least about 4.

1.

8. The composition according to claim 1, further comprising a topical carrier acceptable for cosmetic use.

9. The composition according to claim 8, further comprising niacinamide, tocopheryl acetate, ascorbic acid, acetylglucosamine, trehalose, feverfew extract, glycerin, sodium hyaluronate, and capryloyl glycine (and) sarcosine (and) cinnamon bark extract, and a cosmetic-grade surfactant selected from the group consisting of mixtures thereof.

10. The composition according to claim 9, wherein the activator acceptable for cosmetic use is selected from the group consisting of niacinamide, glycerin, and sodium hyaluronate.

11. The composition according to claim 9, wherein the activator acceptable for cosmetic use is selected from the group consisting of acetylglucosamine, niacinamide, and mixtures thereof.

12. (a) Approximately 2 to 6 weight percent of diethylaminohydroxybenzoylhexylbenzoate, (b) Tris-biphenyltriazine in a weight percentage of 3% or less, (c) Approximately 0.5 to approximately 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyl triazine, (d) Approximately 1.64 to 4.55 weight percent of ethylhexyltriazone, (e) Approximately 2 to 6 weight percent of methylenebis-benzotriazolyltetramethylbutylphenol, (f) Titanium dioxide of 2 weight percent or less, Including 6.31 x 10 －２５ A sunscreen composition that is substantially free of UV absorbers having a molecular weight of 380 daltons or less per kg.

13. The composition according to claim 12, further comprising about 1 to about 5 weight percent of niacinamide, about 0.5 to about 2 weight percent of glycerin, and about 0.01 to about 0.1 weight percent of sodium hyaluronate.

14. The composition according to claim 12, further comprising about 2 to about 6 weight percent of acetylglucosamine and about 1 to about 5 weight percent of niacinamide.

15. A UV absorber, a UV blocker, and a topical carrier acceptable for cosmetic use, wherein the UV absorber and the UV blocker are (a) Approximately 2 to 6 weight percent of diethylaminohydroxybenzoylhexylbenzoate, (b) Tris-biphenyltriazine in a weight percentage of 3% or less, (c) Approximately 0.5 to approximately 3.5 weight percent of bis-ethylhexyloxyphenol methoxyphenyl triazine, (d) Approximately 1.64 to 4.55 weight percent of ethylhexyltriazone, (e) Approximately 2 to 6 weight percent of methylenebis-benzotriazolyltetramethylbutylphenol, (f) A sunscreen composition comprising 2% by weight or less of titanium dioxide.

16. The composition according to claim 15, further comprising about 1 to about 5 weight percent of niacinamide, about 0.5 to about 2 weight percent of glycerin, and about 0.01 to about 0.1 weight percent of sodium hyaluronate.

17. The composition according to claim 15, further comprising about 2 to about 6 weight percent of acetylglucosamine and about 1 to about 5 weight percent of niacinamide.

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