MXPA98005971A - Formulation for protection against ultraviol light - Google Patents

Abstract

The present invention relates to a first aspect, a sunscreen agent, which is especially suitable for use in pharmaceutical or cosmetic applications comprising: a) a micronized organic UV absorbent and one or preferably both of: b) a non-micronized UV absorbent soluble in oil and / or an inorganic micropigment, and c) a polymeric hollow sphere additive and / or a polymer selected from xanthan and / or polyvinyl pyrrolidone. The present invention also provides a sunscreen composition comprising A) 0.1 to 15%, preferably 0.5 to 10% by weight, based on the total composition of a sunscreen agent according to the present invention, and B) a cosmetically acceptable carrier

Description

FORMULATION FOR PROTECTION AGAINST UV LIGHT The present invention relates to new formulations and in particular to new formulations for protection against ultraviolet (UV) light, comprising a combination of a micronized UV absorber and one, or preferably both of i) a non-micronized UV absorbent soluble in oil and / or an inorganic micropigment; and ii) an additive of polymeric hollow spheres and / or polymers selected from xanthan and / or polyvinylpyrrolidone. The new combinations exhibit a sun protection effect, synergistic, unexpected. This synergistic effect is greatly improved when the micronized UV absorbent and the non-micronized, oil-soluble UV absorbent and / or an inorganic micropigment are used in combination with an additive polymeric hollow spheres and / or a polymer selected from xanthan and / or polyvinylpyrrolidone. It has long been known that prolonged exposure to UV radiation reaching the surface of the earth, can lead to the formation of erythema or dermatosis by light, as well as an increased incidence of skin cancers, or aging or accelerated the skin . Various formulations of sunscreens have been proposed, which includes a material that is intended to counteract UV radiation, thereby inhibiting the unwanted effects of the skin. A large number of compounds have been proposed to be used as UV protectants in sunscreen formulations, especially soluble organic UV absorbers and insoluble micronized inorganic compounds, in particular zinc oxide and titanium dioxide. With respect to the use of sunscreen formulations of soluble organic UV absorbers, they have the disadvantages that their effectiveness as UV protectants in terms of sun protection factor (SPF) in a sunscreen formulation is often too much. low for commercial purposes, - as a result of their solubility, they exhibit relatively high allergenic potential; and that, as a result of the intrinsic photochemical ability, the duration of the protective effect is often too low. The high specific gravity of insoluble inorganic compounds such as titanium dioxide leads to reduced stability of formulations containing them.

Even more, these inorganic compounds have been claimed to generate toxic radicals under the influence of light and water ("Redox Mechanisms in Heterogeneous Photocatalysis" (Redox Mechanisms in Heterogeneous Photocatalysis), Serpone and collaborators, "Electrochemistry in Colloids and Dispersions", Editors Mac and an Texter, VCH Publishers Inc., New York 1992). GB-A-2303549 discloses a method for producing micronized insoluble organic UV absorbers, as well as a sunscreen composition comprising a) 0.1 to 15%, preferably 0.5 to 10% by weight, based on the composition total of a micronized formulation of an insoluble organic UV absorbent, produced according to the method; and optionally b) a cosmetically acceptable carrier. The micronized insoluble organic UV absorbers thus obtained, when used in sunscreen formulations, provide excellent UV protection and have at least one SPF rating as high as corresponding sunscreen formulations containing a known inorganic UV absorbent. Unlike the latest UV absorbers, micronized insoluble organic UV absorbers show no tendency, under the influence of light, to generate radicals that can damage or sensitize human skin. In a further development of the concept described in GB-A-2303549, it has now been found that when a micronized organic UV absorbent is used in combination with one or preferably both of i) a non-micronized, oil-soluble UV absorber and / or an inorganic micropigment and ii) an additive of polymeric hollow spheres and / or a polymer selected from xanthan and / or polyvinylpyrrolidone, this combination exhibits an unexpected synergistic sun protection effect. This synergistic effect is greatly improved when the micronized UV absorbent or the soluble non-micronised UV absorbent are used individually or preferably in combination with each other with a polymeric hollow sphere additive. Accordingly, the present invention provides as a first aspect, a sunscreen agent which is especially suitable for use in pharmaceutical or cosmetic applications, comprising: a) a micronized organic UV absorbent; and one or preferably both of; b) a non-micronized UV absorber soluble in oil and / or an inorganic micropigment; and c) an additive of polymeric hollow spheres and / or a polymer selected from xanthan and / or polyvinylpyrrolidone. The relative proportions of components a): b) and / or c) are preferably in the range of 20:80 to 80:20, especially 40:60 to 60:40 in weight. The micronized organic UV absorber, component a), is preferably produced by the method described in GB-A-2303549, ie by a process comprising grinding an organic UV absorbent in the form of coarse particles, in a grinding apparatus , in the presence of 1 to 50%, preferably 5 to 40% by weight based on the micronized organic UV absorbent, of an alkyl polyglucoside having the formula CnH2n + 10 (C6H10O5) xH, where n is an integer in the range of 8 to 16 and x is the average polymerization level of the glucoside portion (C6H10O5) and is in the range of 1.4 to 1.6, or an ester thereof. The grinding apparatus used to produce the micronized organic UV absorbent can for example be a jet, bead, vibration or hammer mill, preferably a high speed agitator mill or impact mill, especially a rotary ball mill, vibratory mill, tube mill or bar mill. The alkyl polyglucoside can consist of an ester with 1 to 12 carbon atoms of the compound of the formula C n H 2n + 10 (C 6 H 100 S) X H, ie an ester formed by reacting an acid with 1 to 12 carbon atoms, such as formic acid , acetic, propionic, butyric, sulfosuccinic, citric or tartaric, with one or more free OH groups in the glucoside portion (C6H10O5). The micronized organic UV absorbent can for example be a triazine, a benziotriazole, an amide containing a vinyl group, a cinnamic acid amide or a sulfonated benzimidazole UV absorber. A preferred class of triazine compounds is one that has the formula wherein R ?, R2 and R3 independently are H, OH, alkoxy with 1 to 3 carbon atoms, NH2, NH-R4 or N (R4) 2 wherein R4 is alkyl with 1 to 3 carbon atoms, OR4 wherein R4 has the prior meaning, phenyl, phenoxy or anilino, or pyrrolo, wherein the respective phenyl, phenoxy or anilino or pyrrolo portions, optionally are substituted by one, two or three substituents selected from OH, carboxy, C0-NH2, alkyl or alkoxy with 1 to 3 carbon atoms, carboxyalkyl with 2 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, a methylidenecamphor group, a group - (CH = CH) mC (= 0) -0R4 where m is 0 or 1 and R4 has the previous meaning, or a group or the corresponding alkali metal, ammonium, mono-, di- or tri-alkyl salts with 1 to 4 carbon-ammonium atoms, mono-, di- or tri-alkanolammonium with 2 to 4 carbon atoms or their alkyl with 1 to 3 carbon atoms esters. Preferred compounds of formula (1) are those having one of the formulas as well as 2, 4,6-tris (diisobutyl-4'-aminobenzalmalonate) -s-triazine and 2, 4-bis (diisobutyl-4-aminobenzalmalonate) -6- (4'-n-n-benzylidenecamphor) -s-triazine. Particularly preferred compounds of the formula (1) are those having the formula: wherein the individual radicals R5 are the same or different and each is hydrogen; an alkali metal; an ammonium group N (R6) 4, wherein R6 is hydrogen or an organic radical; alkyl having 1 to 3 carbon atoms, or a polyoxyethylene radical containing from 1 to 10 ethylene oxide units and the terminal OH group, which may be etherified by an alcohol having 1 to 3 carbon atoms. In relation to the compounds of the formula (24), when R5 is an alkali metal, it is preferably potassium 0 especially sodium; when R5 is a group N (Rd) 4 where Rs has the prior meaning, it is preferably a mono-, di- or tri-alkyl salt with 1 to 4 carbon-ammonium atoms, a mono-, di- or tri-alkanol with 2 to 4 carbon atoms-ammonium or alkyl with 1 to 3 carbon atoms thereof; when R6 is an alkyl group with 1 to 3 carbon atoms, preferably it is an alkyl group with 1 to 2 carbon atoms, more preferably a methyl group, and when R6 is a polyoxyethylene group, this preferably contains 2-6 ethylene oxide units. A preferred class of micronized triazole organic UV absorbers is one that has the formula where T? is alkyl having 1 to 3 carbon atoms or preferably hydrogen, and T2 is alkyl having 1 to 4 carbon atoms, preferably t-butyl or alkyl having 1 to 4 carbon atoms substituted by phenyl, preferably alpha, alpha-dimethylbenzyl. An additional preferred class of absorbents UV organic micronized triazole is one that has the formula: (26) wherein T2 is hydrogen; or alkyl with 1 to 12 carbon atoms, preferably iso-octyl. A preferred yet additional class of micronized triazole organic UV absorbers is one that has the formula wherein T2 is alkyl having 1 to 12 carbon atoms, preferably iso-octyl. A preferred class of micronized organic amide UV absorbers containing vinyl group, is one having the formula (28) R7- (Y) m -CO-C (R8) = C (R9) -N (R10) (R1) ) wherein R7 is alkyl having 1 to 3 carbon atoms, preferably alkyl having 1 to 2 carbon atoms or phenyl optionally substituted with one, two or three substituents, selected from OH, alkyl having 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms or CO-OR4 where R4 has the previous meaning; R8, R9, R10 and Rlx are the same or different and each is alkyl having 1 to 3 carbon atoms, preferably alkyl having 1 to 2 carbon atoms or hydrogen; And it is N u 0; and m has its previous meaning. Preferred compounds of the formula (28) are 4-methyl-3-penten-2-one, ethyl-3-methylamino-2-butenoate, 3-methylamino-1-phenyl-2-buten-1-one and 3-methylamino -l-phenyl-2-buten-1-one. A preferred class of micronized organic UV absorbers of cinnamic acid amide is that which has the formula wherein R 12 is hydroxy or alkoxy with 1 to 4 carbon atoms, preferably methoxy or ethoxy; R 13 is hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl or ethyl; and R14 is - (C0NH) m-phenyl where m has its previous meaning and the phenyl group is optionally substituted by one, two or three substituents selected from OH, alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 atoms carbon or C0-0R4, where R4 has its previous meaning. Preferably R14 is phenyl, 4-methoxyphenyl or the phenylaminocarbonyl group. A preferred class of sulfonated benzimidazole micronized organic UV absorbers is one that has the formula wherein M is hydrogen or an alkali metal, preferably sodium, an alkaline earth metal such as magnesium or calcium or zinc. In the compounds of formulas (1) to (30), alkyl groups having 1 to 12 carbon atoms can be methyl, ethyl, n-propyl or isopropyl, butyl, pentyl, amyl, isoyl, hexyl, heptyl, octyl, iso-octyl, nonyl, decyl, undecyl, or dodecyl, with methyl being preferred; and alkoxy groups with 1 to 3 carbon atoms include ethoxy, ethoxy, propoxy and isopropoxy, methoxy and ethoxy are preferred. Carboxyalkyl with 2 to 4 carbon atoms includes carboxymethyl, carboxyethyl, carboxypropyl and carboxyisopropyl, carboxymethyl is preferred. Cycloalkyl with 5 to 8 carbon atoms includes cyclopentyl, cyclohexyl and cyclooctyl. The compounds of formulas (1) to (30) are known. The compounds of the formula (24) are described, together with their production, in the patent of the U.S.A. No. US-A-4617390.

Preferably, the micronized organic UV absorbent, component a) of the new sunscreen agent, has an average particle size in the range from 0.01 to 2, more preferably from 0.02 to 1.5, especially from 0.05 to 1O. The oil-soluble organic UV absorber, the optional component b) of the sunscreen agent of the present invention, can be any known oil-soluble organic UV absorbent, especially those already approved and commercially available for use. cosmetic. These oil-soluble organic UV absorbers are described, for example, in "Sunscreens", Development, Evaluation and Regulatory Aspects ("Solar Filters", Development, Evaluation and Regulatory Aspects), Editors: N.J. Lowe and N.A. Shaath, M. Dekker Inc., New York and Basel, 1990; and Ken Klein, Encyclopedia of UV absorbers for sunscreen products, Cosmetics & Toiletries (Encyclopedia of UV Absorbents for Sunscreen Products, Cosmetics and Bath Products) 107 45-64 (1992). The non-micronized, oil-soluble UV absorber, for example, may be a pa-benzoic acid derivative such as an ester, salt or derivative emulsified with p-aminobenzoic acid amine, - a salicylic acid derivative such as an ester or its salt; a benzophenone derivative; a dibenzoylmethane derivative, - a diphenylacrylate derivative; a benzofuran derivative; a polymeric UV absorber containing one or more silico-organic residues, - a cinnamate ester; a camphor derivative; a trianilino-s-triazine derivative; phenylbenzimidazole sulfonic acid and its salts; urocanic acid (3-imidazol-4-yl-acrylic acid) or its ethyl ester; Menthyl anthranilate, - a benzotriazole, - a hydroxyphenyltriazine derivative; or a bis-resorcinol-dyalkylaminotriazine. Specific examples of a p-aminobenzoic acid derivative include 4-aminobenzoic acid (PABA), ethyl dihydroxypropyl PABA having the formula PEG-25 PABA that has the formula wherein m, n and x are the same and each is about 25, octyl dimethyl PABA having the formula: and glyceryl aminobenzoate that has the formula Specific examples of a salicylic acid derivative include homosalate (homomenthyl salicylate) having the formula triethanolamine salicylate that has the formula amyl p-dimethylamino benzoate that has the formula octyl salicylate having the formula 4-isopropylbenzilsalicylate having the formula Specific examples of benzophenone derivatives include benzophenone-3- (2-hydroxy-4-methoxybenzophenone), benzophenone-4- (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) and benzophenone-8- (2, 2 '- dihydroxy-4-methoxybenzo-phenone). A specific example of a dibenzoylmethane derivative is butyl methoxydibenzoylmethane [1- (4-tert-butyl) -3- (4-methoxyphenyl) propan-1,3-dione]. Specific examples of a diphenylacrylate derivative include octocrylene (2-ethylhexyl-2-cyano-3,3 '-diphenyl acrylate) and ethocrylene (ethyl-2-cyano-3,3'-diphenyl acrylate). Specific examples of a benzofuran derivative include the 3- (benzofuranyl) -2-cyanoacrylates described in U.S. Pat. No. 5,338,539 or EP 582189, especially the compounds having the formula the 2- (2-benzofuranyl) -5-tert-butylbenzoxazoles described in U.S. Pat. No. 5,518,713 and the 2- (p-aminophenyl) benzofurans described in U.S. Pat. No. 5,362,481. Specific examples of a polymeric UV absorber containing one or more silico-organic residues, are the benzylidenemalonate silicone derivatives described in EP 709080, in particular the compound having the formula: wherein R15 is H or OMe and r is about 7, - and the polymers of the benzotriazole-silicone type described in WO 94/06404, in particular the compound having the formula: Specific examples of cinnamate ester include octyl methoxy cinnamate (2-ethylhexyl ester of 4-methoxycinnamic acid), diethanolamine methoxy cinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (2-isoamyl ester of 4-methoxycinnamic acid), 2,5-diisopropyl methyl cinnamate, the cinnamido derivatives described in the US patent No. 5,601,811 and the derivatives described in WO 97/00851. Specific examples of camphor derivatives are 4-methyl-benzylidene camphor [3- (4'-methyl) benziliden-bornan-2-one], 3-benzylidene camphor (3-benzylidene-2-one-ona), polyacrylamidomethyl benzylidene camphor . { N- [2 (and 4) -2-oxobor-3-ylidene-methyl) benzyl] acrylamide polymer} , benzylidene camphor sulfate tri onium [3- (4'-trimethylammonium) -benzylidene-boronan-2-one methyl sulfate], terephthalenedicarboxylic acid sulfonic acid. { 3,3'- (1,4-phenylenedimethine) -bis- (7,7-dimethyl-2-oxo-bicyclo [2.2.1] heptan-1-methanesulfonic acid} and its salts and benzylidene camphor sulfonic acid [ 3- (4 '-sulfo) benzylidene-bornan-2-one] and its salts.

Specific examples of trianiline-s-triazine derivatives include octyl triazine [2,4,6-trianilino- (p-carbo-2'-ethyl-1'-oxy) -1,3,5-triazine, the trianilino-s derivatives -triazine described in the US patent No. 5,332,568, the trianilino-s-triazine derivatives described in EP 517104, trianilino-s-triazine derivatives described in EP 570838, the trianilino-s-triazine derivatives described in US Pat. Do not. ,252,323, the trianilino-s-triazine derivatives described in the patent of WO 93/17002-A1 and the trianilino-s-triazine derivatives described in WO 97/03642-A1. A specific example of a benzotriazole is 2- (2-hydroxy-5-methyl-phenyl) benzotriazole. Specific examples of hydroxyphenylazine derivatives include, for example, those described in EP-A1-775, 698 such as 2, 4-bis. { [4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine. Specific examples of bis-resorcinol-dialkyl aminotriazines are, for example, those described in EP-A1-780,382. The inorganic micropigment UV absorber, the optional component b) of the new sunscreen agent, may for example be titanium dioxide coated with aluminum oxide or silicon dioxide, zinc oxide coated with aluminum oxide or silicon dioxide or mica .

The polymeric hollow sphere component, component c) of the new sun protection agent, according to the present invention can for example be those described in EP-A-761201 The polymeric hollow sphere component is preferably a commercially available acrylic acid / styrene copolymer hollow sphere material. The acrylic acid / styrene copolymer is supplied as an aqueous dispersion comprising beads of acrylic acid / styrene copolymer having a particle size of less than 1 miera. Said aqueous dispersion preferably has a solids content in the range from 20 to 50%, more preferably 25 to 45% by weight, - a void volume from 15 to 60%, more preferably from 20 to 55%; a particle size of 0.1 to 5 microns, more preferably 0.1 to 1.5 microns, and a wall thickness of 0.01 to 1 micron, especially from 0.02 to 0.5 micron. The polymeric hollow spherical component can of course be derived from any convenient monomer and does not need to be limited to hollow sphere material acrylic acid / styrene copolymer. Suitable hollow spheres material are, for example, acrylonitrile copolymers, such as copolymers of acrylonitrile with acrylic acid, methacrylic acid, styrene or vinylidene chloride.

Preferred polymeric hollow spherical components are those that are substantially insoluble in cosmetic formulation components for sunscreens, since unduly high solubility can lead to an undesirable decrease in the UV protection performance of the resulting sunscreen formulation. The present invention also provides a sunscreen composition comprising A) 0.1 to 15%, preferably 0.5 to 10% by weight, based on the total composition of a sunscreen agent according to the present invention, - and B ) a cosmetically acceptable carrier. The sunscreen composition of the present invention can be produced by physically mixing the sunscreen agent according to the present invention and a cosmetically acceptable carrier by any conventional method, for example by simply stirring the two materials together. The sunscreen composition of the invention can be formulated as a water-in-oil or oil-water dispersion, an alcohol-oil or oil lotion, a vesicular dispersion of a non-ionic or ionic amphiphilic lxido, a gel, a solid stick or an aerosol formulation. When formulating a water-in-oil or oil-in-water dispersion, the cosmetically acceptable carrier preferably comprises 5 to 50% by weight of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of an oil phase. water, each by weight based on the total weight of the carrier. The oil phase can comprise any oil conventionally used in cosmetic formulations, especially an emollient, for example one or more of a fatty alcohol, - hydrocarbon oil, - a natural or synthetic triglyceride; a wax including esters of long-chain acids and alcohols as well as compounds having wax-like properties, - a silicone oil; a fatty acid ester or a fatty alcohol; and products that contain lanolin. Examples of fatty alcohols include cetyl alcohol, stearyl alcohol, octyldodecanol, cetearyl alcohol and oleyl alcohol, examples of hydrocarbon oils are for example mineral oil (light or heavy), petrolatum (yellow or white), polyethylene, paraffin, squalene, microcrystalline wax , Ceresin, Polybutene and Hydrogenated Polyisobutene; examples of natural or synthetic triglycerides include breeding oil, capric / capric triglyceride, Japanese wax, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, wheat germ glycerides, avocado oil, corn oil, trilaurine, hydrogenated oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, saffron oil, macadamia nut oil; olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, and borage oil, - examples of a wax that includes esters of long chain alcohols and acids, as well as compounds that have wax-like properties, for example are carnauba wax, beeswax (white or yellow), lanolin, candelilla wax, ozokerite, lanolin oil, paraffin wax, wax Japan, microcrystalline wax, ceresin, jojoba oil, cetaxyl ester wax, synthetic jojoba oil, synthetic beeswax and lanolin wax; a silicone oil for example is dimethicone or cyclomethicone; examples of fatty acid esters or fatty alcohol include isopropyl myristate, isopropyl palmitate, octyl palmitate, isopropyl lanolate, acetylated lanolin alcohol, benzoate of alcohols with 12 to 15 carbon atoms, cetearyl octanoate, cetyl palmitate, myristyl myristate, iristyl lactate, cetyl acetate, propylene glycol dicaprylate / caprate, decyl oleate, acetylated lanolin, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, octyl hydroxystearate and isopropyl isostearate; and examples of products containing lanolin, include lanolin oil, isopropyl lanolate, acetylated lanolin alcohol, acetylated lanolin, hydroxylated lanolin, hydrogenated lanolin and lanolin wax. The emulsifiers can comprise any emulsifier which is conventionally employed in cosmetic formulations, for example one or more of an ethoxylated ester of a natural oil derivative such as polyethoxylated ester of hydrogenated oil.; a silicone oil emulsifier such as silicone polyol; an ethoxylated fatty acid soap optionally; an ethoxylated fatty alcohol; an optionally ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride. The sunscreen composition of the invention may also comprise additional components known to play a useful role in a sunscreen composition. Examples of these additional compounds include for example emollients, skin moisturizers, skin tanning accelerators, antioxidants, emulsion stabilizers, thickening agents such as xanthan, moisture retention agents such as glycerin, film formers, preservatives, perfumes and dyes. The sunscreen composition of the invention provides excellent protection of the human against the damaging effects of sunlight, while allowing secure tanning of the skin. Still further, the sunscreen composition of the invention has a water impermeable effect on the skin. The following Examples further illustrate the present invention. The parts and percentages illustrated are by weight unless otherwise stated. Examples 1 to 10: The aqueous dispersions of hollow spheres of acrylic acid / styrene copolymer used in the following test methods have the following physical characteristics: Content Volume Thickness Size Polymer of Gap Solids Wall Particles £ jJ ¡rJ Average (microns) ^? pa._ Í HP-9KI *) 27.5 50 1.0 0.1 Ropaqu- ^ -S4-2M (IT. *) 40.0 22 0.5 0.1 Ropaque ....- 90 E (III *) 37.5 33 0.4 0.06 The basic resin used was the following oil-in-water cream: A) oil phase composition Tegin P 1.0% thick viscous paraffin oil 5.0% Stearic acid 1.5% Lanette O 0.4% Propil paraben 0.1% UVA soluble in oil (Parsol MCX) x%. Parsol MCX is octyl methoxycinnamate. B) aqueous phase composition: Water 84.3% Triethanolamine 0.8% Glycerin (85%) 4.0% Carbopol 934P 0.1% Methyl paraben 0.1% UVA micronized aqueous (compound of formula (101)) and% Polymer z% The compound of the formula (101) is 2, 2 '-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1, 1,3, 3-tetramethylbutyl) -phenol]: The individual test formulations are produced as follows. The soluble UVA-in-oil (Parsol MCX) is dissolved in a specific amount (see following Table) in the oil phase. The aqueous micronized UVA (compound of the formula (101)), optionally together with the polymer, is incorporated into the aqueous phase. The two phases are heated separately to 75 ° C and then the oil phase is stirred slowly in the water phase and the whole mixture is stirred cold. The individual test formulations thus obtained are then evaluated, in vi tro, by their SPF performance using an SPF-290 analyzer (Fa. Optometrics). Four brushes of each test formulation are applied in a layer thickness of 2 μl / cm2 to Transpore film (3M) and 9 SPF measurements are made of each applied brushing. The SPF values obtained are illustrated in the following Table 1, along with the average values and standard deviations, for each of the 36 individual measurements. The percentage amounts of the polymer shown in Table 1 are based on the weight of the active substance. Table 1 Example x% (control) - 1 Parsol MCX 2.7 comp. (101) 5! 2 Parsol MCX 2.7 3 Parsol MCX 2.7 comp. (101) 5Í 4 Parsol MCX 2.7 5 - comp. (101) 5% 6 - comp. (101) 5% 7 - comp. (101) 5% 8 Parsol MCX 2.7 comp. (101) 5% 9 Parsol MCX 2.7 comp. (101) 5% 10 Parsol MCX 2.7 comp. (101) 5% Table .1 (continued) Example Polymer Polymer Polymer SPF (I *)% (!! *)% (III *)% (control) - 1.2 + 0 1 17.8 + 1.9 2 2.5% 7.9 + 0.6 3 2.5% 8.2 + 0.9 4 2.5% 8.1 + 0.9 5 2.5% 11.9 + 1.8 6 2.5% 8.9 + 0.8 7 2.5% 8.5 + 1.0 8 2.5% 20.1 + 1.7 9 2.5% 23.1 + 1.1 10 2.5% 23.0 + 3.1 The results in Table 1 show that The basic formulation (without UV absorber) does not offer UV protection. Parsol MCX and micronized compound (101), when used together demonstrate synergistic UV protection. The compound (101) and the polymer spheres, when used together, demonstrate improved UV protection. The combination of three components of Parsol MCX, micronized compound (101) and polymer spheres, when used together, demonstrate outstanding synergistic UV protection.

The results in the table also show that the cosmetic product, by the use of relatively inexpensive polymer spheres, is capable of preparing high SPF sunscreen formulations using relatively small amounts of expensive UV absorbers. Examples 11 to 13: Using the same formulations as described in Examples 1 to 10, but varying the relative proportions of the polymer spheres, the following additional results are obtained. The percentage amounts of polymer illustrated in Table 2 are based on the weight of the active substance. Table 2 Example x% y% Polymer SPF (III *)% (cont.) - - 1.2 11 Parsol MCX 2.7í Comp. (101) 5% 5.0% 28.5 12 Parsol MCX 2.7 'Comp. (101) 5% 7.5% 58.5 13 Parsol MCX 2. V. Comp. (101) 5% 10.0% 47.5 Examples 14 and 15 The following basic oil-in-water formulation is constituted: Oil Phase 1 propylene glycol stearate 1.0% mineral oil 5.0% stearic acid 1.5% cetearyl alcohol 0.4% propylparaben 0.1% Absorbent of UV soluble in oil of test 2.75 Phase Aqueous 2 triethanolamine 0.8% glycerin (85%) 4.0% carbomer 0.1% methylparaben 0.1% water at 100% Inorganic micropigment is incorporated (micro-Ti02, coated with silicon) (6.0% by weight based on the solids content of the total formulation) in the oil phase. Micronized test organic UV absorber is incorporated (6.0% by weight based on the solids content of the total formulation), as a suspension in the aqueous phase. Phases 1 and 2 are heated separately to 75 ° C. With continuous agitation, the oil phase is added to the aqueous phase and while homogenizing, the mixture is cooled to 30 ° C. The individual test formulations thus obtained are then evaluated, in vitro, for their SPF performance using the COLIPA standard. The obtained SPF values are illustrated in the following Table 3: Table 3 Ex. UVA soluble in micronized UVA oil from test SPF (% by weight) Test (% by weight) in vitro 2.7% UVA I 4.2 6.0% by weight UVA II 7.7 6. 0% by weight Ti02 coated with silicon 4.8 14 2.7 UVA 1 6.0% by weight UVA II 14.2 15 2.7 UVA 1 6.0% by weight of Ti02 coated with silicon 4.9 UVA I is 2-ethylhexyl-p-methoxycinnamate and UVA II is a 25% aqueous dispersion of [2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine] having an average size of 0.55 miera. The results in Table 3 demonstrate that the two-component sunscreen agents according to the present invention exhibit unexpected synergistic SPF effects, the results in Example 14 being particularly salient. Examples 16 and 17: Using the oil-in-water base formulation of Examples 14 and 15, various oil-soluble UVAs and micronised UVAs are incorporated in specific amounts. The respective formulations are then examined for their SPF in vitrs performance using an SPF 290 analyzer (Optometrics). The evaluations are made using the Diffey & Robson (J. Soc. Cosmet, 40 127-133, 1989). The results are set forth in the following Table 4: Table 4 Ex. UVA Soluble-UVA Micronized Oil SPF 6.4% by weight UVA III 5.4 16 4.0% by weight UVA 1 6.4% by weight UVA III 22.7 17 4.0% by weight UVA IV 6.4% by weight UVA III 16.7 UVA III is an aqueous dispersion of 50 % [2,2'-methylene-bis-6 (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl-butyl) -phenol] having an average particle size of 0.25 miera. UVA IV is 4-methyl-benzylidene camphor. The results in Table 5 show that the two-component sunscreen or protection agents according to the present invention exhibit unexpected synergistic SPF effects. Examples 18 and 19: A pre-dispersion A is produced consisting of a 50% aqueous dispersion of micronized UVA III. This is added to pre-dispersion A, 2% xanthan gum and 0.4% propylene glycol, to produce pre-dispersion Bl. Then Bl, 2.0% polyvinylpyrrolidone (MW 8000) is added to the pre-dispersion B2 to produce the B2 pre-dispersion. The pre-dispersions A, Bl and B2 are then incorporated into separate samples of the same simple oil-in-water formulation and the final formulations are used for SPF in vi tro determinations using an SPF 290 analyzer (Optometrics). The evaluations are made using the Diffey & Robson (J. Soc. Cosmet, 40 127-133, 1989). The results are set forth in the following Table 5: Table 5 Example of SPF Test Formulation Final formulation with pre-dispersion A 11.7 18 Final formulation with pre-dispersion Bl 18.0 19 Final formulation with pre-dispersion B2 21.1 The results in Table 5 show that two-component sunscreen agents according to the present invention exhibit unexpected improved SPF effects. Examples 20 to 25 The following basic oil-in-water formulation is prepared: Phase 1 cetearyl alcohol; PEG-40; Recinte oil, sodium cetearyl sulfate mixture 3.15% decyl oleate 15.0% UVA IV or V soluble in test oil 4.0% propilparaben 0.1% Phase 2 dispersion at 50% aqueous UVA III micronized 6 or 12% methylparaben 0.3% EDTA disodium 0.1% water 50.75 or 45.75% Phase 3 carbomer (Carbopol 934P) 0.3% sodium hydroxide (45%) 0.3% water 20% Phase 1 is heated to 75-80 ° C, Phase 2 is heated to 80 ° C , while full homogenization is applied. Phase 1 is then added to Phase 2, while continuous agitation is applied. Phase 3 is then added to the mixture of phases 1 and 2, while continuous stirring is applied and then re-homogenized for 3 minutes. After replenishing the water loss, the entire mixture is homogenized until cooled. The individual test formulations thus obtained are then evaluated, in vitro, for their SPF performance using an SPF-290 analyzer (Fa. Optometrics). Four brushes of each test formulation are applied, in a layer thickness of 2 μl / cm2 on Transpore film (3M) and 9 SPF measurements are made from each applied brush. The SPF values obtained are illustrated in the following Table 7, along with the average values and standard deviations, for each of the 36 individual measurements. Table 6 Ex. UVA soluble in UVA micronized oil in SPF 50% suspension 20 4% UVA V 6% UVA III 16.3 + 4.1 21 4% UVA V 12% UVA III 31.4 + 9.4 4% UVA VI 6% UVA III 16.0 + 4.0 23 4 % UVA VI 12% UVA III 30.6 + 9.2 24 4% UVA Vil 6% UVA III 25.3 + 7.6 25 4% UVA VII 12% UVA III 43.2 L4.5 UVA V is octyl-me -.icinnamate; UVA VI is 3- (4-ethylbenzidene) -bornane-2-one, - and UVA VII is 2, 4, 6-trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) -13, 5- triazine. Example 26 The following basic oil-in-water formulation is constituted: Isostearyl Isostearate Oil Phase 4.0% caprylic / capric triglyceride 4.0% liquid paraffin 3.3% stearyl alcohol 1.4% cetyl alcohol 1.4% titanium dioxide (Eusolex T-2000) 4.0 % dimethicone 1.0% propylparaben 0.1% Aqueous phase cytosan sodium methylene phosphonate 0.01% sodium cetearyl sulfate 0.5% methylparaben 0.1% compound (26) (50%) 6.0% water at 100% The two phases are treated separately at 65 ° C and then the oil phase is stirred in the aqueous phase and the whole mixture is stirred cold. The pH of the emulsion thus obtained is adjusted from 6.5 to 7. 0, and then the emulsion is evaluated, in vi tro, to determine its SPF performance, using an SPF-290 analyzer (Fa. Optometrics).

The SPF value obtained is 21. When the experiment is repeated, but omitting the compound (26) from the aqueous phase, the SPF value is only 9.

Claims (31)

1. CLAIMS 1. A sunscreen agent, characterized in that it comprises: a) a micronized organic UV absorbent; and one or both of b) a non-micronized UV absorber soluble in oil and / or inorganic micropigment; and c) an additive of polymeric hollow waxes and / or a polymer selected from xanthan and / or polyvinylpyrrolidone.
2. 2. A sunscreen agent according to claim 1, characterized in that it comprises a) a micronized organic UV absorbent; and b) a non-micronized UV absorber soluble in oil and / or an inorganic micropigment.
3. 3. A sunscreen agent according to claim 1, characterized in that it comprises a) a micronized organic UV absorbent; and c) a polymeric hollow sphere additive and / or a polymer selected from xanthan and / or polyvinylpyrrolidone.
4. 4. A sunscreen agent according to claim 1, characterized in that it comprises a) a micronized organic UV absorbent; b) an oil-soluble non-micronized UV absorber and / or an inorganic micropigment, and c) a polymeric hollow spheres additive and / or a polymer selected from xanthan and / or polyvinylpyrrolidone.
5. 5. A sunscreen agent according to any of the preceding claims, characterized in that the relative proportions of components a): b) and / or c) are in the range of 20:80 to 80:20.
6. 6. A sunscreen agent according to any of the preceding claims, characterized in that the micronized organic UV absorbent is a triazine, a benzotriazole, an amide containing a vinyl group, a cinnamic acid amide or a benzimidazole UV absorber. sulphonated
7. 7. A sunscreen agent according to claim 6, characterized in that the triazine UV absorber has the formula: wherein R x, R 2 and R 3 independently are H, OH, alkoxy with 3 carbon atoms, NH 2, NH-R 4 or N (R 4) 2 wherein R 4 is alkyl with 1 to 3 carbon atoms, 0 R 4 wherein R 4 has the previous meaning, phenyl, phenoxy or anilino, or pyrrolo, wherein the respective phenyl, phenoxy or anilino or pyrrolo portions, are optionally substituted by one, two or three substituents selected from OH, carboxy, C0-NH2, alkyl or alkoxy with 1 to 3 carbon atoms, carboxyalkyl with 2 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, a methylidene camphor group, a group - (CH = CH) mC (= 0) -0R4 where m is 0 or 1 and R4 has the previous meaning, or a group or the corresponding alkali metal, ammonium, mono-, di- or tri-alkyl salts with 1 to 4 carbon atoms-ammonium, mono-, di- or tri-alkanolammonium with 2 to 4 carbon atoms or their alkyl with 1 to 3 carbon atoms esters.
8. 8. A sunscreen agent according to claim 7, characterized in that the triazine compound has the formula wherein the individual radicals R5 are the same or different and each is hydrogen; an alkali metal, - an ammonium group N (R6) 4, wherein R6 is hydrogen or an organic radical; alkyl having 1 to 3 carbon atoms, or a polyoxyethylene radical containing from 1 to 10 ethylene oxide units and the terminal OH group, which may be etherified by an alcohol having 1 to 3 carbon atoms.
9. 9. A sunscreen agent according to claim 7, characterized in that the organic triazole UV absorber has the formula: wherein Tx is alkyl with 1 to 3 carbon atoms or hydrogen; and T2 is alkyl with 1 to 4 carbon atoms, optionally substituted by phenyl.
10. 10. A sunscreen agent according to claim 7, characterized in that the triazole organic UV absorber has the formula wherein T2 is hydrogen or alkyl with 1 to 12 carbon atoms.
11. 11. A sun protection agent according to claim 10, characterized in that T2 is hydrogen.
12. 12. A sunscreen agent according to claim 10, characterized in that T2 is iso-octyl.
13. 13. A sunscreen agent according to claim 7, characterized in that the organic UV absorber benzotriazole has the formula: wherein T2 is as defined in claim 10.
14. 14. A sunscreen agent according to claim 7, characterized in that the organic amide UV absorber containing the vinyl group has the formula: (28) R7- (Y ) m-CO-C (R8) = C (Rg) -N (R10) (R1?) wherein R7 is alkyl having 1 to 3 carbon atoms or phenyl, optionally substituted by one, two or three substituents selected from OH , alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms or C0-0R4 wherein R4 is as defined in claim 7; R8, R9, R10 and Rl? they are the same or different and each is alkyl with 1 to 3 carbon atoms or hydrogen, - Y is N or O, - and m is as defined in claim 7.
15. 15. A sun protection agent according to claim 7, characterized in that the organic UV absorber of cinnamic acid has the formula: wherein R 12 is hydroxy or alkoxy with 1 to 4 carbon atoms; R13 is hydrogen or alkyl with 1 to 4 carbon atoms; and R 14 is - (CONH) m-phenyl wherein m is as defined in claim 6 and the phenyl group is optionally substituted by one, two or three substituents selected from OH, alkyl having 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms or C0-0R4, wherein R4 is as defined in claim 7.
16. 16. A sunscreen agent according to claim 7, characterized in that the sulfonated benzimidazole organic UV absorber has the formula : wherein M is hydrogen or an alkali metal, an alkaline earth metal or zinc.
17. 17. A sunscreen agent according to any of the preceding claims, characterized in that the micronized organic UV absorbent, component a), has an average particle size in the range from 0.01 to 2μ.
18. 18. A sunscreen agent according to any of the preceding claims, characterized in that the organic oil-soluble UV absorber, component b) is a derivative of p-amino-benzoic acid, - a derivative of salicylic acid; a benzophenone derivative; a dibenzoylmethane derivative; a diphenylacrylate derivative, - a benzofuran derivative, a polymeric UV absorber containing one or more silico-organic residues; a cinnamate ester; a camphor derivative, - a trianilino-s-triazine derivative; a phenylbenzimidazole sulfonic acid or a salt thereof, - urocanic acid (3-imidazol-4-yl-acrylic acid) or its ethyl ester; Menthyl anthranilate; a benzotriazole; a hydroxy-phenyltriazine derivative; or a bis-resorcinol-dialkylaminotriazine.
19. 19. A sunscreen agent according to claim 18, characterized in that the cinnamate ester is octyl methoxy cinnamate (2-ethylhexyl ester of 4-methoxycinnamic acid), diethanolamine methoxy cinnamate (salt diethanolamine of 4-methoxycinnamic acid), isoamyl p -methoxy-cinnamate (2-isoamyl ester of 4-methoxycinnamic acid), 2,5-diisopropyl methyl cinnamate or a cinnamido derivative.
20. 20. A sunscreen agent according to any of the preceding claims, characterized in that the inorganic micropigment UV absorber, component b), is titanium dioxide coated with aluminum oxide or silicon dioxide, zinc oxide coated with aluminum oxide or silicon dioxide, or mica.
21. 21. A sunscreen agent according to any of the preceding claims, characterized in that the polymeric hollow sphere component, component c) is a hollow sphere material based on acrylic acid / styrene copolymer.
22. 22. A sunscreen agent according to claim 21, characterized in that the styrene / acrylic acid copolymer is in the form of an aqueous dispersion comprising styrene / acrylic acid copolymer beads having a particle size of less than 5. mieras
23. 23. A sunscreen agent according to claim 22, characterized in that the aqueous dispersion has a solids content in the range from 20 to 50%, a void volume of 15 to 60%, an average particle size of 0.1 to 5 microns and a wall thickness of 0.01 to 1 miera.
24. 24. A sunscreen composition, characterized in that it comprises A) 0.1 to 15% by weight of a sunscreen agent according to claim 1; and B) a cosmetically acceptable carrier.
25. 25. A composition according to claim 24, characterized in that the sunscreen agent is as defined in any of claims 2 to 23.
26. 26. A composition according to claim 24 or 25, characterized in that the UV absorber micronized organic, component a), has an average particle size in the range from 0.01 to 2.0μ.
27. 27. A composition according to any of claims 24 to 25, characterized in that the sunscreen agent is used together with one or more additional UV absorbers that are conventionally employed in cosmetic compositions for the protection of human skin from radiation of UV
28. 28. A sunscreen composition according to any of claims 24 to 27, characterized in that it is formulated as a water-in-oil or water-oil dispersion, an oil or oil-alcohol lotion, a vesicular dispersion of a non-ionic or ionic amphiphilic lipid, an alcohol or alcohol-alcohol gel, a solid stick or an aerosol formulation.
29. 29. A composition according to claim 28, characterized in that it is formulated as a water-in-oil or oil-in-water dispersion and component B) comprises 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% water, each by weight based on the total weight of the carrier.
30. 30. A composition according to claim 29, characterized in that the oil phase comprises an emollient selected from one or more of a fatty alcohol; hydrocarbon oil; a natural or synthetic triglyceride, - a wax that includes esters of long-chain acids and alcohols, as well as compounds having wax-like properties; a silicone oil; an ester of fatty acid or a fatty alcohol, - and products containing lanolin.
31. 31. A sunscreen composition according to any of claims 24 to 30, characterized in that the sunscreen composition also comprises one or more additional components selected from additional emollients, skin moisturizers, skin tanning accelerators, antioxidants, emulsion stabilizers, thickening agents, moisture retention agents, film formers, preservatives, perfumes and colorants.