(12) United States Patent (10) Patent No.: US 9,656,103 B2 Müller Et Al

USOO96561 03B2

(12) United States Patent (10) Patent No.: US 9,656,103 B2 Müller et al. (45) Date of Patent: May 23, 2017

(54) LIGHT PROTECTING-EFFECTIVE 6,159,481 A * 12/2000 Fallick ...... 424/401 6,210,658 B1 * 4/2001 Bonda ...... 424,59 COSMETIC ORDERMATOLOGICAL 6,235,271 B1 5/2001 Luther et al...... 424,59 PREPARATIONS 6,294,143 B1* 9, 2001 Deutsch et al. .... 423.432 6,355.230 B2 * 3/2002 Gers-Barlag et al. 424,59 (75) Inventors: Stefan Müller, Weil am Rhein (DE): 6,485,713 B 1 * 11/2002 Bonda et al...... 424,59 6,495, 122 B2 12/2002 Fankhauser et al...... 424,59 Thomas Ehlis, Freiburg (DE): Jochen 6,511,655 B1* 1/2003 Muller et al...... 424,59 Giesinger, Grenzach-Wyhlen (DE); 6,627, 179 B2 * 9/2003 Candau ...... 424,59 Gilbert Kreyer, Saint-Louis (FR) 6,746,666 B1* 6/2004 Luther ...... 424,59 2003/0082464 A 1 * 5/2003 Takashima et al...... 430.7 (73) Assignee: BASF SE, Ludwigshafen (DE) 2003/O124048 A1* 7/2003 Hardinghaus et al...... 423/554 2003/O161894 A1* 8/2003 Yaniv ...... 424,687 2004/0081633 A1* 4/2004 Mercier et al. . 424.70.12 (*) Notice: Subject to any disclaimer, the term of this 2005/0008665 A1 * 1/2005 Batzer et al...... 424/401 patent is extended or adjusted under 35 2005, 0196360 A1 9/2005 Comte et al...... 424,59 U.S.C. 154(b) by 1467 days. 2006/0058430 A1* 3/2006 Dyllick-Brenzinger et al...... 524/115 (21) Appl. No.: 11/632,686 FOREIGN PATENT DOCUMENTS

(22) PCT Filed: Jul. 11, 2005 EP O 893 119 1, 1999 EP 1 068 866 1, 2001 (86). PCT No.: PCT/EP2005/053301 EP 1308154 A2 * 5, 2003 JP 60149517 A * 8, 1985 S 371 (c)(1), NL WO 2004 110614 A1 * 12/2004 ... B01J 13.06 (2), (4) Date: Aug. 30, 2007 WO OO,78277 12/2000 WO WO 0200190 A1 * 1/2002 (87) PCT Pub. No.: WO2006/008252 WO O3,063814 8, 2003 PCT Pub. Date: Jan. 26, 2006 OTHER PUBLICATIONS (65) Prior Publication Data Gerhard J. Nohynek and Hand Schaefer, Benefit and Risk of US 2008/OO75746 A1 Mar. 27, 2008 Organic Ultraviolet Filters, Regulatory Toxicology and Pharmacol ogy 33, 285-299 (2001).* (30) Foreign Application Priority Data Federal Register vol. 64, No. 98, p. 27666 (1999).* Dolomite Product information and Date; available at http://www. Jul. 20, 2004 (EP) ...... O4103462 mindat.org/min-1304.htm.* Oct. 14, 2004 (EP) ...... O4105034 Dolomite Powder; available at http://www.steatiteindia.com/dolo mite.htm. (51) Int. Cl. Wetting behavior of magnesite and dolomite surfaces; , Applied Surface Science; vol. 252, Issue 10, p. 3744-3750; available online A610 17/04 (2006.01) Ju1, 5, 2005.* A6 AIK 8./92 (2006.01) Melamine Fact Sheet from Fisheries Perspective (2008). Available A6 AIK 9/97 (2006.01) at: www.globefish.org/filedownload.php?fileld=690.* A6 AIK 8./96 (2006.01) 2,4,6-triphenyl-1,3,5-triazine MSDS.* (52) U.S. CI. Weber, Handbook of Optical Materials, CRC Press (2003) Table CPC ...... A610 17/04 (2013.01). A6IK 8/02 1.3.3. (2013.01); A61 K 9/107 (2013.01); A61 K (Continued) 2800/412 (2013.01) (58) Field of Classification Search Primary Examiner — Kortney L. Klinkel CPC ...... A61K 8/29: A61K 8/42: A61K 8/4946; Assistant Examiner — Lisbeth C Robinson A61K 8/496; A61K 8/4966; A61K 8/73: A61K 8/8147: A61K 8/8176; A61 K (74) Attorney, Agent, or Firm — Marshall, Gerstein & 8/0241; A61K 8/0279; A61K 2800/412: Borun LLP A61K 2800/652: A61K 2800/654; A61Q 17/04: Y1OS 514/937 (57) ABSTRACT See application file for complete search history. Disclosed is the use of an insoluble or sparingly soluble (56) References Cited micronized substance class which is not a cosmetic UV absorber and which is dispersed in the oil- or water-phase of U.S. PATENT DOCUMENTS a cosmetic or dermatological composition for the enhance ment of light protecting action of this cosmetic or derma 3,988,437 A * 10/1976 Bradner ...... 424,59 tological composition comprising at least one cosmetic UV 4,800,076 A * 1/1989 Bhat et al...... 424f69 5,486,233 A * 1/1996 Mitchell et al...... 106,416 filter which is soluble in the water- or oil-phase. The 5,733,531 A 3, 1998 Mitchnick et al...... 424,59 cosmetic preparation according to the invention shows a 5,853,705 A * 12/1998 Nakayama et al. . ... 424,59 remarkable increase in SPF. 5,869,030 A * 2/1999 Dumler et al. ... 424,59 6,007,799 A * 12/1999 Lee et al...... 424,65 6.015,548 A * 1/2000 Siddiqui et al...... 424,59 12 Claims, No Drawings US 9,656,103 B2 Page 2

(56) References Cited pTerphenyl MSDS, accessed at http://www.sciencelab.com/msds. php?msdsld=9925178, May 23, 2013.* Hawley's, Hawley's Condensed Chemical Dictionary, Lewis, eds. OTHER PUBLICATIONS Wiley & Sons, Inc. New York, (2007) p. 1067.* Machine Translation of EP1308154, Google Patents, downloaded Wypych, “Barium Sulfate'. Handbook of Fillers, ChemTec Pub Jan. 9, 2014.* Machel et al., Luminescence Microscopy and Spectroscopy (1991) lishing, Toronto (2010) pp. 31-35.* pp. 1-2 (submitted by Applicant).* Bala et al., Colloids and Surfaces A, 274: 71-76 (2006).* Hassan, American Mineralogist, 63: 732-736 (1978).* Mizuguchi et al. JP, 60-0149517. English language Abstract English Language Abstract for EP 1 068 866 printed from (1985).* esp(a)cenet.com on Apr. 30, 2007. Mizuguchi et al. JP, 60-0149517, Derwent Abstract 1985-2342456 UV Spectrum Melamine; Journal of Chromatography A; vol. 815; (1985).* Issue 2: Jul. 31, 1998; pp. 197-204. Ultraviolet. The American Heritage Dictionary (2007). Retrieved Reaxys ID #45961; N-N-N-triphenynll-triazine. from http://www.credoreference.com/entry/himmedicaldict/ultra Reaxys ID #293951; 2-4-6-tris-methyl-phenyl-triazine. violet, Dec. 5, 2012.* Reaxys ID #239186; 2-4-6-triphenyl-triazine. Derwent Abstract 1992-344665 for JP 4-248877 (1992).* Baudour et al., Acta Crystal., B34: 625 (1978) (Abstract).* * cited by examiner US 9,656,103 B2 1. 2 LIGHT PROTECTING-EFFECTIVE melem, (-2,5,8-triamino 1,3,4,6,7,9,9b -heptaaZa COSMETIC ORDERMATOLOGICAL phenalene) 1502-47-2 of the formula PREPARATIONS

The present invention relates to the use of specific 5 NH2 micronized insoluble substances for the enhancement of light protecting action in cosmetic or dermatological com positions and cosmetic or dermatological compositions comprising these specific micronized insoluble Substances. ??? It is well known that specific organic UV filters, like 10 s????? sparingly soluble benzotriazoles or triazine compounds exhibit pronounced UV filter properties and are therefore als ??< used in cosmetic UV filter compositions. HN ? ? NH2: A problem of these organic UV filters is their low solu bility in cosmetic oils. Their use in oil phase containing cosmetic formulations is therefore limited to only low 15 melon, (poly 8-amino-1,3,4,6,7,9.9b-heptaaza concentration levels. phenalene-2,5-diyl)imino of the formula Micronized organic UV filters are generally used as aqueous dispersions and can therefore only be formulated in the water phase. Surprisingly it was found that dispersions of micronized insoluble Substances are able to enhance the light protecting action of a cosmetic or dermatological composition com prising an organic UV filter which is dissolved in the oil- or water-phase of this composition. Therefore, the present invention relates to the use of an 25 insoluble or sparingly soluble micronized substance class which is not a cosmetic UV absorber and which is dispersed in the oil- or water-phase of a cosmetic or dermatological composition for the enhancement of light protecting action of this cosmetic or dermatological composition comprising at least one cosmetic UV filter which is soluble in the water 30 1,3,5-triazin-2(1H)-one, 4,6-diamino- (Registry Num or oil-phase. ber: 645-92-1) of the formula The micronized insoluble substance class is preferably a birefringent Substance having an average refraction index of n=1 to 2.5 and a An=0.001 to 0.8 n. “Birefringent” substances are understood as non-absorb 35 ing materials, wherein the pass of electromagnetic radiation is dependent on the propagation direction of the light (optical anisotropy). If the overall light ray is regarded as two perpendicular linear polarized light rays the Velocity of propagation and 40 consequently the refraction index is different for both rays. 1,3,5-triazine-2,4(1 H.3H)-dione, 6-amino-(Registry Preferably the micronized insoluble or sparingly soluble Number: 645-93-2) of the formula substances have a hydrophobic or hydrophilic surface. Preferably they are present in the composition in crystal line or in part crystalline form. 45 Preferably the micronized insoluble or sparingly soluble Substance has a high melting point, which is normally >80° C., more preferably >100° C., and most preferably >120° C. Most preferably substances are used which have an aro matic or heteroaromatic moiety. 50 Examples for micronized insoluble Substances having an aromatic or heteroaromatic moiety are: Triazine derivatives, like melamine, 2,4,6-triamino-s-tri aryl-triazines and arylamino-triazines of the formulae azin; melamine polyphosphate (CAS Regno. 218768 84-4); melamine cyanurate (CAS Regno. 37640-57-6); 55 melamine phosphate (CAS Regno. 41583-09-9); melam, (1,3,5-triazine-2,4,6-triamine-n -(4,6-diamino 1,3,5-triazine-2-yl) of the formula

? ?????N ...... IN1 oxalate CdCO and cadmium sulfide CdS, 10 Calcium slats, like calcium carbonate CaCO (Calcit), calcium magnesium carbonate (dolomite), calcium chromate CaCrO, calcium fluoride CaF2, calcium hydrogen phosphate CaFIPO, calcium hydroxide Ca(OH), calcium oxalate CaCO, calcium phosphate 15 CaPO, calcium sulfate CaSO and calcium sulfite CaSO: Calcium carbonate 471-34-1 occurs naturally as chalk, limestone, and marble. It can be used according to the present invention. Preferably used in the present invention are ground cal cium carbonate (GCC), fine-ground calcium carbonate (FGCC) and ultrafine ground calcium carbonate which are often referred to as natural carbonate. Calcium carbonate has three polymorphic forms: calcite 25 (rhombohedral), aragonite (orthorhombic), and Vaterite (trigonal). All three forms are preferably used in the present invention. Most preferably used is calcite. Preferably used in the present invention are also calcium Furthermore, the following organic micronized Sub carbonates which are produced chemically by precipitation stances are Suitable for the present invention: 30 (precipitated calcium carbonate, PCC). They are character Amides, like benzene-1,2,4,5-tetracarboxamide, biphe ized by greater particle fineness. There are many PCC ny1-44"-dicarboXamide, biphenyl-4-carboxylic amide, morphologies possible that are based on rhombohedral, isophthalamide and terephthalamide; prismatic, scalenohedral and also spherical and needlelike Urea derivatives, like cyanuric acid, diphenyl urea, crystal structures. Examples are Rhombohedral (PCC-R) or propoylurea and 3-methyl-1,1-di-phenylurea; 35 barrel-shaped calcium carbonate particles, Prismatic PCC Isatin: calcium carbonate particles, Scalenohedral (PCC-S) or 5-amino-isophthalic acid; rosette-shaped calcium carbonate particles. phenyl compounds, like diphenyl Sulfone, p-quaterphenyl Dolomite is alyo preferably used in the present invention. or p-terphenyl; and 40 The typical physical properties of Calcium Carbonates are the triazine compound of formula listed in the Table below:

NH2 Typical physical properties of Calcium Carbonates GCCPCC Dolomite O ES = EO 45 molecular weight (Dalton) 100.09 1844 density (kg II") 2.71 2.87 Mohs” hardness 3 decomposition T (K) from 1150 from 675 solubility at 288° K (kg II") 14 10-6 320 10-6 50 thermal conductivity (WK' m) 2.4-3.0 S-9 specific heat (kJ kg · K) O.86 O.9 NH linear coefficient of expansion (K) 9 10-6 15 10-6 mean refractive index 1.59 1.60 birefringence indices 1.480-1650 1.500-1679 % brightness (DIN 1053163) (%) 88-96 88-95 dielectric constant 6.1 7.3 -selss 55 H Appropriate forms of (precipitated) calcium carbonates are described for instance in: Microemulsion-based synthe ????\ S/n sis of Stacked calcium carbonate (calcite) SuperStructures. HN \, / NH2. 60 Viravaidya, Chulanapa; Li, Mei; Mann, Stephen. School of Chemistry, University of Bristol, Bristol, Chemical Com munications (Cambridge, United Kingdom) (2004), (19), Furthermore, micronized, insoluble substances are useful 2182-2183; Tong, Zhongliang. Production situation of nano for the present invention which have mineral character, like calcium carbonate and its application process in China. the following metal salts: 65 Huagong Jinzhan (2003), 22(4), 372-375; Ma, Jing: Li, Aluminum salts, like aluminum hydroxide Al(OH) and Qingshan; Yang, Zhanguo; Li, Chao; Zhang, Weixing. aluminum phosphate AlPO; Manufacture and application of nano calcium carbonate. US 9,656,103 B2 5 6 Huagong Shikan (2002), 16(7), 11-13; Hu, Qingfu: Hu, Fengqing; Liu, Baoshu: He, Fenglin; Xu, Zhao. Economical Xiaobo: Liu, Baoshu. New retrofitted spraying carbonation scale of production of basic magnesium carbonate, light technology for preparation of nanometer grade calcium magnesia, and Superfine magnesium-containing calcium car carbonate. Feijinshukuang (2002), 25(4), 42-44, 21; Kato, bonate from dolomite by carbonization. Wujiyan Gongye Takashi, Yabuuchi, Kazuhiro; Sugawara, Ayae; Kishimoto, (1999), 31(6), 21-22, 39; Ueyama, Norikazu. Strong binding Kenji. Self-assembly of nano- and micro-structured func of polymer ligand to calcium carbonate. Kobunshi (1999), tional materials. Materia (2003), 42(6), 453-456; Colfen, 48(4), 262; Ukai, Kenji; Toyokura, Ken. Reactive crystalli Helmut. Precipitation of carbonates: recent progress in con Zation of calcium carbonate. Nippon Kaisui Gakkaishi trolled production of complex shapes. Current Opinion in (1998), 52(5), 292-298; Brown, Alan J. Ground calcium Colloid & Interface Science (2003), 8(1), 23-31; Sugihara, 10 Hisao. Regulation of morphology of calcium carbonate. carbonate fillers. Retention of Fines and Fillers during Nippon Setchaku Gakkaishi (2003), 39(4), 157-162; Onoe, Papermaking (1998), 271-279: Zhang, Shicheng Zhuge Kaoru: Matsumoto, Masakazu, Shikata, Yohei: Furukawa, Lanjian; Han, Yaoxin; Jiang, Junhua. Preparation and appli Yuko. Reactive crystallization of calcium carbonate from cation of calcium carbonate with nanometer particle size. view point of equilibrium theory of multicomponent aque 15 Feijinshukuang (1997), (4), 22-25; Prescott, P. I.; Pruett, R. ous solution: Journal of the Society of Inorganic Materials, J. Ground calcium carbonate: ore mineralogy, processing Japan (2003), 10(302), 3-11; Berdonosov, S. S.; Berdono and markets. Transactions of Society for Mining, Metal sova, D. G.; Znamenskaya, I. V. Industrial synthesis, prop lurgy, and Exploration, Inc. (1997), Volume Date 1996, 300 erties, and use of ultrafine calcium carbonate. Khimiches 79-84; Ikegami, Tsukasa. Calcium carbonate filler. Kogyo kaya Tekhnologiya (Moscow, Russian Federation) (2002), Zairyo (1996), 44(10), 36-37; Chen, Ching Chih: Chen, (8), 2-11.: Korenaga, Takashi. Changes of the manufacturing Chih Hsien. High-purity calcium carbonate powders. technique of calcium carbonate and its applications. Journal Kuangye (Taipei, Taiwan) (1991), 35(4), 75-87; Nukui, of the Society of Inorganic Materials, Japan (2002), 9(300), Tokuzo. Development of calcium carbonate fillers. Gypsum 346-352; Ji, Hongwei. Xu Huan: Xin, Huizhen: Xia, Ning. & Lime (1990), 228 303-9: Hu, Zhitong. New types of Industrial synthesis and application of nano-Calcium car 25 calcium carbonate. Huaxue Shijie (1986), 27(3), 99-101; bonate. Qingdao Haiyang Daxue Xuebao (2002), 32(4), Ikegami, Tsukasa. History of calcium carbonate powder. 634-640; Qian, Jun-min; Jin, Zhi-hao. New progress in Toso Kogaku (1981), 16(6), 224-8. Kamiya, Kanichi: Sakka. preparation of filler CaCO3 and control of its shape and Sumio. Formation of calcium carbonate polymorphs. Gyp crystal types. Huagong Kuangwu Yu Jiagong (2002), 31(4), sum & Lime (1979), 163 243-53. Coated or Surface modified calcium carbonate can be used 1-4, 10; Zhao, Chun-xia; Man, Rui-lin; Yu, Jia-geng. Prepa 30 ration and application of nanometer light calcium carbonate. according to the present invention. Surface treatment meth Yingyong Huagong (2002), 31(2), 4-6; Jiang, Luhua: Du, ods and appropriate materials are described in: Fanglin: Zhang, Zhikun; Cui, Zuolin. Preparation and appli cation of ultra-fine calcium carbonate. Zhongguo Fenti Jishu P 54107929 Surface treatment of calcium carbonate for solvent (2002), 8(1), 28-32: Qian, Haiyan. Wang, Yaqin: Ye Xuchu: 35 type coating compositions. Bi, Yunhua. Production and application of ultrafine ground P 62148572 Pigments for coated paper PO1090235 Polyolefin resin compositions and laminated products calcium carbonate in China. Feijinshukuang (2001), 24(6), of metals and resin composition layers. 8-9, 19; Chikazawa, Masatoshi, Fuji, Masayoshi. Nanopar PO4004O75 Process for coating fillers with surface modifiers. ticles of lime and calcium carbonate. Journal of the Society PO4OO6105 Surface treatment of calcium carbonate for of Inorganic Materials, Japan (2001), 295 507-514; Zhu, 40 improvement of its dispersibility. Yingquan; Cao, Jianlin; Wang, Chengzhen; Xi, Shaohua; P 0823.1760 Surface-treated, heavy calcium carbonate and its use in vinyl chloride-based polymer compositions Tan, Jianhua. Quality of high purity CaCO3 made in China P 11349846 Surface treatment of calcium carbonate filler. and Japan. Dianzi Yuanjian Yu Cailiao (2001), 20(4), 27-29, P 2001072,890 Surface-treated calcium carbonate, their Han, Xiushan. Production and application of nano CaCO3. thermoplastic resin compositions, and manufacture of 45 porous films from the compositions. Huagong Shikan (2001), 15(5), 51-53; Xiao, Pindong. Fac P 2001288371 Antibacterial polymer compositions containing tors affecting shape and size of superfine CaCO3 powder Surface-treated inorganic fillers and their prepared by carbonation. Wujiyan Gongye (2001), 33(3), manufacture. 28-30; Hu, Xiaobo: Liu, Baoshu: Hu, Qingfu. Advances in P 2003034760 Surface-treated heavy calcium carbonate with good dispersibility, their manufacture, and resin ground CaCO3. Zhongguo Fenti Jishu (2001), 7(1), 24–28, compositions containing them. Hu, Qingfu; Hu, Xiaobo: Liu, Baoshu. Production of super 50 Zhang, Yi; Ma, Surface treatment of nano CaCO3 and its composite fine ground CaCO3. Feijinshukuang (2001), 24(1), 23-25. Xiuqing; Jin, with polymers CODEN: FEIJDJ ISSN:0253-2298: Wu, Zhijian: Lin, Riguang; Tian, Yanxin, Huang, Liyao. Synthesis of inorganic non-metal Miao. Beijing University of films on organic Substrates. Gongneng Cailliao (2000), 31(6), Chemical Tech 587-589; Hirasawa, 1zumi. Formation of calcium carbonate 55 nology, Beijing, by reaction crystallization. Journal of the Society of Inor Peop. Rep. China. ganic Materials, Japan (2000), 287 307–312: Imppola, Olavi. Suliao (2003), Precipitated calcium carbonate PCC. Papermaking Sci 32(3), 59-64. ence and Technology (2000), 11 140-151; Huggenberger, Ludwig: Arnold, Manfred; Koster, Hans-Heinz. Ground 60 According to the present invention acid resistant calcium calcium carbonate. Papermaking Science and Technology carbonate can be used. The following references describe (2000), 1194-105; Hu, Qingfu; Hu, Xiaobo: Liu, Baoshu. appropriate forms of modified calcium carbonate: Preparation methods and application of nanometer calcium WO 2003075874; Guo, Fen: Wu, Hai-Xia; Chen, Jian carbonate. Feijinshukuang (2000), 23(4), 24-26, 12; Ji, feng; Liu, Run-jing; Wang, Dong-guang: “Preparation of Guangbin, Chai, Xiaoli, Chen, Weizhong. Application and 65 acid-resistant calcium carbonate” Huagong Kuangwu Yu preparative process of ultra-fine ground CaCO3. Shanghai Jiagong (2003), 32(5), 5-7, 23; WO 9902608: WO 9856860; Huagong (2000), 25(11), 19-20, 29; Hu, Qingfu; Zhao, WO 9820079; WO 9714847; WO 9714651; U.S. Pat. Nos. US 9,656,103 B2 7 8 5,593,489 A; 5,593.488 A: Patel, M.; Panigrahi, J. C.: “Acid dral or trioctahedral layer); for example expanding resistant calcium carbonate for sizing in paper manufactur lattice Smectite group (equidimensional montmorillo ing, Journal of Scientific & Industrial Research (1996), nite, Sauconite, Vermiculite, elongate nontronite, 55(11),879-884; U.S. Pat. Nos. 5531821 A; 5,164,006 A; Saponite and hectorite) and nonexpanding lattice, Illite AND DE-A-2059624 group; Instead of calcium carbonate kaolins 14808-70-7. (C) regular mixed-layer types (ordered Stacking of alter 14808-60-7, 1332-58-7 or natural calcium or magnesium nate layers of different types, Chlorite group); and silicates can be used. These products occur naturally as talc (D) chain-structure types (hornblende-like chains of silica [14807-96-6), or wollastonite tetrahedrons linked together by octahedral groups of Instead of calcium carbonate, crystalline silicon dioxide 10 Oxygens and hydroxyls containing aluminum and mag can be used. nesium ions), hormite group palygorskite, (attapulgite) Silicon dioxide occurs naturally in both the crystalline and and sepolite. the amorphous forms. Crystalline silicon dioxide is used Furthermore, silica and layered silica, preferably micro mostly in the form of ground quartz. Neuburger Kieselerde crystalline silica minerals are preferably used as micronized (trade name sillitin) has a particular structure. It consists of 15 inorganic, insoluble Substances. corpuscular quartz, 14808-60-7 and laminar kaolinit 1318 Examples and properties of these materials are listed in 74-7. the table below: Chromium salts, like chromium(II) hydroxide Cr(OH) and chromium(III) hydroxide Cr(OH); Cobalt salts like cobalt(II) carbonate CoCOs: cobalt(II) Mineral or phase Species Microstructure hydroxide Co(OH)2, cobalt(III) hydroxide Co(OH), Quartz microquartz granular grains <20 m and cobalt(II) sulfide CoS: chalcedony length fast fibers, fiber axis <11.0> Copper salts like copper(I) chloride CuCl, copper(I) parallel fibrous iodide CuI, copper(II) carbonate CuCO, copper(II) spherulites of radiating fibers quartzine length slow fibers, fiber axis <00.1> ferrocyanide Cu[Fe(CN)6], copper(II) hydroxide 25 Moganite crystal blades Cu(OH) and copper(II) sulfide CuS: Opal opal-CT length slow fibers (lussatite) Iron salts, like iron(II) carbonate FeCO iron(II) hydrox lepidospheres of platelets ide Fe(OH), iron(II) sulfide Fees, iron(III) ferrocya opal-C parallel platy {101. nide Fe4Fe(CN)6]; iron(II) hydroxide Fe(OH) and maSSy, tangled platy iron(III) phosphate FePO; 30 Lead salts, like lead(II) fluoride PbF, lead(II) hydroxide Further preferred inorganic micronized insoluble sub Pb(OH), lead(II) iodide PbI, lead(II) sulfate PbSO, Stances are and lead(II) sulfide PbS: talc: Lithium salts, like lithium carbonate LiCO, lithium The talc lattice is composed of infinite two-dimensional fluoride LiF and lithium phosphate LiPO; 35 (3-) silicate double layers {[SiO'} or & SiO, Magnesium salts, like magnesium ammonium phosphate in which the apical O atoms of all of the SiO4 tetrahe MgNH4PO4, magnesium carbonate MgCO2, magne dral within one individual layer point in the same sium fluoride MgF2 magnesium hydroxide Mg(OH), direction, and the OH groups occupy the centers of the magnesium oxalate MgCO and magnesium phos hexagons formed by these apical oxygen atoms. The phate Mg3PO4; 40 apical O atoms of all of the SiO4 tetrahedral within an Manganese salts, like manganese(II) carbonate MnCO, individual layer point in the same direction, and the OH manganese(II) hydroxide Mn(OH) and manganese(II) groups occupy the centers of the hexagons formed by sulfide MnS: these apical oxygen atoms. Within a double layer, the Nickel salts, like nickel(II) hydroxide Ni(OH)2 and nickel apical Oatoms and OH groups of one layer are in direct (II)sulfide NiS: 45 contact with the corresponding atoms of the other layer, Silver salts, like silver sulfate AgSO, silver sulfide forming octahedral voids. These voids are filled by AgS, silver sulfite AgSO and silver thiocyanate positively charged magnesium ions, which compensate AgSCN: for the negative charges of the silicate. One magnesium Strontium salts, like strontium carbonate SrCO, stron ion is coordinated octahedrally by 4 O and 2 OH, the tium fluoride SrE and strontium sulfate SrSO; 50 coordination number being symbolized by Mg. Thallium salts like thallium(III) hydroxide Tl(OH); Pyrophyllite: Tin salts, like tin(II) hydroxide and tin(II) sulfide SnS: The pyrophyllite structure contains an infinite coherent Zinc salts like Sn(OH); Zinc carbonate ZnCO; zinc two-dimensional silicate double layer of linked SiO, hydroxide Zn(OH), Zinc oxalate ZnCO, Zinc phos tetrahedral: i. si Oslº-} or *. [SiOo]“, in which all phate Zn-PO; and zinc sulfide ZnS. 55 apical Oatoms of the SiO4 tetrahedra within one SiOs Furthermore, clay minerals are preferably used as micron layer point in the same direction, and the OH groups ized Substances in the present invention. occupy the centers of the hexagons formed by these Preferred are oxygen atoms. In the double layer, the oxygen layers (I) Amorphous Allophane group, and formed by the O atoms and OH groups are situated (II) crystalline clay minerals, which may be categorized into 60 directly opposite each other, and they are linked (A) two-layer types (sheet structures composed of units of together by Al", which is octahedrally coordinated by one layer of silica tetrahedrons and one layer of alu 4 O and 2 OH. This coordination number is symbolized mina octahedrons), for example equidimensional by All. The resulting silicate double layer (“pyrophyl kaolin group, kaolinite, dickite and nacrite and elongate lite layer') is therefore electrically neutral and is only halloysite: 65 weakly bonded to the neighbouring double layers by (B) three-layer types (sheet structures composed of two Van der Waals forces. This results in the laminar layers of silica tetrahedrons and one central dioctahe structure and pronounced cleavage of pyrophyllite in US 9,656,103 B2 10 the direction (001). In talc, unlike pyrophyllite, the two ing rings to form ZigZag bands (or "double crank-shaft single layers are bonded by Mg (“talc layer”) instead chains') making use of three of the four common of Al". Thus, in pyrophyllite only 24of the octahedral vertices. These bands are bonded in both the b and c coordination centers are occupied by All, while all % direction by the fourth common oxygen atom of each in talc are occupied by Mg. 5 (Si, Al) atom to form three-dimensional tetrahedral Mica: frameworks. As a result, the (010) and (001) planes are Micas are members of a class of silicates known as rather weakly bonded and readily cleaved. This prop phyllo- or sheet silicates, a term which reflects their erty is characteristic of all feldspars. The cations K. crystal structure. The general chemical formula for Na", and Ca", and more rarely Sri" and Ba", occupy mica is WCX, Y), ZO(OH, F), where W corre 10 the large spaces within the framework of tetrahedra, sponds to K, Na, and Ca, or more rarely Ba, Rb, and Cs. and are coordinated to oxygen in a fairly irregular The X, Y site is occupied by any two ions of Al, Mg, a. Fe, or Li, and less frequently of Mn, Cr, and Ti. Nepheline and Related Compounds: Normally Z is Si or Al, but may also be Fe or Ti. As The alkali aluminosilicate nepheline, KNaAlSiO, a with other silicates the primary building unit of mica is 15 feldspathoid, belongs to the nepheline group of tecto the SiO4 tetrahedron. The tetrahedra are linked together silicates without nontetrahedral anions. The aluminum: via their three basal oxygen ions to form a network of silicon ratio is 1:1. Structure and Mineralogy. As in all hexagonal cells with the apical oxygen ions all pointing tectosilicates, the oxygen ions at the vertices of the in the same direction. The idealized basic structural unit AlO and SiO4 tetrahedra in nepheline are linked to of mica comprises two layers of tetrahedra in which the the four neighbouring tetrahedra. This produces a apical oxygen ions point toward each other. The Voids three-dimensional open framework in which the rela between the bases of tetrahedra in adjacent layers and tively large Na" and K" cations are located in the spaces between adjacent apical oxygen ions provide the cation between the tetrahedra. In tectosilicates, these spaces sites. The interapical plane is occupied by the octahe can be occupied by alkaline-earth ions, nontetrahedral drally coordinated X, Y ions which may be any two of 25 anions (e.g., in the feldspathoids Sodalite and Scapo Al. Mg. Fe, or Li. The W sites (filled by K. Na, and less lite), or water (in zeolites). In minerals of the nepheline frequently Cacations) are in 12-fold coordination with group the tetrahedra exhibit a hexagonal or pseudohex the basal oxygen ions. Most commonly these stacking agonal arrangement. In nepheline, alternating AlO sequences lead to either one- or two-layered mono and SiO4 tetrahedra are linked together at common clinic cells (denoted as 1 M and 2 M), an alternative 30 vertices to form an easily distorted high-tridymite two-layered monoclinic cell (2 M2), or a three-layered structure with six-membered rings. The apices of the trigonal unit (3 T). AlO4 tetrahedra point parallel to the c axis, and those Most important types of mica are listed in the table below: of the SiO4 tetrahedra point in the opposite direction.

CAS registry Name number Formula Muscovite 994.01-63-5 K2Al4SiAl2O2(OH,F). Biotite [112593-95-0] K2(Mg, Fe°*)64(Fe°", Al, Ti)o 2[Si65Al2-3,O2o] (OH, F)4 Phlogo.pite [110710-26-4] K2(Mg, Fe°*)[SiAl2O,0] (OH, F) Lepidolite [1147O5—28—1] K2(Li, Al),5[Si_7Al2_Obo] (OH, F),3 K(Li, Al)2. 53o[Si335Al_o,5Oo] (OH, F)2 Zinnwaldite (116813-68-4 K2(Fei'", Li2-3A12) (Si6-7Al-O-ol (OH, F) Paragonite 106495-33-4 Na2Al4SiAl-O (OH) Glauconite 102785-61-5) (K, Na, Ca).22o(Feº, Al, Fe, Mg).oSizzºAll-oOo] (OH)-ºn (H2O) Margarite 1318-86-1 Ca2Al4SiAl4O2(OH) Clintonite, [12199—34—7] Ca2(Mg, Fe)Al4[Si5AlssO2o] (OH) Xan-thophyllite

Bentonite: Unlike the high-tridymite structure, Si" ions in neph Smectite is the name for a group of sodium, calcium, eline are replaced by Al" ions in half of the tetrahedral magnesium, iron, lithium aluminum silicates, which 50 positions. In order to maintain charge neutrality, 3 Na" include the individual minerals sodium montmorillo ions and 1 K ion are found per formula unit in the nite, calcium montmorillonite, nontronite, saponite, centers of the channels parallel to the c axis. and hectorite. The rock in which these smectite min Leucite: erals are usually dominant is bentonite. 55 The potassium aluminum silicate leucite, a feldspathoid, Feldspar: belongs to the analcime—leucite group oftectosilicates Feldspars 68.476-25-5 are anhydrous alkali/alkaline without nontetrahedral anions. The aluminum:silicon earth aluminosilicates that closely resemble each other ratio is 1:2. Structure and Mineralogy. As with all the in structure and properties. The feldspars are tectosili tectosilicates, the oxygen ions at the vertices of the cates. The (Si,Al)O tetrahedra are linked at all four 60 vertices yielding a framework Si Al Os. The AlO and SiO4 tetrahedra are linked to four neigh voids within the tetrahedral framework contain alkali bouring tetrahedra. This produces a three-dimensional metal or alkaline-earth ions for charge compensation. open framework in which K' ions are located in the The structure is composed of four-membered rings, spaces within the framework. Whereas in the nepheline [(Si, Al)4O2), containing (AlSi3) or (Al2Si2) in each 65 group the arrangement of tetrahedra is hexagonal or ring. The rings are linked by common oxygen atoms pseudohexagonal, the minerals of the analcime—leu (two on each side) in the a direction to two neighbour cite group have a cubic or pseudocubic arrangement. US 9,656,103 B2 11 12 Leucite 001302-34-7, KIAlSiO, is dimorphous. sillimanite are laterally bonded by Al-O and isolated Below 605°C., it exists as low leucite and above 605 SiO4 tetrahedra which form bands of AlSiO, C. as high leucite tetrahedra from two linked chains of AlSiO. The Olivine: four-coordinated aluminum in sillimanite cannot be Olivine (peridot, chrysolite) 1317-71-1 is a rock-form substituted by silicon. Parallel to b (010), very strongly ing nesosilicate (an orthosilicate, i.e., a silicate with bonded layers are formed from the AIO chains and isolated SiOI tetrahedra hold together by metallic AlSiO bands. These can easily be cleaved from the ions) belonging to the olivine series of minerals (Mg, neighbouring layers by separation at the apices of the Fe)SiO. There is an infinite series of solid solutions AlO octahedra. This explains the perfect cleavage of of the end members forsterite (Fo) 015118-03-3), 10 sillimanite parallel to {010. The chain structure also Mg2SiO4], and fayalite (Fa), Fe2SiO4), The interme- accounts for the generally fibrous structure of silliman diate members are olivine (Mgoozo, Feo-so)2SiO4. ite crystals (fibrolite). As sillimanite has chains of hyalosiderite (Mgzo-so, Feso-so)2SiO4), hortonolite tetrahedra, it is classified as an inosilicate (chain sili (Mgsoo, Fesozo)SiO, and ferrohortonolite cates, i.e., silicates with infinite chains of SiOI (Mgolo, Fezo-oo)SiO4. Other members of the oliv- 15 tetrahedra). ine series include tephroite Mn2[SiO], knebelite, (Mn, Mullite Fe)SiO, and iron knebelite (Fe,Mn)2SiO4). Mullite 1302–93-8 belongs to the nesosubsilicates (or Andalusite: thosilicates that contain isolated SiO4 tetrahedra and Andalusite 12183-86-1 belongs to the nesosubsilicates additional nontetrahedral anions) and is very similar to (orthosilicates that contain isolated SiO4 tetrahedra 20 sillimanite (Section Sillimanite) in its structure and and additional nontetrahedral anions), and, like kyanite properties. Structure and Mineralogy. Mullite has a (Section Kyanite and sillimanite (Section Sillimantite), sillimanite structure, but differs from sillimanite in is a mineral of the AlSiOs group. Structure and Min- having a deficiency of oxygen. Since Some of the eralogy. AlSiOs can form three different crystal struc- silicon atoms in the SiO4 tetrahedra are replaced by tures, i.e., AlSiOs exhibits polymorphism in the form 25 Al", some of the positions normally occupied by of andalusite, sillimanite and kyanite. In all three oxygen atoms are left unoccupied to maintain charge phases one aluminum atom always has the coordination balance. Therefore, mullite has a higher aluminum number six, i.e., it is Surrounded octahedrally by six content than sillimanite and has a chemical composi oxygen ions. The AlAO octahedra are linked by tion between 3 Al-O.2 SiO, and 2 Al-O.SiO. common edges to form chains parallel to the c axis. The 30 Vermiculite: co dimension in all three minerals is therefore approxi- Vermiculite belongs to the phyllosilicates (sheet or layer mately the same (ca. 0.55 nm). The other aluminum silicates) and has a mica-like foliated structure. It atom in andalusite has the coordination number five, in displays the typical properties of the montmorillonite— sillimanite four, and in kyanite six. The chains of Saponite group to a pronounced degree: the layers have octahedra in andalusite are held together by AlOs and 35 a greater excess charge and a greater capacity for cation SiO groups. In andalusite none of the bonds break exchange than talc or pyrophyllite layers. The structure preferentially, so that andalusite has a higher Mohs contains layers similar to those found in talc, pyrophyl hardness (7/2) than sillimanite or kyanite. Libethenite lite, biotite, and muscovite. It comprises infinite, two CuOH/PO, adamine ZnOH/ASO and eveite Mn dimensional double silicate layers & SiOo. Part of [OH/AsO4) are isotypical with andalusite. 40 the Si" is substituted by Al", and the terminal oxygen Kyanite: ions of the (Si,Al)O tetrahedra are always on the Kyanite 1302-76-7 (cyanite, disthene) belongs to the same side. The hexagons formed by these oxygen ions nesosubsilicates (orthosilicates that contain isolated have hydroxyl groups at their centers. In this double SiO4 tetrahedra and additional nontetrahedral anions) layer, the oxygen layers formed from O (bound to one and, like andalusite (Section Andalusite) and silliman- 45 Si) and OH groups face each other directly, forming ite (Section Sillimanite), is a mineral of the AlSiOs octahedral voids. These voids are occupied mainly by group. Structure and Mineralogy. One aluminum atom Mg", but also by Fe" and Al", which hold together always has the coordination number six, the [AlO] the two Si-Os/OH sheets. The octahedral voids are octahedra being linked by common edges to form formed by four oxygen atoms and two hydroxyl chains parallel to the c axis. The other aluminum atom 50 groups. Due to the partial replacement of Si" by Al", in kyanite also has the coordination number six. The the double layer pocket Mga(SiAl) Oo/(OH)2] has a chains of[AlO] octahedra are joined to other [AlO] slight excess negative charge, which is compensated by octahedra, which are attached alternately to the right additional cations, e.g., Mg. These cations, together and left and are also linked via isolated SiO4 tetra- with water molecules, are interlayered between the hedra to form stable planar structures parallel to 100. 55 layer pockets, usually Mg" or, less frequently, Ca". Vacant octahedra form open channels parallel to (001). This interlayer (intermediate layer) has a positive Sillimanite: excess charge and consists of a double layer of H-O- Sillimanite (fibrolite) belongs to the nesosubsilicates (or- Mg" HO, in which the HO locations may be only thosilicates that contain isolated SiO4 tetrahedra and partially occupied. Each HO in this interlayer is linked additional nontetrahedral anions) and, like andalusite 60 to an oxygen atom in the neighbouring silicate double (Section Andalusite), kyanite (Section Kyanite) and layer by a hydrogen bond. Thus, vermiculite structur mullite, is a mineral of the AlSiOs group. Structure ally resembles a kind of talc expanded by HO that has and Mineralogy. One aluminum atom always has the been formed from (hydrous) mica by potassium deple coordination number six. The [AlO] octahedra are tion. linked by common edges to form chains parallel to the 65 Perlite: c axis. The other aluminum atom in sillimanite has the Perlite of rhyolitic composition is a natural, Volcanic glass coordination number four. The chains of octahedra in that is usually black or gray, but sometimes brownish US 9,656,103 B2 13 14 red. It has curved shrinkage cracks and therefore breaks can be used as single Substances or as mixtures of more than up into spheroidal granules. It is usually produced by one, for example 2, 3 or 4 single components. rapid cooling of rhyolitic melts (rhyolite being the The insoluble substances, which are preferably used in the Volcanic equivalent of granite). Being a volcanic glass, micronised state, may be prepared according to any known perlite contains few crystals and only a small amount of 5 process Suitable for the preparation of microparticles, for water (2-6% combined water). Naturally-occurring example wet-milling, wet-kneading spray-drying, by the glasses containing 3-8% water are known as pitchstone expansion according to the RESS process or by reprecipi (hydrated glass). tation from suitable solvents. The micronised particles so obtained usually have an Pumice: average particle size from 0.02 to 10 micrometer, preferably Pumice 001332-09-8) is not a crystalline silicate mineral, 10 from 0.03 to 5 micrometer and more especially from 0.05 to but a light-colored, highly vesiculated, foamed Volca 3 micrometer. nic glass of mainly acid character (>66% SiO, rhyo Cosmetic UV absorbers are substances, which signifi lite), with a high melt viscosity, high pore Volume cantly reduce the transmission of UV light when applied on (>50%) and variable water content. human skin. Typical is an SPF value higher than 4 if the Wollastonite: 15 cosmetic formulation contains at least 5% of such a cosmetic Wollastonite [013983-17-0), Cas[SiO3). is polymorphic. UV absorber. Three modifications occur naturally, the commonest As cosmetic UV filters which are soluble in the oil phase being low wollastonite which has two polytypical of the cosmetic composition especially non-micronised structural modifications: triclinic wollastonite (-1T) compounds are preferred, i.e. organic UV absorbers selected and monoclinic Wollastonite (-2M, parawollastonite). from the class of the p-aminobenzoic acid derivatives, In monoclinic wollastonite, the SiO4 tetrahedra are salicylic acid derivatives, benzophenone derivatives, diben linked to form infinite one-dimensional dreier single Zoylmethane derivatives, diphenyl acrylate derivatives, ben chains of SiO, units. These are bonded together by Zofuran derivatives, polymeric UV absorbers, comprising Ca" ions (which balance the electrical charge), and the one or more organosilicon radicals, cinnamic acid deriva chains lie parallel to b 010. This explains why the 25 tives, camphor derivatives, trianilino-s-triazine derivatives, crystals are always extended in the direction of b 010. S-triazine derivatives, phenylbenzimidazolesulfonic acid The monoclinic structure is derived from the triclinic and salts thereof, menthyl anthranilates and benzotriazole by “inner twinning on the (100) plane. Wollastonite derivatives. (-1T) and wollastonite (-2M) are therefore inosilicates Preferably, the following UV filters are of special interest: (silicates containing SiO4 tetrahedra in infinite 30 aminobenzophenone derivatives of formula chains). Further examples for micronized insoluble substances which can be used according to the present invention are O birefringent nanocomposites, birefringent glitter particles as OH O A R3, described in U.S. Pat. No. 6,475,609, birefringent materials 35 as described in WO0121678, U.S. Pat. No. 4,461,886, R EP1134270, anisotropic organic compounds as described in ??? WO9216519, birefringent polymer particles as described in: -N ?? Mikhailov, N. V.; Maiboroda, V. I.; Nikolaeva, S. S. Kol ?? ??? pi loidnyi Zhurnal (1959), 21 246-7., WO2004024778; 40 Meeten, G. H.; Navard, P. Dep. Phys. City London Poly wherein tech., London, UK. Journal of Polymer Science, Polymer R and R independently from each other are: Physics Edition (1984), 22(12), 2159-63; Nichols, Mark E.: C-Coalkyl, C2-Coalkenyl: Cs-Cocycloalkyl, Robertson, Richard E. Dep. Mater. Sci. Eng., Univ. Michi Cs-Cocycloalkenyl: or R and R together with the gan, Ann Arbor, Mich., USA. Journal of Polymer Science, 45 linking nitrogen atom form a 5- or 6-membered Part B: Polymer Physics (1994), 32(3), 573-7. heterocyclic ring Furthermore, starch and chemically modified Starches can n is a number from 1 to 4: be used as micronized insoluble Substances according to the when n=1, present invention, like Zea Mays (Amidon De Mais MST R is a saturated or unsaturated heterocyclic radical; (Wackherr), Argo Brand Corn Starch (Corn Products), Pure 50 Dent (Grain Processing), Purity 21 C (National Starch)), rice hydroxy-C-C-alkyl, cyclohexyl optionally substi starch (D.S.A. 7 (Agrana Stärke), Oryzapearl (Ichimaru tuted with one or more C-C alkyl; phenyl option Pharcos)); distarch Phosphate (Corn PO4 (Agrana Stärke): ally substituted with a heterocyclic radical, amin corn PO4 (Tri-K)): sodium corn starch octenylsuccinate (C* ocarbonyl or C-C alkylcarboxy: EmCap—Instant 12639 (Cerestar USA)); aluminium starch 55 when n is 2. octenylsuccinate (Covafluid AMD (Wackherr), Dry Flo-PC R is an alkylene-, cycloalkylene, alkenylene or phe (National Starch), Dry Flo Pure (National Starch), Fluid nylene radical which is optionally substituted by a amid DF 12 (Roquette)); textile fibers and cellulose-par carbonyl- or carboxy group; a radical of formula ticles. * CH-C=C CH * or R together with A forms a bivalent radical of the formula Preferably polymer microparticles like hollow polymer 60 microparticles, porous polymer microparticles, like polyeth ylene-particles, polypropylene-particles, polyamide-par ticles, polyacrylonitrile-particles, polyester-particles, polymethylmethacrylate particles and polyurethane particles can be use as micronized insoluble particles. 65 The insoluble or sparingly soluble micronized substances used in the present cosmetic or dermatological composition US 9,656,103 B2 15 16 wherein in which na is a number from 1 to 3: R and R2, independently of one another, are when n is 3. C-C salkyl, C-C salkenyl; a radical of the formula R is an alkanetriyl radical; —CH—CH(—OH)—CH—O-T; or if n is 4, R and R are a radical of the formula R is an alkanetetrayl radical; A is —O—, or —N(Rs)—, and Rs is hydrogen; C-C alkyl; or hydroxy-C-Calkyl. (4a) aminobenzophenone derivatives of the formula 10

15 R is a direct bond; a straight-chain or branched C-C alkylene radical or a radical of the formula CH2—, or —CH2—O—: R. R. and Rs, independently of one another, are C-C salkyl, C-C salkoxy or a radical of the for R", R independently from each other is hydrogen, mula C-Coalkyl, C2-Coalkenyl: Cs-Cocycloalkenyl: wherein R' and R* may forma five- or six-membered r1ng, R. R' independently from each other is C-Coalkyl: 25 C2-C2oalkenyl; C3-C1o cycloalkenyl, C1-C2oalkOXy, Cl-C2oalkoxycarbonyl, C-C2oalkylamino, di(C- R16 Coalkyl)amino, optionally substituted aryl or Het eroaryl; Re is C-Csalkyl; X is hydrogen; COOR; CONR°R7; 30 R. R. R” independently from each other is hydrogen, m and m, independently of one another, are 1 to 4: C-Coalkyl, C-Coalkenyl: Cs-Cocycloalkyl: p is 0 or a number from 1 to 5: Cs-Cocycloalkenyl: (Y-O)-Z: optionally substi A is a radical of the formula tuted aryl; Y is —(CH.) : (CH.) : (CH.) : CH 35 (1b) (CH)—CH2—, Z is –CH2–CH3; –CH2–CH2–CH3; CH CH2—CH2—CH3; CH(CH3)—CH; m is 0; 1; 2; or *; (1c) n is 0; 1; 2: 3; or 4; and 40 Q is a number from 1 to 20. the compound of formula CO2R4

45 or of the formula OH O

(1d)

50 ?? compound of formula 55 Rs is hydrogen; C1-Coalkyl, -(CH2CHRs O), Ra; or a radical of the formula —CH2— CH(—OH)—CH—O-T,;

R4 is hydrogen; M: C1-C5 alkyl; or a radical of the 60 formula -(CH2), O-T: Rs is hydrogen; or methyl; T is hydrogen; or C1-C3alkyl: M is a metal cation; m2 is 1 to 4; and R-O 65 Ill is 1-16.

US 9,656,103 B2 19 20 TABLE 1-continued UV absorber present in the oil phase No. Chemical Name CAS NO. 25 Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-2-methyl-3- 1SS633-54-8 1,3,3,3-tetramethyl-1-(trimethylsilyl)oxydisiloxanylpropyl 26 Dimethicodiethylbezalmalonate 2O7574-74-1 27 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexylester 302776-68-7 28 1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)- 7753-12-0 29 1,3,5-Triazine, 2,4,6-tris(4-(2-ethylhexyl)oxyphenyl- 208114-14-1 30 2-Propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 31 Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester 94134-93-7 32 1,2,3-Propanetriol, 1-(4-aminobenzoate) 136-44-7 33 Benzeneacetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1 34 2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester S232-99-5 35 Anthralinic acid, p-menth-3-yl ester 134-09-8 36 1,3,5-Triazine-2,4,6-triamine, N,N'-bis(4-5-(1,1- 288254-16-0 dimethylpropyl)-2-benzoxazolylphenyl-N"-(2-ethylhexyl)- or Uvasorb K2A

If an organic UV filter is present in the water-phase it is selected from the compounds listed in Table 2. TABLE 2 UV absorber present in the Water-phase

No. Chemical Name CAS NO. 37 2-Hydroxy-4-methoxy benz ophenone-5-sulfonic acid 4065-45-6 38 Alpha-(2-oxoborn-3-ylidene)toluene-4-Sulphonic acid and its salts 56039-58-8 39 Methyl N,N,N-trimethyl-4- (4,7,7-trimethyl-3- 52793-97-2 Oxobicyclo2.2.1]hept-2-ylidene)methylanilinium Sulphate: 40 4-aminobenzoic acid 150-13-0 41 2-phenyl-1H-benzimidazole -5-Sulphonic acid 27503-81-7 42 3,3'-(1,4-phenylenedimethy ene)bis 7,7-dimethyl-2- 90457-82-2 oxo-bicyclo2.2.1]heptane-1 -methanesulfonic acid] 43 H-Benzimidazole-4,6-disu fonic acid, 2.2'-(14- 18O898-37-7 phenylene)bis-, disodium salt 44 Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4- 92484-48-5 hydroxy-5-(1-methylpropyl)-, monosodium salt 45 -Dodecanaminium, N-3- 4- 156679-41-3 (dimethylamino)benzoylamino-propyl N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) 46 -Propanaminium, N.N.N-trimethyl-3-(1-oxo-3-phenyl-2- 177190-98-6 propenyl)-amino-, chloride 47 H-Benzimidazole-4,6-disu fonic acid, 2.2'-(14- 170864-82-1 phenylene)bis 48 -Propanaminium, 3-3-3- (2H-benzotriazol-2-yl)-5-(1,1- 34O964-15-0 dimethyl-ethyl)-4-hydroxyp henyl)-1-oxopropyl)amino]- N,N-diethyl-N-methyl-, me hyl sulfate (salt) 49 2,2'-bis(1,4-phenylene)-1H benzimidazole-4,6- 349580-12-7, isulphonic acid mo-no so ium Salt or Disodium phenyl i'benzimidazole tetrasulfonate or Neolhelio pan AP

Preferably used in the present cosmetic dermatological 50 organic UV absorber present in the oil phase and selected composition of the present invention are the combinations of organic UV absorber present in the oil phase and selected from triazine compounds of formula (e1) and from triazine compounds of formula (e1) and melamin CaMgCO3 (dolomite). derivatives; The following combinations of micronized, insoluble organic UV absorber present in the oil phase and selected 55 from triazine compounds of formula (e1) and CaCo. particles and organic UV absorbers, soluble in the water or (cacite): in the oil phase are preferred:

UV absorber (A) Bifringent micronized particle (B) 1-4-(1,1-dimethylethyl)phenyl-3-(4- Micronized Melamine Micronized Carbonate or methoxyphenyl)propane-1,3-dione O. 1-5% Sulfate of Ca, Sr, Ba O. 1-5% 2-Ethylhexyl 2-cyano,3,3-diphenyl- Micronized Melamine Micronized Carbonate or acrylate 1-10% Sulfate of Ca, Sr, Ba 1-10% US 9,656,103 B2 21 22 -continued

UV absorber (A) Bifringent micronized particle (B) 2-ethylhexyl 4-methoxycinnamate Micronized Melamine Micronized Carbonate or 1-10% Sulfate of Ca, Sr, Ba O-10% 2.4-bis-(4-(2-ethylhexyloxy)-2-hydro Micronized Melamine Micronized Carbonate or xyphenyl}-6-(4-methoxyphenyl)- 1-5% Sulfate of Ca, Sr, Ba (1,3,5)-triazine O-5% Benzoic acid, 2-[4-(diethylamino)-2- Micronized Carbonate or Micronized Carbonate or hydroxybenzoyl-, hexyl ester Sulfate of Ca, Sr, Ba. Sulfate of Ca, Sr, Ba 1-5% O-5%

A further aspect of the present invention is a cosmetic or tological preparation; an oily continuous phase leads to an dermatological composition comprising 15 admixture into the oil- or fatty- or wax-phase. (a) a micronized, insoluble or sparingly solulble Substance In a preferred embodiment of the present invention the which is not a cosmetic UV absorber having a refraction oil-soluble UV absorber is dissolved and mixed with the index of n=1 to 2.5 and a An=0.001 to 0.8 n; non-micronized insoluble non UV-absorbing substance, or (b) a UV-Filter which can be formulated in the oil- or both components are mixed and the micronization is carried water-phase; out in the oil phase. (c) a water phase, The cosmetic or pharmaceutical preparations may be, for (d) an oil phase, example, creams, gels, lotions, alcoholic and aqueous/alco and a cosmetically acceptable carrier. holic solutions, emulsions, waX/fat compositions, stick Preferably, the cosmetic or dermatological composition 25 preparations, powders or ointments. In addition to the above comprises as component (a), a micronized, insoluble Sub mentioned micronizable insoluble substance and the oil stance which has a particle size of 0.01 to 5 um and the soluble UV filter, the cosmetic orpharmaceutical prepara average refractive index of this particle (nparallel--nper tions may contain further adjuvants like fatty alcohols, fatty pendicular/2) differs not more than 0.3 from the refractive acids, natural or synthetic triglycerides including glyceryl index of the oil phase in which the particle is dispersed. 30 esters and derivatives, pearlescent waxes, hydrocarbon oils, Preferably, the concentration of the micronized, insoluble silicones or siloxanes (organosubstituted polysiloxanes), substance (a) is >0.5% of the cosmetic composition, more fluorinated or perfluorinated oils, emulsifiers super-fatting preferably >1%, and most preferably >2%. agents, Surfactants, consistency regulators/thickeners and The LSF- and/or SPF factor indicates the prolongation of rheology modifiers, polymers, biogenic active ingredients, the exposure to the sun of an individual, which is enabled by 35 deodorising active ingredients, anti-dandruff agents, antioxi the use of the Sun protective agent. It is the quotient of dants, hydrotropic agents, preservatives and Bacteria-inhib erythema threshold time with Sun protective agent and iting agents, bacteria-inhibiting agents, perfume oils, colou erythema threshold time without Sun protective agent. rants or polymeric beads or hollow spheres as SPF The cosmetic or dermatological compositions are prefer enhancers. 40 Cosmetic or Pharmaceutical Preparations ably used as boosters for UV-absorbance of cosmetic Sun Cosmetic or pharmaceutical formulations are contained in screen formulations. a wide variety of cosmetic preparations. There come into A measure for the UV protection determination in the consideration, for example, skin-care preparations, -bath sense of the present invention is for example the light preparations, cosmetic personal care preparations, foot-care protecting factor (LSF and/or SPF (SunProofPactor)) or 45 preparations, light-protective preparations, skin-tanning also IPD values. preparations, insect-repellents, deodorants, antiperspirants, The composition of the present invention may be obtained preparations for cleansing and caring for blemished skin, as follows: hair-removal preparations in chemical form (depilation), The insoluble or sparingly soluble birefringent substance having preparations, fragrance preparations or cosmetic (dispersed phase) is slurred in water or in cosmetically 50 hair-treatment preparations, acceptable oil and optionally mixed with an emulsifying Presentation Forms agent or a surfactant as dispersing agent. The final formulations listed may exist in a wide variety If water is used as continuous phase the dispersion may of presentation forms, for example: also be stabilized with an electrolyte. in the form of liquid preparations as a W/O, O/W, O/W/O, Using a cosmetic oil as continuous phase the oil-soluble 55 WIO/W or PIT emulsion and all kinds of microemul UV absorber can be added, or, in case of a liquid UV sions, absorber the dispersion process can be carried out directly in in the form of a gel, the liquid UV absorber as continuous phase (for example in the form of an oil, a cream, milk or lotion, octyl methoxy cinnamate). in the form of a powder, a lacquer, a tablet or make-up, The mixture is kneadable if it is high-viscous and grind 60 in the form of a stick, able if it is low-viscous, depending from the moiety of the in the form of a spray (spray with propellent gas or continuous phase. pump-action spray) or an aerosol, The grindable slurry is grinded in a ball mill until the in the form of a foam, or dispersion has a particle size from 0.03 to 10 um, preferably in the form of a paste. from 0.03 to 5 um, and most preferably from 0.03 to 3 um. 65 The cosmetic preparation according to the invention is If the continuous phase of this dispersion is aqueous it can distinguished by excellent protection of human skin against be placed into the aqueous phase of a cosmetic or derma the damaging effect of Sunlight. US 9,656,103 B2

EXAMPLES By simple adding the materials a slurry is obtained, which is micronized in a laboratory agitator ball mill. A very Example 1 coarse-grained material (a) having a starting grain size of General Dispersion Formulations (in Oil) s >0.5 um must be precutted first, for example by milling in a corundum disk mill, a dissolver and/or a colloid mill or by A dispersion is prepared comprising the following com- kneading. ponents: Also a dry grinding process may be used. 10 (1a) birefringent particle 40-60 parts (1b) emulsifier (as disclosed in chapter "emulsifier) 0-10 parts Examples 2-11 (1c) dissolved UV filter 01-20 parts (1d) cosmetic oil according 0-60 parts Preparation Examples for Dispersions in Oil0 - (inAW 0 96 b.w)

Ex 2 Ex3 Ex4 Ex5 Ex 6 Ex 7 Ex 8. Ex9 Ex 10 Ex 11 Dispersion Com- Disp Disp Disp Disp Disp Disp Disp Disp Disp Disp number ponent 1o 2O 3o 4o So 6o 7C 8O 9o 1 Oo

Melamine (1a) 55 40 O O O 50 O O O O Phatalimide (1a) O O 40 O O O O O O O 5-Aminophtalic (1a) O O O 40 O O O O O O acid Montmorillonite (1a) O O O O 40 O O O O O Tonsi| 414 FF (Sid-Chemie) Compound of (1a) O O O O O O 40 40 40 40 ormula (101) Polystearylgly- (1b) S 10 1 0 1 0 10 O 10 1 0 1 0 10 ceride-PEG 30 Dehymuls (1b) O O O O O O O O O O PGHS Compound of (1c) O O O O O O O 5 O O ormula (102) Compound of (1c) O O O O O O O O 5 O ormula (103) DHHB (1c) O 10 BEMT (1c) O 10 10 10 10 10 O O O O Cyprylic/Capric (1d) 40 O O O O 40 O O O O Triglyceride C12-C15 Alkyl (1d) O 40 40 40 40 O 50 45 45 40 b?ZOat?

(101)

O = S=t ( )

? ?? N ? N????H N H O O HN 1N WM My4. H, O O (102) US 9,656,103 B2

-continued

Ex 2 Ex3 Ex 4 Ex5 Ex 6 Ex 7. Ex 8. Ex9 Ex 10 Ex 11 Dispersion Com- Disp Disp Disp Disp Disp Disp Disp Disp Disp Disp number ponent 1 o 2O 3o 4o So ?? 7C 8O 9o 1Oo (103) ?????? ????? ?????? ???

OH HO O?? ??.O O O

2O Examples 12 to 17 -continued Dispersions in Water (Electrolyte Stabilized, in % Trade Name INCI name % b.w b.w. ) Pemulen TR-2 Acrylates/C10-30 Alkyl O.15 25 Acrylate crosspolymer A dispersion is prepared comprising the following com- Part B Water Aqua qs to 100 ponents: Rhodicare S Xanthan Gum O.15 Disodium EDTA Disodium EDTA O.1 Glycerine Glycerine 4 (2a) birefringent particle 40-60 parts Part C Germaben II Diazolli dinyl Urea/Methyl O.70 (2b) Electrolyte 0.1-10 parts 30 paraben/Propyl (2c) Water 30-60 parts paraben/Propylene Glycol (1d) dissolved UV filter 0.1-20 parts Part D NaOH ad 10% Sodium Hydroxide qS

Disp 1 w Disp 2w Disp 3w Disp 4w Disp 5w Disp 6w Dispersion number Component (Ex. 12) (Ex. 13) (Ex. 14) (Ex. 15) (Ex. 16) (Ex. 17) Melamine (2a) 49 49 O 49 Phatalimide (2a) O O O O 5-Aminophtalic Acid (2a) O O O O Monmorillonite Tonsil (2a) O O 49 O 414 FF (Süd-Chemie) Sodium chloride (2b) 1 O 1 O Magnesiumchloride (2b) O O O 1 Potassium sulfate (2b) O 1 O O Phenylbenzimidazol (2d) 9 10 10 10 sulfonic acid water, deion. (2c) 40 40 40 40

Example 18 50 Manufacturing Instruction: Preparation of a Cosmetic Formulation Comprising Dispersion 1 (in the Oil Phase) Phase A is prepared by incorporation of all the ingredients except Pemulen TR-2, then the mixture is stirred under Trade Name INCI name moderate speed and heat up to 80° C. 55 Part A AXol C62 Glyceryl Stearate Citrate 1.5 At the latest stage of incorporation, Pemulen TR-2 is Disp 1o Melamine in miglyol 812 N 1O.O dispersed into the oil-phase. The phase B is heated up to (55%) Cetiol (OE Dicaprylyl Ether 3.00 75-800 C. Eutanol G Octyll dodecanol 2.0 Phase A is poured into phase B under increase of stirring. Lanette 18 Stearyl Alcohol 1.5 Softisan 100 Hydrogenated Cocoglycerides 1.O 60 The mixture is homogenized for 15 seconds at 10 000 TinOSOrb OMC Ethylhexyl Methoxycinnamate 2.0 rpm. Tinosorb S 2.4-bis-(4-(2-ethylhexyloxy)- 1.7 2-hydroxyl-phenyl-6-(4- At approximately 70° C. Pemulen TR-2 is neutralized methoxyphenyl)-(13,5)- with NaOH solution. triazine Neo Heliopan Octocrylene 1.1 65 Under 45° C. phase D is added, then pH is adjusted to Antaron V-216 PVP/Hexadecene Copolymer 1.3 about 6-7. Sunscreen: in-vitro SPF=27; In Vivo SPF=23. US 9,656,103 B2 27 28 Example 19 (a) 20 parts of one of the dispersions from Examples(19a)- (19h), Preparation of a Cosmetic Formulation Comprising (b) 17 parts Capric/Caprylic Triglyceride, Dispersion 1 (in the Water-phase) (c) 5 parts Brij 72 (PEG-2-Stearate),

Trade name INCI-Name (as Supplied) Part A AXol C62 Glyceryl Stearate Citrate 1.5 Miglyol 8810 Butyle Glycol Dicaprylate/DiCaprate 6.O Cetiol (OE Dicaprylyl Ether 4.0 Eutanol G Octyll dodecanol 2.5 Lanette 18 Stearyl Alcohol 1.5 Softisan 100 Hydrogenated Cocoglycerides 1.O TinOSOrb OMC Ethylhexyl Methoxycinnamate 2.0 BEMT BEMT 1.7 Neo Heliopan Octocrylene 1.1 Antaron V-216 PVP/Hexadecene Copolymer 1.3 Pemulen TR-2 Acrylates/C10-30 Alkyl Acrylate O.15 crosspolymer Part B Water Aqua qS to 100 Disp 1 w 1O.O Rhodicare S Xanthan Gum O.15 Disodium EDTA Disodium EDTA O.1 Glycerine Glycerine 4.0 Part C Germaben II Diazolidinyl Urea/Methyl paraben/ O.70 Propylparaben/Propylene Glycol Part D NaOH ad 10% Sodium Hydroxide

Phase A is prepared by incorporation of all the ingredi (d) 5 parts Eutanol G 16 (C-16 alkylalcohol), ents, then the mixture is stirred under moderate speed and (e) 3 parts glycerine, and heated until 80° C. At the latest incorporation, Pemulen TR-2 is dispersed 30 (f) 50 parts water, deion. into the oil-phase. The components of the oil phase (a)-(d) are added The phase B is heated at 75-80° C. together and warmed up to 75° C. Phase A is poured into phase B under accelerated stirring. Under stirring the water phase (e) and (f) which is also The mixture is homogenized for 15 seconds at 10 000 35 warmed up to 75° C. is added and homogenized with a rpm. Ultra-Turrax (10,000 rpm). At approximately 70° C. Pemulen TR-2 is neutralized The formulation so obtained is applied on sand blasted with NaOH solution. PMMA plates according to a process described by Wendelet Under 45° C. phase D is added, then the pH is adjusted to al (Wendel et al., SOFW-Journal, 127(11); 2001). about 6-7. 40 After that the MPF values and the SPF value are deter Sunscreen In-vitro SPF=20 mined with an Optometrix-SPF-290. For determination of SPF/MPF values of the dispersions Formulations having a particle content of 8% and a below the following formulation is prepared: content of dissolved UV absorber of 2% are obtained. TABLE 3

Determination of the SPF factor

Birefringent Dissolved UV- SPF with SPF without particles AbSOrber particle particle

Example 19a Phtalimide BEMT 4 6.5 (a = Disp 3o (2% BEMT) (2% BEMT) rom Ex. 2-11) Example 19b Melamine BEMT 13.5 6.5 (a = Disp 2o (2% BEMT) (2% BEMT) rom Ex. 2-11) Example 19c montmorillonite BEMT 12.6 6.5 (a = Disp 5o TOnSil 414 FF (2% BEMT) (2% BEMT) rom Ex. 2-11) (Sid-Chemie) Example 19d 5-Aminoiso- BEMT 8 6.5 (a = Disp 4o phtalic acid (2% BEMT) (2% BEMT) rom Ex. 2-11) Example 19e Compound of BEMT 9 6.5 (a = Disp 7o formula (101) (2% BEMT) (2% BEMT) rom Ex. 2-11) Example 19 Compound of DHHB 4.8 (a = Disp 8o formula (101) (1,6% DHHB) (1.6% DHHB) rom Ex. 2-11) US 9,656,103 B2 29 30 TABLE 3-continued

Determination of the SPF factor

Birefringent DiSSolved UV- SPF with SPF without particles Absorber particle particle Example 19g Compound of Compound of 9 5.5 (a = Disp 9o formula (101) formula (103) (1.6% Compound (1.6% Compound from Ex. 2-11) of formula (103)) of formula (103)) Example 19h Compound of Compound of 8 6.5 (a = Disp 10o formula (101) formula (102) (1.6% Compound (1.6% Compound from Ex. 2-11) of formula (102)) of formula (102)) BEMT = Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine DHHB = Diethylamino Hydroxybenzoyl Hexyl Benzoate

15 Results: As can be seen from Table 3 the compositions of the SO% dispersion 20a present invention comprising a birefringent particle show a 0.75% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine remarkable increase in SPF. 49.25% wo emulsion a Example 20 Preparation of UV Absorber Dispersions wfo Emulsion a: Containing Micronized Calcium Salts 25 Dispersion 20a: Oil Phase: Paraffinum Liquidum 12 Cyclomethicone 7 SO wt.-96 Calcite (CaCO3) 4 wit-% Arlacel P135 (PEG-30-Polyhydroxy stearinic acid) sohexadecane 6 ad 100% Miglyol 812N (Capric/Caprylic triglyceride) 30 sopropyl Palmitate 5 Cera Microcristallina 2 PEG-40 Sorbitan Perisostearate 1.8 Dispersion 20b: Polyglyceryl-3-Diisostearate 1.7 Prunus Dulcis 0.7 35 Tocopheryl Acetate O.S SO wt.-% Calcite (CaCO3) Lanolin Alcohol O.S 4 wit-% Arlacel P135 (PEG-30-Polyhydroxy stearinic acid) 10 wt.-% Ethylhexyl methoxy cinnamate Water Phase: 7.5 wt.-96 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine ad 100% Miglyol 812N (Capric/Caprylic triglyceride) Sodium Lactate 1.1 40 Lactic Acid 1.O MgSO O.8 Dispersion 20c: NaHCO 0.4 Citric Acid O.2 odopropymyl Butylcarbamate O.2 SO wt-9/6 Calcite (CaCO3) Fragrance O.1 4 wit-% Arlacel P135 (PEG-30-Polyhydroxy stearinic acid) 45 10 wt.-% Ethylhexyl methoxy cinnamate Water ad 100 7.5 wt.-96 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Glycerine 8 ad 100% C2-C5 Alkylbenzoate

Dispersion 20d. Both phases are heated separately to 80°C. The oil phase 50 is added to the water phase under stirring prior emulsifica tion. SO wt.-% Calcite (CaCO3) 4 wit-% Arlacel P135 (PEG-30-Polyhydroxy stearinic acid) This emulsion is measured in a Perkin-Elmer UV-Vis 15 wt.-% Octocrylene spectrometer using 8 um cuvettes. The extinction measured 7.5 wt.-96 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 55 for this formulation is E=1.2 at 340 nm, whereas the placebo ad 100% Miglyol 812N (Capric/Caprylic triglyceride) without any calcite is E=0.65 at 340 nm. Preparation Method: SPF Measurements: The slurries of dispersion 20a-20d are homogenized using For SPF measurements the dispersions 20a-20d are incor a high shear apparatus (Ultra-turrax) prior wet-milling with 60 porated in an analogous way into a commercially available a bead mill, down to a particle size (calcite) of 0.5 to 5 um. wfo-lotion. Such dispersions can be incorporated into cosmetic w/o or Basic formulation: X % dispersion Y o/w emulsions. Extinction Measurement: ad 100% w/o emulsion a For the extinction measurement a formulation using dis 65 These preparations are applied on transpore tape (2 persion 20a is prepared by heating all components on 60° C. ul/cm) and measured using an Optometrix-SPF 290S-ana prior stirring and homogenizing using an ultra-turrax: lyzer. US 9,656,103 B2 31 32 Results (SPF Values) are listed in Table 4 1,3,5-triazine-2,4(1H.3H)-dione, 6-amino- of the formula TABLE 4

SPF of dispersions containing micronized calcium salts 5 HN NH ? = 5 ? = 1 ? ? = 20 X = 30

Y = 16b 2.7 5.3 13.7 25.3 O Placebo (y = 16b 2.1 4.1 7.6 11.1 without Calcite) benzene-1,2,4,5-tetracarboxamide, biphenyl-4,4'-dicar Y = 16c 3.1 5.5 14.5 28.1 10 boxamide, biphenyl-4-carboxylic amide, Y = 16d 8.2 19 35 isophthalamide and terephthalamide; cyanuric acid, diphenyl urea, propylurea, 3-methyl-1,1- The invention claimed is: diphenylurea; 1. A method for the enhancement of light protection of a cosmetic or dermatological composition, said method com 15 Isatin: 5-amino-isophthalic acid: diphenyl sulfone, and prising a triazine compound of the formula dispersing insoluble or sparingly soluble micronized bire fringent particles having an average refractive index of t n=1 to 2.5 and a An=0.001 to 0.8 in an oil or water O ES E O phase of a cosmetic or dermatological composition and the birefringent particles are selected from the group consisting of melamine polyphosphate, melamine cya nurate, melamine phosphate, melam (1,3,5-triazine-2, 4,6-triamine-n-(4,6-diamino-1,3,5-triazine-2-yl) of the formula 25 NHs ? ? ??? ?? ? H H ON 4.O melem (-2.5.8-triamino 1,3,4,6,7,9.9b-heptaaza HN ???? M nYNH phenalene) of the formula 35 ?N? \ / ,NH NH2 wherein the insoluble or sparingly soluble micronized birefringent particles have a particle size from 0.02 to 10 micrometers, and N?????? wherein said composition further comprises at least one 40 cosmetic UV filter that is soluble in the water or oil ?? phase. 2. A method according to claim 1, wherein the birefrin gent particles contain a hydrophobic or hydrophilic Surface. ??????? ??????? 3. A method according to claim 1, wherein the birefrin 45 gent particles are crystalline or semi-crystalline. melon (poly 8-amino-1,3,4,6,7,9.9b-heptaazaphenalene 4. A method according to claim 1, wherein the birefrin 2,5-diyl)imino) of the formula gent particles are a high melting Solid, wherein the high melting solid has a melting point of >80° C. 5. A method according to claim 1, wherein the oil phase 50 comprises a UV filter selected from the group consisting of p-aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, dibenzoylmethane derivatives, diphenylacrylate derivatives, benzofuran derivatives, poly meric UV absorbers comprising one or more organosilicon 55 radicals, cinnamic acid derivatives, camphor derivatives, trianilino-s-triazine derivatives, S-triazine derivatives, phe nylbenzimidazolesulfonic acid and salts thereof, menthyl 1,3,5-triazin-2(1H)-one, 4,6-diamino of the formula anthranilates and benzotriazole derivatives. 6. A method according to claim 5, wherein the UV filter 60 is selected from the group consisting of (+/-)-1,7,7-trimethyl-3-(4-methylpheny)methylenelbi cyclo[2.2.1]heptan-2-one; 1,7,7-trimethyl-3-(phenylm ethylene)bicyclo2.2.1]heptan-2-one; (2-hydroxy-4- methoxyphenyl)(4-methylphenyl)methanone; 2,4- 65 dihydroxyben Zophenone; 2,2',4,4'- tetrahydroxybenzophenone; 2-hydroxy-4-methoxy benzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzo

US 9,656,103 B2 35 36 Isatin: 5-amino-isophthalic acid: diphenyl sulfone, and and a cosmetically acceptable carrier, a triazine compound of the formula wherein the insoluble or sparingly soluble micronized NH birefringent particles have a particle size from 0.01 to 5 micrometers and are dispersed in the oil phase or in OESEO 5 the water phase. 9. A cosmetic composition according to claim 8, wherein the average refractive index of the particles (d) (nparallel + nperpendicular/2) differs not more than 0.3 from the 10 refractive index of the oil phase in which the particles are NH dispersed. wherein??????N 10. A cosmetic composition according to claim 8, ? ? is the concentration of the particles (a) is >0.5%. ??? 11. A cosmetic composition according to claim 8, wherein O O the concentration of the particles (a) is >1%. HN1 \ MS YNH, 20 12. A cosmetic composition according to claim8, wherein O O the concentration of the particles (a) is >2%. ? ? ? ? ?