US007250174B2

(12) United States Patent (10) Patent N0.: US 7,250,174 B2 Lee et al. (45) Date of Patent: Jul. 31, 2007

(54) COSMETIC, PERSONAL CARE, CLEANING 4,994,414 A 2/1991 Yamamoto et a1. AGENT, AND NUTRITIONAL SUPPLEMENT 5,034,216 A 7/1991 Barone et a1‘ COMPOSITIONS AND METHODS OF 5,074,916 A 12/1991 Hench et al. MAKING AND USING SAME 5,290,544 A * 3/1994 Shimono et al. (75) Inventors: Sean Lee, Karlsruhe (DE); Susanna 5380360 A 1/ 1995 Noguchi et 31' Kessler’ Ergolding (DE); Oliver 5,614,489 A 3/ 1997 Mohammadi et al. Forberich, Oberursel (DE); Claire 5,658,332 A 8/1997 Ducheyne et al. BuchWar, Wiesbaden (DE); David C. 5,735,942 A 4/ 1998 Litkowski et a1. Greenspan, Gainesviiie, FL (Us) 5,766,611 A * 6/1998 Shimono etal. (73) Assignee: Schott AG, MainZ (DE) 5’827’882 A 10/1998 Yu et 31' 5,834,008 A 11/1998 Greenspan et al. ( * ) Notice: Subject to any disclaimer, the term of this 5,874,101 A 2/ 1999 Zhong ei ai~ patent is extended or adjusted under 35 5,891,233 A 4/1999 Salonen et al. U-S-C- 154(1)) by 0 days- 5,891,470 A 4/1999 Rinaldi et al. (21) Appl' NO‘: 09/818,466 5,972,384 A 10/1999 Thut et al. 5,977,204 A 11/1999 Boyan et al. (22) Filed; Man 27, 2001 5,990,380 A 11/1999 Marotta et al. 5,997,887 A 12/1999 Ha et al. (65) Prior Publication Data 6,010,713 A 1/2000 Zhong et al. Us 2002/0086039 A1 ]u1_ 4, 2002 6,086,374 A 7/2000 Litkowski et al. 6,224,888 B1 * 5/2001 Vatter et a1. Related U-S- Application Data 6,517,863 B1* 2/2003 LaTorre et a1. (60) Provisional application No. 60/ 197,162, ?led on Apr. 14, 2000, provisional application No. 60/192,216, ?led on Mar. 27, 2000. FOREIGN PATENT DOCUMENTS (51) Int. Cl. A61K 6/00 (200601) EP 0 261 593 3/1988 A61]; 9/00 (200601) W0 WO 97/27148 7/1997 A61K 25/34 (2006.01) W0 WO 98/11853 3/1998 A61K 8/00 (200691) W0 WO 98/46164 10/1998 A61K 8/18 (2006.01) (52) US. Cl...... 424/401; 424/400; 424/404; 424/64; 424/69; 424/70.1 (58) Field of Classi?cation Search ...... 424/400, (Continued) 424/401, 63, 64, 69, 59, 404 See application ?le for complete search history. OTHER PUBLICATIONS (56) References Cited Ogina, M et al., “Compositional dependence of the formation of calcium phosphate ?lms on bioglass”, Journal of Biomedical mate US. PATENT DOCUMENTS rials Research, vol. 14, pp. 55-64, 1980. 3,922,155 A 11/1975 Broemer et a1. (Continued) 3,981,736 A 9/1976 Broemer et a1. 4,120,730 A 10/1978 Trojer et al. Primary ExamineriHumera N Sheikh 4,171,544 A 10/1979 Hench et a1. (74) Attorney, Agent, or FirmiKramer, Levin, Naftalis & 4,189,325 A 2/1980 Barrett et a1. Frankel LLP 4,234,972 A 11/1980 Hench et a1. 4,366,253 A 12/1982 Yagi (57) ABSTRACT 4,478,904 A 10/1984 Ducheyne et al. 4,560,666 A 12/1985 Yoshida et a1. 4,604,097 A 8/1986 Graves et al. 4,652,534 A 3/1987 Kasuga The present invention involves neW cosmetic, personal care, 4,698,318 A 10/1987 Vogel et a1. cleaning agent, biocidal agent, functional food, and nutri 4,737,411 A 4/1988 Graves et al. tional supplement compositions. These neW compositions 4,775,646 A 10/1988 Hench et a1. incorporate bioactive glass into cosmetics, personal care 4,777,041 A 10/1988 Mercado items, cleaning agents, biocidal agents, functional foods, and 4,783,429 A 11/1988 Shibuya et a1. nutritional supplements. The present invention also involves 4,786,555 A 11/1988 Howard methods of making and methods of using such composi 4,814,165 A * 3/1989 Berg et a1. tions. 4,851,046 A 7/1989 Low et a1. 4,871,384 A 10/1989 Kasuga 4,965,071 A 10/1990 Kawan 14 Claims, N0 Drawings US 7,250,174 B2 Page 2

FOREIGN PATENT DOCUMENTS Gross, U. et al., “The Response of Bone to Surface-Active Glasses/ Glass-Ceramics”, CRC Critical Reviews in Biocompatibility, vol. 4, W0 WO 98/46170 10/1998 No. 2, pp. 155-179, 1988. W0 WO 99/13852 3/1999 Gross, U. et al., “Surface Activities of Bioactive Glass, Aluminum W0 WO 99/16423 4/1999 Oxide, and Titanium in a Living Environment”, Annals New York WO 9937287 * 7/1999 Academy ofSciences, pp. 211-226. W0 WO 99/37287 7/1999 W0 WO 00/15167 3/2000 Niemi, L. et al., “In vivo behaviour of glasses in the SiO2-Na20 W0 WO 00/42977 7/2000 CaO-P205-Al203-B2-O3-system”, pp. 1-16. W0 WO 00/76486 12/2000 Hench, L., “Bioactive Glasses and Glass-Ceramics: A Perspective”, W0 WO 01/03650 1/2001 CRC Handbook ofBioactive Ceramics, vol. 1, pp. 7-23. W0 WO 01/72145 10/2001 Birchall, J ., The interrelationship between silicon and aluminum in the biological effects of aluminum:, Silicon and Aluminum in OTHER PUBLICATIONS Biology, pp. 50-67. Williams, D, Biocompatibility of Orthopedic Implants, chapter 6, Hench, L. et al., “Biological Applications of Bioactive Glasses”, pp. 130-170, Sep. 1, 1982. Life Chemistry Reports, vol. 13, pp. 187-241, 1996. Hulbert, S., “History of Bioceramics”, Ceramics International, vol. Schepers, E. et al., “Bioactive Glass Particles of Narrow Size 8, pp. 131-140, 1982. Range: A new material for the repair of bone defects”, Implant Hench, L., et al., Biomaterials.‘ An Interfacial Approach, pp. 145 Dentistry, vol. 2, No. 3, pp. 151-156, 1993. 148, Academic Press, 1982. European Search Report for EP 01922745.3 dated Mar. 10, 2006. Hench, L. et al., “Surface-Active Biomaterials”, Science, vol. 226, pp. 630-636, Nov. 9, 1984. * cited by examiner US 7,250,174 B2 1 2 COSMETIC, PERSONAL CARE, CLEANING of bioactive glass for unrelated purposes such as orthopedic AGENT, AND NUTRITIONAL SUPPLEMENT repair is described by Larry L. Hench and Jon K. West in COMPOSITIONS AND METHODS OF “Biological Applications of Bioactive Glasses” Life Chem MAKING AND USING SAME istry Reports, 1996, Vol. 13, pp. 187-241, the contents of Which are incorporated herein by reference. RELATED APPLICATIONS DETAILED DESCRIPTION OF THE This application claims priority from co-pending US. INVENTION Provisional Application No. 60/192,216, ?led Mar. 27, 2000, co-pending US. Provisional Application No. 60/ 197, Bioactive glass is a sodium-calcium-phospho-silicate 162, ?led Apr. 14, 2000, co-pending US. application Ser. glass. As used herein, the term “bioactive glass” may refer No. 09/456,196, ?led Dec. 7, 1999, and co-pending US. to particulate melt-derived and/or sol-gel derived bioactive application Ser. No. 09/456,195, ?led Dec. 7, 1999. The full glass. In addition, the term “bioactive glass” may be used to disclosure of each of these applications is incorporated refer to an aqueous extract of particulate melt-derived an/or herein by reference. sol-gel derived bioactive glass. The present invention utiliZes bioactive glass preferably FIELD OF THE INVENTION betWeen 40 and 96% by Weight of silicon dioxide oxide (SiO2), betWeen about 0 and 35% by Weight of sodium oxide The present invention involves neW cosmetic, personal (NazO), betWeen about 4 and 46% by Weight calcium oxide care, cleaning agent, biocidal agent, functional food, and 20 (CaO), and betWeen about 1 and 15% by Weight phosphorus nutritional supplement compositions. These neW composi oxide (P205). As referred herein, bioactive glasses are tions incorporate bioactive glass into cosmetics, cleaning typically silicon dioxide based compositions capable of agents, personal care products, biocidal agents, functional forming hydroxycarbonate apatite (HCA). More preferably, foods and nutritional supplements. The present invention the glass includes betWeen 40 and 60% by Weight of silicon also involves methods of making and methods of using such 25 dioxide oxide (SiO2), betWeen about 5-30% by Weight of compositions. sodium oxide (N a2O), betWeen about 10 and 35% by Weight calcium oxide (CaO), and betWeen about 1 and 12% by BACKGROUND OF THE INVENTION Weight phosphorus oxide (P205). The oxides can be present as solid solutions or mixed oxides, or as mixtures of oxides. Preservatives are necessary and important ingredients that 30 CaF2, B2O3, A1203, MgO and K20 may be included in the ensure the stability and safety of di?cerent products. Many composition in addition to silicon, sodium, phosphorus and problems exist With respect to known preservatives. Many calcium oxides. The preferred range for B203 is betWeen 0 have unWanted effects on the products they are in or on the and 10% by Weight. The preferred range for K20 is betWeen person or thing for Which the products are used. Many are 0 and 8% by Weight. The preferred range for MgO is relatively expensive and have no bene?cial e?cects besides 35 betWeen 0 and 5% by Weight. preservation. Many, in fact, are not ef?cacious as preserva Typically, bioactive glasses have the folloWing composi tives. Many have e?cects on the products’ texture or taste that tion by Weight percentage: make them undesirable. Better preservatives are needed. There has also been a great need for ingredients that can be used safely and bene?cially in products that have anti 40 bacterial, antifungal, antiviral, ion releasing, anti-in?amma Component Wt. Percent tory and/or pH properties in the products themselves and/or $102 40490 on the person or thing for Which the product issued. Ingre CaO 445 dients that can express one or more of these properties are Na2O 0435 P205 2416 needed. 45 Cal:2 0425 B203 04 SUMMARY OF THE INVENTION K20 048 MgO 045 Applicants have found that bioactive glass When used in a Wide variety of cosmetics provides exceptional qualities to 50 A more prefered composition by Weight percentage for the cosmetic including a bene?cial preservative e?‘ect. bioactive glass is as folloWs: Applicants also have found that bioactive glass preserves a variety of standard household and industrial cleaning agents. Further, certain bioactive glass compositions provide excel lent cleaning properties and greatly enhance the cleaning 55 Component Wt. Percent properties of standard household and industrial cleaning $102 40468 agents. In addition, applicants have found that certain bio CaO 5430 active glass compositions are useful as a functional food and Na2O 10435 nutritional supplement or used in such. Moreover, certain P205 1412 bioactive glass compositions act as an excellent preservative 60 for food. The present invention includes formulations Which may In addition, the compositions of this invention can be comprise metal ions such as AgNO3, CuO, and ZnO, or formulated as disclosed herein to have enhanced and ben other antimicrobial salts, including but not limited to, silver, e?cial properties that include antibacterial, antiviral, anti copper and Zinc ions. These metals may be in nitrate or fungal, ion-releasing, anti-in?ammatory and pH elfects. As 65 acetate form. The preferred range for these salts is betWeen used herein “bioactive glass” is an inorganic glass material 0 and 15% by Weight. The present invention also includes having an oxide of silicon as its major component. The use formulations Which do not comprise metal ions. US 7,250,174 B2 3 4 The most preferred glass is Bioglass®TM (a trademark of When highly porous bioactive glass is used in place of or University of Florida), Which has a composition including in addition to small particles of bioactive glass, the pore siZe about 45% by Weight silicon dioxide, about 24.5% by is betWeen about 0 and 500 um, preferably betWeen about 10 Weight sodium oxide, about 6% by Weight phosphorus and 150 um, and more preferably, betWeen about 50 and 100 oxide, and about 24.5% by Weight calcium oxide. Another pm. The degree of porosity of the glass is betWeen about 0 preferred material is hydroxyapatite. Another preferred and 85%, preferably betWeen about 30 and 80%, and more material for several applications are the porous sol-gel preferably betWeen about 40 and 60%. Porous bioactive glasses. glass can be prepared, for example, by incorporating a Particulate, non-interlinked bioactive glass is preferred leachable substance into the bioactive glass composition, for many embodiments of the present invention. That is, the and leaching the substance out of the glass. Suitable leach glass is in the form of small, discrete particles, rather than a able substances are Well knoWn to those of skill in the art, fused matrix of particles or a mesh or fabric (Woven or and include, for example, sodium chloride and other Water non-Woven) of glass ?bers. Note that under some conditions soluble salts. The particle siZe of the leachable substance is the discrete particles of the present invention may tend to roughly the siZe of the resulting pore. The relative amount cling together because of electrostatic or other forces but are and siZe of the leachable substance gives rise to the degree still considered to be non-interlinked. Preferably the particle of porosity. Also, as described herein, porosity can be siZe is less than about 90 microns; more preferably, less than achieved using sintering and/or by controlling the treatment about 20 microns; even more preferably, less than about 5 cycle of glass gels to control the pores and interpores of the microns, and most preferably, less than about 2 microns, as material. measured by SEM or laser light scattering techniques, 20 In addition, anti-microbial and anti-in?ammatory compo although different uses may advantageously use different sitions derived from aqueous extracts of bioactive glass can particle siZes. be formed by placing bioactive glass in an aqueous solution, The preferred particle siZe range for the bioactive glass is alloWing the glass to dissolve over a suitable period of time, site and use dependent. Particle siZes less than about 1000 for example, a Week or more, and ?ltering out the dissolved microns and greater than about 2 microns can also be used. 25 glass particles. The solvent can also be evaporated to pro Particles of such a small siZe range generally provide for the vide a solid material With anti-microbial properties. These advantages of the present invention Without eliciting unde compositions can be used in situations Where elimination, sirable immune responses. reduction, or prevention of microbes, including but not Without being bound to a particular theory, it is believed limited to bacteria, viruses, and fungi Would be advanta that there is a complex relationship betWeen the type of ion 30 geous, for example, in cosmetic formulations, cleaning being released from the glass, the amount of that ion, the rate agent formulations, functional foods and as a preservative at Which release occurs, the pH of the surrounding environ for foods. ment, and the resulting anti-microbial or anti-in?ammatory The glass composition can be prepared in several Ways to response. This effect is observed With respect to the particles provide melt-derived glass, sol-gel derived glass and sin of bioactive glass themselves and also in the aqueous 35 tered glass particles. The sintered particles may be in sol-gel solutions derived from the glass particles. Accordingly, in derived, unreacted, or pre-reacted melt-derived form. the compositions and uses described beloW, particulate and/ The glass composition is preferably melt-derived. Melt or bioactive glass solutions derived from the particles may derived glass is generally prepared by mixing grains of be used. oxides or carbonates, melting and homogenizing the mix Large particles of bioactive glass do not have appreciable 40 tures at high temperatures, typically betWeen about 1250 and antimicrobial properties. HoWever, small particles of bioac 14000 C. The molten glass can be ?itted and milled to tive glass and highly porous bioactive glass do have appre produce a small particulate material. ciable antimicrobial properties. Bioactive glass has bacteri In each preparation, it is preferred to use reagent grade cidal properties and is effective against, for example, Staph. glass, especially When the glass is used to prepare materials aureus, Staph. epidermidis, and various streptococci. These 45 Which ultimately may be administered topically. Bioactive bacteria may be found in and on the skin. These antimicro glass particles may be prepared using the melt-derived and bial properties are enhanced in an aqueous environment. grinding process described previously in Us. Pat. No. While not being bound by a speci?c mechanism of action, 5,204,106, the disclosure of Which is incorporated herein by it is believed that this action is a result, inter alia, of the reference. Where particular particle siZe ranges are desired, greatly increased bioactivity of the small particulates, Which 50 sifting may be used to obtain such particles. For optimum leads to an increased pH of the surrounding environment. sterility, glass particles may be ultrasonically cleaned, pack The combined properties of being both broadly bactericidal aged in syringes and steriliZed With gamma radiation. While at the same time maintaining tissue biocompatibility The particulate biologically active material used in the make a variety of formulations comprising small particles of present invention may be prepared according to the methods bioactive glass resistant to microbial contamination and 55 of the art such as taught in Us. Pat. Nos. 4,159,358; especially suitable for formulations Which Will contact the 4,234,972; 4,103,002; 4,189,325; 134,171,544; 4,775,646; skin. 4,857,046 and 5,074,916. For example, the raW materials The antimicrobial action increases With decreasing par (e.g., SiO2, CaO, Na2O and PZOS) are mixed in a Nal ticle siZe. The preferred particle siZe depends, in part, on the gene®TM plastic container on a ball mill for four hours. The expected microbial challenge and the desired purity of the 60 mix is then melted in a platinum crucible at 13500 C. and formulation comprising bioactive glass For example, for homogenized for 24 hours. The molten glass is poured into mulations having bioactive glass particles averaging 20 distilled, deioniZed Water to produce a glass frit. Altema microns ordinarily is suf?cient. HoWever, for a longer last tively, ribbons may be prepared by pouring the glass over ing preservative effect or to maintain a higher degree of moving rollers. The frit or ribbons may be ground, for purity, particles averaging less than ?ve microns as mea 65 example, by one of several means. In one method the frit or sured by SEM or laser light scattering techniques may be ribbons are ground in a mortar and pestle and passed through used. ASTM sieves to produce the required particle siZe range. US 7,250,174 B2 5 Alternatively, the frit or ribbons may be ground using a ball-milling or jet milling process. Bioactive glass may be derived using a drying step, Which Component Wt. Percent may include near-equilibrium drying. Near-equilibrium dry ing in place of or in addition to drying under dry conditions SiO2 49472 CaO 5435 provides for much larger average pore siZe in the ?nal P205 59 composition at a given level of SiO2 In addition near equilibrium drying results in a higher rate of resorption as compared to traditionally prepared sol-gel bioactive glass The sol-gel-derived bioactive glass readily reacts With materials. For example, in-vivo testing of one has shoWn aqueous solutions because of the high SSA (i.e., there is a that more than 50% of sol-gel material made in this manner tremendous amount of surface area Where glass/solution resorbed at eight Weeks. Comparable prior 4555 melt reactions can take place). When immersed in an aqueous derived bioactive glasses, do not resorb at all by eight Weeks. solution, the sol-gel-derived bioactive glass begins to react, releasing soluble silica, calcium and phosphate anions. Once Indeed, it has been suggested that glasses including more 15 the concentration of calcium and phosphate anions is than 55% silicon dioxide are not bioactive. increased to the saturation limit for HAp, a mineralogical, As used herein, near-equilibrium drying is drying under HAp-rich layer Will form on the surfaces that comprise the the conditions near the tWo phase boundaries in the phase sol-gel-derived bioactive glass, and surrounding surfaces diagram at a temperature and pressure su?icient to yield a (i.e., hard and soft human tissues). bioactive glass With large pore structure, i.e., a pore structure 20 For example, a reaction mixture including tetraethoxysi su?icient to yield a bioactive glass . For example, near lane (TEOS), triethylphosphate (TEP), and calcium nitrate equilibrium drying may be drying under the conditions near can be used to make sol-gel bioactive glasses. Alkoxides of the line for Water as illustrated in conventional phase dia calcium, titanium, Zirconium, magnesium, aluminum, iron grams (or other liquids such as methanol, ethanol, acetone, and potassium also can be used. Other appropriate ingredi liquid (CO2, benZene and so on). By manipulating the 25 ents Will also be apparent to those of ordinary skill in the art. sealing of the designed drying chamber to adjust the extent In addition, aerogels may be used. When an aerogel is used, of the drying condition aWay from the equilibrium line and increased pressure is used instead of near-equilibrium drying relative humidity (from environmental humidity to 98%), to achieve larger pore siZe and greater resorbability. the duration of near-equilibrium drying, and the temperature Sol-gel processing Which uses a near-equilibrium drying at Which the drying is conducted, one can drastically alter 30 step yields larger pore siZe in the ?nal product and permits pore siZe of resultant bioactive glass. For example, increas development of HCA very rapidly for both high and loW ing the sealing of the drying chamber during drying typically silicon dioxide content gels. Indeed, these compositions results in an increase in relative humidity and pore diameter. form HCA more rapidly than other gels When exposed to Near-equilibrium drying temperature can also be varied, for 35 SBF (Simulated Body Fluid, Kokubo, T. et al., J. Biomed. example, With Water drying. When using liquids other than Mater. Res., 24, 721-34, 1990) or physiological ?uids. The Water, such as those referred to above, one may obtain a near equilibrium drying technique also provides for more faster drying or increase the pore siZe range of the gel to a homogeneous gels Which can be heated to higher tempera large extent. tures While retaining large pore diameter. This permits much A sol-gel process is any process that includes the use of better control of the ?nal product eg resorbability, homo a sol-gel in the preparation of bioactive glass. Sol-gel geneity and physical structure. For example, sol-gel com derived glass is generally prepared by synthesizing an positions derived Without using near-equilibrium drying inorganic network by mixing metal alkoxides in solution, techniques are not able to provide adequate resorbability at folloWed by hydrolysis, gelation, and loW temperature higher levels of silicon dioxide. In contrast, the near-equi (around 200-900° C.) ?ring to produce a glass. Sol-gel librium drying technique provides gels having excellent derived glasses produced this Way are knoWn to have an resorbability even When high amounts of silicon dioxide are initial high speci?c surface area (SSA) compared With either included. Such sol-gel glasses are also more homogeneous melt-derived glass or porous melt derived glass. The result than other sol-gel glasses and calcium is distributed uni ing material contains nanometer-sized purosity and has a formly. SSA ranging from 50-400 m2/g. The sol-gel derived glass This drying technique can be used to prepare all types of does not contain sodium. Thus, When this material comes sol-gel bioactive glasses. For example, the technique can be into contact With an aqueous solution, the dissolution used to prepare frit, ribbons, monoliths, poWders, coatings, mechanisms are different from those associated With non ?bers, mats, Weaves and composites. sol-gel-derived bioactive glass. Frit can be ground to very broad ranges of particle siZe Typically, sol-gel-derived bioactive glasses have the fol such as from about 2 pm up to 1 mm for any purpose. The loWing composition by Weight percentage: monolith can be formed to complex shapes such as various implants. PoWders can be made to spherical form and from submicron to a feW hundred microns. Such compositions are useful, for example, in bone repair and other orthopedic Component Wt. Percent 60 applications, drug delivery, treating tooth hypersensitivity as SiO2 49490 Well as the remineraliZation of tooth structure, burn healing CaO 542 and Wound healing. P205 1412 While not being bound to any particular theory, it is believed that the near-equilibrium drying step reduces cap A more prefered composition for sol-gel-derived bioac illary force inside the pore structure of the gel Which results tive glasses comprises the folloWing composition by Weight in large pore siZe. Gels are netWorks of small colloid percentage: particles. The netWorks includes voids Which become pores US 7,250,174 B2 7 8 and pore channels in the ?nal glass composition. It is preparations. In another embodiment the present invention believed that the moisture of the near-equilibrium drying provides a preservative Which itself contains bioactive glass. step enhances the reaction at the neck betWeen tWo particles The preservative Which contains bioactive glass may be in the netWork and the strength of the neck and “back bone” added to or included in cosmetic formulations. of the gel structure Which reduces shrinkage of the drying A cosmetic formulation in accordance With the present structure and ultimately results in gels With large pores. invention may contain an amount of bioactive glass up to On the other hand, due to the liquid tension, the pressure 95% of the total Weight of the cosmetic formulation, espe difference betWeen the different siZe of pores and channels cially up to 70%, more especially up to 50%, or 40%, and is: even more preferably up to 30% of the Weight of the cosmetic formulation. Upper limits of 7% of the Weight or APIZY cos 0/r 5% of the Weight are preferred for some formulations, Where, y is liquid tension, 0 is contact angle and r is the Whereby 3% of the Weight is especially preferred in some radius of pores and pore channels. During drying, the formulations. LoWer limits are 0.01% of the Weight, espe pressure difference, AP, Will pull the netWork tight enabling cially 0.1% of the Weight, Whereby 0.5% of the Weight and pore collapse and gel shrinkage as liquid evaporates. It is 1% of the Weight are especially preferred as the loWest believed that near-equilibrium drying alloWs the liquid effective amounts. inside the pore structure to evaporate under the condition of In one embodiment the cosmetic formulation comprises a near equilibrium at a range of temperatures. This keeps protic solvent. In another embodiment the cosmetic formu liquid vapor pressure inside the channels and pores at high lation contains bioactive glass Which has components Within heating conditions Which resists the shrinkage and collapse 20 the folloWing ranges on a % Weight basis: 40-60% SiO2; of the gel structure and results in large pore siZes. 10-30% CaO; 10-35% Na2O; 2-8% P205; 0-25% CaF2; Bioactive glass, sol-gel derived bioactive glass and/or 0-10% B203; 0-8% K20; and 0-5% MgO. Cosmetic formulations in accordance With the present aqueous extracts of bioactive glass may be incorporated into various cosmetic, cleaning agent, functional foods, nutri invention can be Well preserved using bioactive glass, With tional supplements and other products as described beloW. 25 out having to add skin-irritating cytotoxic and possibly allergen producing chemical preservatives to the prepara Cosmetics tion. Furthermore, an additional nurturing effect may be achieved through the antimicrobial and in?ammation-inhib General iting effect of bioactive glass. The anti-in?ammatory effects The present invention provides novel cosmetics compo 30 of bioactive glass make it particularly useful in skin care sitions comprising bioactive glass. While current manufac formulations by promoting reductions in irritation, itching, turing processes generally control microbial contamination redness and rashes. When the products are in sealed containers, after unsealing In special cases it might be desirable to add the preser the package, bacteria, fungi and/or mold may contaminate vative in accordance With the present invention to prepara the cosmetics. Often, various antibacterial agents are added 35 tions Which have been preserved using standard preserva to the cosmetics to minimiZe this process. These antibacte tives in order to achieve synergetic effects. rial agents, hoWever, often create negative effects such as Bioactive glass has the ability to react With aqueous skin irritation for the cosmetic user. solutions (i.e., human perspiration, humidity, body ?uids) to A goal of the present invention is to produce cosmetic elicit biological effects such as anti-microbial/antibacterial formulations Which, in contrast to presently available cos 40 behavior, UV screening, anti-in?ammatory behavior, min metics, exhibit an ability to Withstand microbial contami eralogical ?lm forming, and therapeutic release of inorganic nation Without creating negative effects such as skin irrita ions. These effects are considered advantageous for many tion. cosmetic applications, and several examples of cosmetic In one embodiment of the present invention, bioactive formulations that can be used to include bioactive glass glass may be included in cosmetic formulations to minimiZe 45 and/or sol-gel-derived bioactive glass Within a cosmetic microbial contamination, including contamination by bac product are described herein. teria, fungi and/or mold. The cosmetic compositions can Bioactive glass forms a hydroxy carbonate layer (HCA) include the aqueous extracts of bioactive glass and/or par on protein-containing surfaces such as hair, skin, nails and ticles of bioactive glass. teeth. This HCA layer can desensitiZe teeth, harden/thicken In one embodiment the cosmetic formulation comprises 50 nails, protect skin and modify hair texture. particulate bioactive glass having an average particle siZe Bioactive glass and/or sol-gel-derived bioactive glass less than 10 microns. In another embodiment particulate may be effective at absorbing and scattering visible and UV bioactive glass having an average particle siZe less than 5 light, making these materials attractive for soft focus and microns, and preferably less than 2 microns is used. Pre -screening applications. ferred cosmetic preparations are especially creams, make-up 55 In one embodiment cosmetic products comprise sol-gel compounds, lipsticks, lotions and salves since the micro derived bioactive glass. The sol-gel-derived bioactive glass biocidal effect of bioactive glass is further enhanced by the is extremely porous, and thus effective at scattering visible moisture contained in these preparations. HoWever, bioac and UV light. The scatter of visible light is important for soft tive glass can be added to virtually any cosmetic presently focus cosmetic products, Which are intended to scatter light available to improve its resistance to contamination. Accord 60 from the skin in such a Way that skin Wrinkles become less ingly, the cosmetic may be liquid based, or alternatively, visible to the human eye. Further, the scatter of UV light is other than liquid based. Cosmetic formulations may include, important for products. Thus, the sol-gel-derived for example, creams, lotions, lipsticks, make-up compounds bioactive glass is effective at scattering UV light in the UVA and tinctures. and UVB regions of the solar spectrum and provides a soft In one embodiment the invention provides bioactive glass 65 focusing effect. for use as a preservative of perishable goods. The perishable Further, the sol-gel-derived bioactive glass reacts With goods may be, for example, cosmetic and/ or pharmaceutical aqueous solutions to form a solution that becomes concen US 7,250,174 B2 10 trated in calcium, phosphate anions and soluble silica. When Applicants have unexpectedly discovered that a combi this solution becomes saturated, it can form a mineralogical, nation of bioactive glass With standard skin creams give the HAp-rich layer on the to surrounding human tissue. Thus, skin a pleasant-non-oily feeling and look When compared the sol-gel-derived bioactive glass is expected to be effective With the same cream applied Without the added bioactive in soft focus products because it is effective at scattering glass. Without being bound to any mechanism, it is believed visible light, and the precipitation of the mineralogical layer that the bioactive glass has an af?nity for oils as Well as could act as a skin-tightening agent that Would further aid in Water and protenaceous matter, Which is consistent With the hiding skin Wrinkles. unexpected effect observed by Which bioactive glass and oil It should also be noted that in addition to bioactive glass, form a smooth, homogeneous cream consistency. Thus antibiotics may also be added to cosmetic formulations. The bioactive glass is suitable as an effective treatment for addition of antibiotics to cosmetic products Which include oily/fatty skin. bioactive glass is particularly useful in formulations Which Bioactive glass and sol-gel derived bioactive glass exhibit require topical application. many desirable characteristics that Would improve cosmetic products. HoWever, the dif?culty lies in formulating the Methods of Making cosmetic products in such a Way that the bioactive glass The present invention also provides a method of making and/or sol-gel-derived bioactive glass remain unreacted cosmetic compositions comprising bioactive glass. An effec (passive) While packaged, and then become reactive (active) tive antimicrobial amount of the bioactive glass is added to When applied onto the human body. or included in a cosmetic formulation. An “effective, anti Bioactive glass and sol-gel-derived bioactive glass react microbial amount of bioactive glass” refers to a suf?cient 20 With aqueous solutions, but are inert When immersed in amount of bioactive glass having an appropriate particle siZe anhydrous liquids. Thus, bioactive glass and/or sol-gel to effectively prevent or control microbial contamination. derived bioactive glass may be formulated in liquids, pastes, The amount and particle siZe of bioactive glass to include in gels or creams that are anhydrous, but Water-soluble (or a cosmetic formulation Will vary depending on the desired Water permeable). In this instance, the bioactive glass length and degree of purity as Well as the anticipated 25 remains un-reacted While immersed in the anhydrous liquid, microbial challenge. An “effective antimicrobial amount of paste, gel or cream, but Would be activated When applied to bioactive glass” also may refer to a suf?cient amount of an the human body and alloWed to react With perspiration, aqueous extract of bioactive glass to effectively prevent or humidity, and/or other aqueous-containing bodily liquids. control microbial contamination. An “effective antimicro In one embodiment, bioactive glass and/or sol-gel-derived bial amount” of bioactive glass may also refer to a combi 30 bioactive glass for cosmetic products are used in a dispens nation of particulate bioactive glass and aqueous extract of ing system containing tWo separate vessels (i.e., similar to bioactive glass to effectively prevent or control microbial the dispensing system used for an epoxy). The bioactive contamination. glass and/or sol-gel-derived bioactive glass may be could be Bioactive glass may be added to or included in cosmetic formulated in an anhydrous liquid, paste, cream or gel formulations using, for example, techniques or combina 35 Within one vessel, While an aqueous liquid, past, cream or tions of techniques such as general mixing With sloW gel may be contained Within the second vessel. medium, moderate, or even vigorous agitation. Suf?cient In another embodiment bioactive glass and/or sol-gel agitation should be provided to achieve relative homogene derived bioactive glass are mixed With an anhydrous liquid, ity. Preferably, mixing and agitation Will avoid excessive paste cream or gel that evaporated or is metaboliZed into the aeration and Will have a loW sheer rate. In addition, anti 40 skin after being applied to the body. The anhydrous liquid, ?oculants may be used to keep the particles from clumping paste, cream or gel protects the bioactive glass While in the together. cosmetic package, yet disappears once applied to the body, Other methods or combinations of methods of blending, thus alloWing the bioactive glass to react With perspiration, dispersing, mixing, combining and/or emulsifying may be humidity, and/or other aqueous-containing body liquids. utiliZed. Agitation may be achieved, for example, With 45 In yet another embodiment, the desirable characteristics standard mixing devices. General mixing and blending may associated With bioactive glass and/or sol-gel-derived bio be achieved, for example, With an impeller. active glass are achieved by utiliZing an aqueous extract of It has been unexpectedly discovered that for many cos derived from bioactive glass. The bioactive glass and/or metic base formulations, bioactive glass is easier to homo sol-gel-derived bioactive glass may be reacted With an geneously mix than other common inorganic poWders, such 50 aqueous solution until the solution became saturated With as and poWder, for example. calcium, phosphate anions and soluble silica. This solution Bioactive glass may be added to or included in virtually could then be ?ltered, buffered to an appropriate pH, and any knoWn cosmetic formulation. Applicants anticipate as then added to cosmetic formulations to develop cosmetic Well that bioactive glass Will be suitable for inclusion in any products in accordance With the present invention. In this as yet to be developed cosmetic formulation. In one embodi 55 embodiment, the formulation may contain aqueous cosmetic ment the bioactive glass may be particulate. In another ingredients, since there Would be no solid bioactive glass or embodiment the bioactive glass may be an aqueous solution sol-gel-derived bioactive glass available for reaction. derived from particulate bioactive glass. In still another In many cosmetic applications it is desired that the embodiment the bioactive glass may be a combination of product have pH value of betWeen 5 and 8. Maintaining this particulate bioactive glass and an aqueous solution derived 60 pH level With bioactive glass in an aqueous suspension, from bioactive glass. hoWever, is di?icult as the glass Will continuously react in Applicants have unexpectedly discovered that bioactive solution, increasing the pH value. Applicants have discov glass mixed With oil forms a cream. LikeWise, bioactive ered that as little as 1% citric acid can effectively bulfer glass mixed With Water unexpectedly forms a cream. The bioactive glass toWard more neutral pH values over a long cream resulting from mixing bioactive glass With either oil 65 period in an aqueous suspension. This is to be contrasted or Water possesses a consistent homogenized texture par With the effect of adding a standard bulfer, such as HCL ticularly suitable for cosmetic formulations. based bulfers to the same suspension, Which do not maintain US 7,250,174 B2 11 12 pH levels for suitable periods of time. Thus, citric acid is one preferred method of buffering aqueous based solutions With TABLE II bioactive glass. Bioactive glass is especially useful in an RaW Materials Combined With Sol-Gel-Derived Bioactive Glass aqueous containing formulation When the formulation is appropriately buffered to ensure that the pH remains near RaW Material neutral and When the bioactive glass is coated With a Dermol M5 hydrophobic material that prevents the glass from reacting PPG l0 Cetyl ether While in formulation. PEG7 Glyceryl Cocoate d-Limonene In another embodiment the bioactive glass and/ or sol-gel Oleth-3 derived bioactive glass can be formulated into a dry form Stepanquat ML Ammonium Lauryl Sulfate incorporating other ingredients, for example colorants and Incromectant LQ fragrances, and packaged in small packets or caches for Tergitol NP-9 Coco Hydroxy Sultaine single use cosmetic products for skin, hair or nail applica Crodesta SL-4O tions, for example. The dry form may be a poWder. POE2O Sorbitan monooleate Propylene Glycol The folloWing raW materials listed in Table 1 Were mixed Ethanol With bioactive glass and produced stable compositions. Na Laureth-2 Sulfate Sorbitan Isostearate Glycerin TABLE I 20 Procetyl AWS Crodafos SG RaW Materials Combined With Bioactive Glass Glycerox 767 Cocamide DEA RaW Material Jojoba Oil Incromectant AQ Incromectant AQ 25 Promyristyl PM-3 Foamtaine CABG (45%) Promyristyl PM-3 Dermol DPG — 2B Transcutol CG Abil EM-90 Dermol DPG-2B Crodafos N3N Transutol CG Triethanolamine Octyl Methoxycinnamate 30 Crodafos N3N Mineral Oil Triethanolamine Incrodet TD7C Menthyl Anthranilate Polyderm PPI SiWI Mineral Oil PEG2 Oleamine Incrodet TD7C Crodafos CAP Polyderm PPI SiWI Plantaren APB 35 PEG2 Oleamine Polyderm PPI SiWS Crodafos CAP Finsolv TN Plantaren APB Crodasinic O Polyderm PPI SiWS Dermol B-246 Finsolv TN GE 1202 Crodasinic O Dermol B-246 Crovol A-4O 40 Crovol A-7O GE 1202 GE SF 96 350 cps Crovol A-4O Probutyl l4 Crovol A-7O Foamtaine CABG GE SF 96 (350 cps) Dermol MS Probutyl l4 PPG l0 Cetyl ether 45 PEG 7 Glyceryl Cocoate d-Limonene Bioactive glass, including sol-gel derived bioactive glass Oleth-3 may be combined With anyhydrous cosmetic ingredients to Stepanquat ML Ammonium Lauryl Sulfate created stable, non-irritating cosmetic formulations. A list of Incromectant LQ exemplary anhydrous ingredients is provided in Table III. Tergitol NP-9 50 Coco Hydroxy Sultaine Crodesta SL-40*** TABLE III POE2O Sorbitan monooleate Propylene Glycol Anhydrous Cosmetic Ingredients Combined With Bioactive Glass Ethanol 55 Cosmetically acceptable Glycols — including, but not limited to the Na Laureth-2 Sulfate following: Sorbitan Isostearate Glycerin Glycerin Procetyl AWS Propylene Glycol Crodafos SG Butylene Glycol Glycerox 767 Hexylene Glycol Cocamide DEA 60 2-methyl propane diol Jojoba Oil Cosmetically acceptable Alcohols — including, but not limited to the Abil EM-90 following:

Ethanol Isopropanol The folloWing raW materials listed in Table 2 Were mixed 65 n-propanol With sol-gel-derived bioactive glass and produced stable lauryl alcohol compositions. US 7,250,174 B2 13 14

TABLE III-continued TABLE IV-continued

Anhydrous Cosmetic Ingredients Combined With Bioactive Glass Anhydrous and Hydrous Ingredients Which May Be Used in a TWo Compartment Dispensing System oleyl alcohol Cosmetically acceptable Esters — including, but not limited to the HeXylene Glycol following: 2-methyl propane diol Cosmetically acceptable Alcohols — including, but not limited to the Isopropyl Myristate folloWing: Isopropyl Palmitate Jojoba Oil Ethanol Glyceryl tri caprate/caprylate Isopropanol Propylene glycol di caprate/caprylate n-propanol Sorbitan Esters lauryl alcohol Diesters of diacids oleyl alcohol Cosmetically acceptable Ethoxylated Materials — including, but not Cosmetically acceptable Esters — including, but not limited to the limited to the folloWing: folloWing: Ethoxylated Fatty Alcohols Isopropyl Myristate Ethoxylated Fatty Acids Isopropyl Palmitate Ethoxylated Sorbitan Esters Jojoba Oil Ethoxylated Glycerides Glyceryl tri caprate/caprylate Cosmetically acceptable PropoXylated Materials — including, but not Propylene glycol di caprate/caprylate 20 limited to the folloWing: Sorbitan Esters Diesters of diacids PropoXylated Fatty Alcohols Cosmetically acceptable Ethoxylated Materials — including, but not PropoXylated Fatty Acids limited to the folloWing: Esters of PropoXylated Fatty Alcohols Ethoxylated PropoXylates Ethoxylated Fatty Alcohols Cosmetically acceptable anhydrous ionic surfactants — including, but 25 Ethoxylated Fatty Acids not limited to the folloWing: Ethoxylated Sorbitan Esters Ethoxylated Glycerides Phosphate esters Cosmetically acceptable PropoXylated Materials — including, but not Sulfaters limited to the folloWing: Carboxylates Fatty amine salts 30 PropoXylated Fatty Alcohols Quaternary nitrogen salts PropoXylated Fatty Acids Cosmetically acceptable mineral, vegetable and animal derived oils and Esters of PropoXylated Fatty Alcohols fats. Cosmetically acceptable silicones including, but not limited to the Ethoxylated PropoXylates folloWing: Cosmetically acceptable anhydrous ionic surfactants — including, but not limited to the folloWing: Dimethicone 35 Simethicone Phosphate esters Cyclomethicone Sulfaters Dimethicone ethoXylates and propoXylates CarboXylates Cosmetically acceptable ?uorocarbons and derivatives — including, but Fatty amine salts not limited to the folloWing: Quaternary nitrogen salts Cosmetically acceptable mineral, vegetable and animal derived oils and Zonyls 40 fats. Cosmetically acceptable silicones including, but not limited to the Fluorcarbon alcohols folloWing: Cosmetically acceptable aerosol propellants — including, but not limited to the folloWing: Dimethicone Simethicone Propane Cyclomethicone Butane 45 Dimethicone ethoXylates and propoXylates Pentane Cosmetically acceptable ?uorocarbons and derivatives — including, but Isobutane not limited to the folloWing: HFC, CFC, HCFC Zonyls Fluorcarbon alcohols Bioactive glass, including sol-gel derived bioactive glass 50 Cosmetically acceptable amides — including, but not limited to the may be combined With anyhydrous and hydrous cosmetic folloWing: ingredients to created stable, non-irritating cosmetic formu Fatty acid diethanolamides lations. Anhydrous and hydrous cosmetic ingredients may Fatty acid monoethanolamides be used in a two-compartment dispensing system. A list of Fatty acid dimethylamnopropylamides exemplary anhydrous and hydrous cosmetic ingredients is 55 Cosmetically acceptable Polymers — including, but not limited to the provided in Table IV. folloWing: Polyalkenes TABLE IV Polyoxethylenes PolyoXypropylenes Anhydrous and Hydrous Ingredients Which May Be Used in a TWo Polyamides Compartment Dispensing System Polyesters Polyurethanes Cosmetically acceptable Glycols — including, but not limited to the Cellulosics and derivatives folloWing: Polyacrylics Polymethacrylics Glycerin PolysiloXanes Propylene Glycol 65 Cosmetically acceptable copolymers Butylene Glycol Cosmetically acceptable cosmetic formulation bases — including, but US 7,250,174 B2 15 16 toning and exfoliating products and makeup removal prod TABLE IV-continued ucts; facial moisturizing, anti-wrinkle, eye treatment, hand lotion and body lotion products; foot care products; anti-itch Anhydrous and Hydrous Ingredients Which May Be Used in a Two products; anti-bacterial, antiseptic, antibiotic and ?rst aid Compartment Dispensing System products; bath and shower soap in bar, liquid and gel form not limited to the following: and bath salt products; shampoo and hair detangling prod ucts; hair mousse, hair gel and hair spray products; antiper Emulsifying Waxes Lubrajels spirant and deodorant products in powder, creme, roll-on, Zilgels aerosol and stick form; aftershave and shaving lotion prod Jojoba Glaze ucts; shaving products in creme, gel, powder and soap Absorption Bases forms; depilatory, epilatory and hair bleaching products in creme, wax and powder forms; toothpaste products; mouth Bioactive glass, including sol-gel derived bioactive glass wash and mouth rinse products; wig and toupee powder also may be combined with cosmetic ingredients which products; shoulder pads; freckle coating products, eye drop evaporate shortly after being applied to the skin. Such products; and contact lens treatment products. combinations may used to create stable, non-irritating cos Pigmentation Products metic formulations. A list of exemplary cosmetic ingredients The present invention includes novel formulations which which may evaporate after being applied to the skin is incorporate bioactive glass into various brands of pigmen provided in Table V. tation products, such as the products marketed under the 20 brand names , Banana Boat, , Fruit TABLE V of the Earth, Good Sense, Hawaiian Tropic, Kiss My Face, Evaporating Ingredients Neutrogena, and products produced by high-end and generic manufacturers. Cosmetically acceptable Alcohols — including, but not limited to the Generally, pigmentation products comprise the active following: 25 ingredient dehydroxyacetone (DHA). Ethanol Common formulations of pigmentation products com Isopropanol prise water, glycerin, dihydroxyacetone, octyl palmitate, n-propanol butylene glycol, cetyl alcohol, PPG-20 methyl glucose ether Cosmetically acceptable Esters — including, but not limited to the distearate, stearyl alcohol, acrylates/Cl0-30 alkyl acrylate following: 30 crosspolymer, aloe gel, cocoa butter, DEA-cetyl phosphate, Ethyl acetate dimethicone, disodium EDTA, DMDM hydantoin, eucalyp Butyl acetate tus oil, fragrance, glyceryl stearate, iodopropyl butylcarbam Cosmetically acceptable Ethoxylated Materials — including, but not ate, lanolin, magnesium aluminum silicate, PEG-100 stear limited to the following: ate, polysorbate 60, sodium metabisul?te, sorbic acid, 35 Ethoxydiglycol steareth-20, xanthan gum and various vitamin, mineral, fruit Cosmetically acceptable silicones — including, but not limited to the and plant extracts. following: Pigmentation products may also include one or more of Cyclomethicone the following: isoceteth-3 acetate, sorbitan isostearate, Dimethicone polyquatemium-37, glycereth-7 triacetate, dicaprylate/dica 40 Cosmetically acceptable ketones — including, but not limited to the prate, PPG-l trideceth-6, bisabolol, PEG-20 methyl glucose following: sesquistearate, caprylic/capric triglyceride, unasaponifables, Acetone benzyl alcohol, butylparaben, C12-15 alcohol benzoate, Methyl Ethyl Ketone caprylic/capric, triglyceride, caramel, carbamate/acrylate Cosmetically acceptable Aliphatic compounds — including, but not copolymer, carbomer, ceteareth-20, ceteth-lO, ceteth-2, limited to the following: 45 cetyl hydroxyethylcellulose, citric acid, diazolidinyl , n-alkanes dimethyl isosorbide, dipropylene glycol, disodium EDTA, branched alkanes emulsifying wax, ethoxydiglycol, ethylparaben, imidazo Permethyls lidinyl urea, isoceteth-20, isopropyl palmitate, melanin, Aerosol propellant gases methyl gluceth-20, methylparaben, octyl methoxycinamate, Cosmetically acceptable fluorocarbons, chloro ?uoro carbons, hyd_ro 50 ?uoro carbons and hydro chloro ?uoro carbons — including, but not panthenol, PEG-7 glyceryl cocoate, petrolatum, phenoxy limited to the following: ethanol, polydimethylsiloxane-PPG ether/IPDI copolymer, polysorbate 20, polysorbate 80, propylene glycol, propylpa Aerosol propellant gases raben, silicone, sodium PCA, sorbitol, steareth-2, stearic acid, tocopheryl acetate, triethanolaminel and witch hazel. 55 One aspect of the present invention will be more clearly The present invention provides for novel formulations of understood with reference to the following non-limiting pigmentation products by incorporating bioactive glass into examples of cosmetic and personal care products and for a combination of any of the above-listed ingredients. In mulations which are suitable for use with bioactive glass. addition, bioactive glass itself can act as a pigment. Also, bioactive glass can be doped with various metals, including Categories of Cosmetics and Personal Care Health Products 60 The present invention will produce novel formulations of but not limited to iron, cobalt, and/or manganese, to produce a desired pigmentation. a variety of cosmetic and personal care products including but not limited to: pigmentation and sun care products; Sun Care Products diaper, baby wipe and hand wipe, baby powder and body The present invention includes novel formulations which powder and diaper rash products; nursing pads (for bras); 65 incorporate bioactive glass into various brands of sun care makeup products; tampon, maxipad and pantiliner products; products, such as the products marketed under the brand acne prevention and treatment products; facial cleansing, names A-FIL, Alba Botanica, Aloe Vera 80, Ambrelle, Bain US 7,250,174 B2 17 18 de Soleil, Banana Boat, Biosun, Blue Lizard, Brite-Life, (palm oil), jojoba oil, menthyl anthranilate, methylparaben, Bull Frog, Coppertone, DuraScreen, Elta Block, Esoterica, mineral oil, octadecene/MA copolymer, , octyl Flents, Fruit of the Earth, Good Sense, Hawaiian Tropic, palmitate, octyldodecy neopentanoate, , paraf Jason, Kiss My Face, L.A. Tan, Lily of the Desert, Native ?n, petrolatum, phenethyl alcohol, phenylbenzimidazole Tan, Nature’s Gate, Neutrogena, No Ad, Off, Panama Jack, sulfonic acid, polyglyceryl-3 distearate, PPG-12/SMDI PreSun, Sea & Ski, Shade Sunblock, Sol Bar, Sunbrellas, copolymer, PPG-15 stearyl ether, proplyene glycol, propy Sun Splash, Ti-Screen, Water Babies, and products produced lparaben, PVP/hexadecene, SD alcohol 40, shea butter, by high-end and generic manufacturers. silica, sorbitan sesquioleate, sorbitol, stearic acid, stearox Pigmentation and sun care formulations comprising bio ytrimethylsilane, stearyl alcohol, titanium dioxide, tribehe active glass provide enhanced UV protection as compared to nin, tri?uoromethyl C1-4 and zinc oxide. formulations not comprising bioactive glass. While not The present invention provides for novel formulations of being bound by any speci?c theory, the high and irregular sun care products by incorporating bioactive glass into a surface area of particulate bioactive glass is thought to combination of any of the above-listed ingredients. contribute to this enhanced UV protection. In addition, the Examples 1-3 beloW provide exemplary embodiments of sun reactive glass surface provides a protective HCA layer to care formulations incorporating bioactive glass, including offer additional UV protection, Moreover, these formula sol-gel-derived bioactive glass. tions help to mitigate the effects of sun allergies by releasing soluble calcium. EXAMPLE 1 Bioactive glass begins to absorb UV light at Wavelengths beloW 380 nm, and 0% transmittance Was observed through Composition of Sunscreen Gel With Bioactive a polished, 5 mm glass blank for UV light With a Wavelength 20 Glass beloW 280 nm. Thus, bioactive glass should be an excellent sunblock for the UVB (270-320 nm) region, and a moder ately good sunblock for the UVA (320-400 nm) region of solar radiation. The sun-blocking, effectiveness of bioactive glass should 25 INGREDIENTS Wt % improve as a function of time, after it is applied to human Jojoba Glaze 82.5 skin. Bioactive glass is expected to react With human per Octyl Methoxycinnalnate 7.5 spiration to form a porous, mineralogical, HAp-rich precipi Benzophenone-3 5.0 tate at the glass surface. This porous, surface precipitate is Schott Glass Bioactive Glass (<4 11 ave. part. size) 5.0 expected to scatter solar radiation, thus improving the sun 30 blocking characteristics of the bioactive glass With reaction 100.0 time. Thus, bioactive glass is considered an active sunscreen ingredient that Would improve over time as perspiration from the skin Would activate the scattering characteristics EXAMPLE 2 that are associated With the HAp-rich surface precipitate. 35 The transmittance through a 5 mm thick, polished sample Composition of Sunscreen Gel With Sol-gel-derived of bioactive glass that Was reacted With tris-bulfered saline Bioactive Glass solution to form a surface precipitate of HAp Was tested. The transmittance through the pre-reacted bioactive glass Was found to be less than that through the un-reacted bioactive glass at any Wavelength from 280 to 600 nm. Thus, the HAp 40 layer formed by pre-reaction appears to scatter UV and INGREDIENTS Wt % visible light, and the bioactive glass should be more effective at blocking UV radiation once it begins to react With human Jojoba Glaze 82.5 Octyl Methoxycinnalnate 7.5 perspiration on the skin. Benzophenone-3 5.0 Generally, sun care products comprise the active ingre 45 Schott Glass sol-gel-derived bioactive glass 5.0 dient , titanium oxide, zinc oxide, oxybenzone, or . 100.0 Common formulations of sun care products comprise octyl methoxycinnamate, , , ben zalkonium chloride, Water, PVP/eicosene copolymer, dioctyl 50 phosphate, triethanolamine, cetyl alcohol, retinyl palmitate, EXAMPLE 3 oat extract, tocopherol acetate, panthenol, dimethicone, tri methylsiloxysilicate, bisabolo, disodium EDTA, sorbitan Composition of Sunscreen Gel isostearate, butylene glycol, phenoxyethanol, carbomer, xanthan gum and diasolidinyl urea. POI-111111215 CPD3-32, J, K, N, o, R, s 55 Sun care products may also include one or more of the folloWing: PVP/hexadecene, isopropyl myristate, 2-ethyl Sunscreen Base Formula hexyl salicylate, acrylates/C10-30 alkyl acrylate crosspoly mer, acrylates/octylacrylamide copolymer, aloe extract, alu minum stearate, avobenzone (parsol 1789), barium sulfate, 60 benzophenone-3, benzyl alcohol, butylcarbamate, C12-15 INGREDIENTS % alkyl benzoate, ceteareth-20, cetearyl alcohol, cetyl palmi tate, cyclomethicone, DEA-cetyl phosphate, DMDM hydan Jojoba Glaze 87.5 toin, edetate disodium, elastin, emulsifying Wax NF, ethyl Octyl Methoxycinnalnate 7.5 hexyl P-methoxycinnamate, ?uoroalkyldimethicone, Benzophenone 3 5.0 fragrance, glyceryl monostearate-450, glyceryl stearate SE, 65 100.0 hydrolyzed collagen, hydroxypropyl cellulose, imidazolidi nyl urea, iodopropynyl, isohexadecane, isopropyl palmitate US 7,250,174 B2 19 20 Formulas to be tested ethicone, sodium benZoate, sodium nonoxynol-9, sorbic CPD3-32 JISunscreen Base Formula (above), SPF~l5 acid, tetrasodium EDTA, tocopherol acetate and various CPD3-32 K:Jojoba Glaze, SPF~0 vitamin and plant extracts. CPD3-32 NISunscreen Base Formula+2% 45s, d50:l.6p. The present invention provides for novel formulations of baby and hand wipe products by incorporating bioactive CPD3-32 OISunscreen Base Formula+2% 58s, d50:0.77l p. glass into a combination of any of the above-listed ingredi CPD3-32 RISunscreen Base Formula+4% 45s, d50:l.6p. ents. CPD3-32 SISunscreen Base Formula+4% 58s, d50:0.77u Generally, baby powder and body powder products com Diaper, Baby Wipe and Handwipe, Baby Powder and Body prise talc and/or corn starch, Zinc oxide and fragrance. Powder Products, and Diaper Rash Products Common formulations of baby powder and body powder products comprise corn starch or talc, sodium bicarbonate, The present invention includes novel formulations which aloe vera gel, tricalcium phosphate and fragrance. incorporate bioactive glass into various brands of diaper, Baby powder and body powder products may also include baby wipe and hand wipe, baby powder and body powder one or more of the following: tricalcium phosphate, bento products such as the products marketed under the brand nite (natural clay), kaolin clay, polysaccharides, puri?ed rice names A&D, Aloe Vesta, Alpharma, Ammens, Aveeno, Baby bran ?our, silica, Zinc oxide, hydroxyquinoline, 8-hydrox Magic, Balmax, Borofax, Boudreaux’s, Brite-Life, Burt’s yquinoline sulfate, isostearic acid, PPG-20, methyl glucose Bees, Caldesene, Calmoseptine, Cashmere Bouquet, ether, magnesium carbonate, Zinc stearate, camphor, benZa Cetaphil, Chubbs, Clinipad, Comfort Bath, Cottonelle, Des lkonium chloride and various fruit, mineral, vitamin and itin, Diaparene, Diaper Doubler, Diaper Guard, Dr. Smith’s, 20 herbal extracts. Drypers, Flander’s, Fougera, Gerber, Gold Bond, Goodnites, The present invention provides for novel formulations of Good Sense, G&W, Huggies, Johnson & Johnson, Kid baby powder and body powder products by incorporating Fresh, Kleenex, Little Bottoms, Little Forest, Luvs, Mex bioactive glass into a combination of any of the above-listed sana, Nature Boy & Girl, Neutrogena, Nice ’N Clean, ingredients. Paladin, Pampers, Phisoderm, Playtex, Pull Ups, Pure ’N 25 Generally, diaper rash products comprise Zinc oxide and Gentle, Purell, Shower to Shower, Smiles, Suave, Sween, Tom’s of Maine, Tushies, Vaseline, Wash-Up, Weleda, Wet ?sh or cod liver oil. Ones, and products produced by high-end and generic Common formulations of diaper rash products comprise manufacturers. petrolatum, lanolin, cod liver oil, fragrance, mineral oil, microcrystalline wax and para?in. The anti-in?ammatory, antimicrobial, and hygroscopic 30 Diaper rash products may also include one or more of the properties of bioactive glass are particularly useful in dia following: balsam, benZoic acid, water, bismuth subnitrate, pers, baby powders, body powders, diaper rash products and borax, silicone, methylparaben, talc, trihydroxystearin, bis moist towelettes to reduce in?ammation, rash and odors. In abolol, polyparaben and imidaZolidinyl urea. addition, bioactive glass can reduce the acidity of urine and The present invention provides for novel formulations of is activated by the aqueous nature of urine. 35 diaper rash products by incorporating bioactive glass into a Generally, diaper products comprise synthetic or natural combination of any of the above-listed ingredients. absorbent materials which absorb moisture, synthetic mate The antimicrobial, anti-in?ammatory, and hygoscopic rials which prevent leakage, and fragrance and/or antibac properties of bioactive glass are particularly useful in diaper terial agents. rash products to reduce in?ammation, rash and odors. The present invention provides for novel formulations of 40 diaper products by incorporating bioactive glass into a Nursing Pads (for Bras) combination of any of the above-listed ingredients. In addi Bioactive glass may also be incorporated into various tion, bioactive glass may be used in so-called adult brand brands of nursing pad (for bras), including nursing pads diaper products. marketed under the brand names Curity, Health?ow, Gerber, Generally, baby wipe or hand wipe products comprise the 45 J ohnson’s, Even?o, Omron, and products produced by high active ingredient disodium cocoamphodiacetae, a protectant end and generic manufacturers. such as silicon oil, mineral oil, fatty acids, fatty alcohols or The antimicrobial and anti-in?ammatory effects of a plant oils, and a moisturizer such as aloe gel, propylene bioactive glass are particularly useful in nursing pads (bras) glycol and PEG-60. to reduce in?ammation, rash and odors. 50 Common formulations of baby and hand wipe products Makeup Products comprise water, propylene glycol, PEG-75 lanolin, cocoam The present invention includes novel formulations which phodiacetate, polysorbate 20, methylparaben, 2-bromo-2 incorporate bioactive glass into various brands of makeup nitropane-l,3-diol, propylparaben, aloe vera gel and fra products including mascara, eyeshadow, eyeliner and eye grance. 55 brow pencil, blush, concealer foundation, face powder, Baby and hand wipe products may also include one or lipstick, lip gloss, lip treatment, lipliner, nail polish and nail more of the following: cocamidopropyl PG-dimonium chlo polish remover products such as the products marketed ride phosphate, acrylates/Cl0-30 alkyl acrylate crosspoly under the brand names Almay, Alpha Hydrox, Aromathera mer, acetamidopropyl trimonium chloride, acrylates copoly paes, Bari, Black Radiance, Blistex, Bonnie Bell, Brite-Life, mer, alkyl polyglycoside, aminomethyl propanol, 60 Burt’s Bees, Caboodles, Carmex, Chap-et, Chapstick, Chat benZalkonium chloride, benZoic acid, Cl2-l5 alkyl ben term, Clinipad, Coty, Cover Girl, Curity, Cutex, Dermatone, Zoate, citric acid, diaZolidinyl urea, dimethicone, disodium Garden Botanika, Herpecin-L, Jane, Jason, Kid Care, EDTA, disodium phosphate, DMDH hydantoin, ethyl alco L’Oreal, Liquimat, Loud Music, M Professional, Max Fac hol, glycerin, isopropyl myristate, malic acid, nonoxynol 9, tor, Maybelline, Milani, Natural Ice, Neutrogena, NoxZema, oleth-20, phosphate, phospholipid CDM, phospholipid EFA, 65 Ocusoft, Oil of Olay, Orly, Peterson’s, Purpose, Revlon, polyaminopropyl biguanide, potassium laureth phosphate, Sally Hansen, Savex, Softlips, Stay Free, Tampax, United potassium sorbate, retinyl palmitate, SD alcohol 40, sim Colors of Benetton Cosmetics, Ultimates, Vaseline, Viractin, US 7,250,174 B2 21 22 Wet ‘n’ Wild, Woltra, Zilactin, and products produced by manganese violet, methyl polysiloxane, mica, mineral oil, high-end and generic manufacturers. octyldodecyl stearoyl stearate, paraf?n, parahydroxyben The anti-in?ammatory and antimicrobial effects of bio Zoate ester, polymethyl methacrylate, polyvinylidene active glass are particularly useful in makeup products to copolymer, propylene carbonate, quaternium-l5, saturated reduce bacteria and in?ammation. fatty acid glycerides, sodium dehydroacetate, soybean phos Generally, mascara products comprise talc, a Wax prod pholipid soybean lecithin, stearic acid, titanium dioxide, uct, a preservative and coloring agents. trilaurin, trioctanion, ultramarines, Zinc oxides, iron oxides, Common formulations of mascara products comprise ferric ferrocyanide, ferric ammonium ferrocyanide, carmine, Water, beesWax, cyclopentasilosane, glyceryl stearate, PPG polyglyceryl-3 diisostearate, hydrogenated coco-glycerides, 17 copolymer, camuba Wax, stearic acid, paraf?n, butylene ethylene/methacrylate copolymer, nylon-l2, pentahy glycol, EDTA, polyethylene, nylon-l2, polymethyl drosqualene, acrylates copolymer, polyglycery-4 isostearate, methacrylate, PVP copolymer, PVP silica, triethanolamine, laurylmethicone copolyol, per?uoropolymethyliospropeth synthetic Wax, hydrolyZed corn starch, panthenol, dimethi phosphate, butylparaben, phenoxyethanol and various col conol, isoceteth-20, hydroxyethyl cellulose, diaZolidyl urea, oring agents. methylparaben, simethicone, butylparaben, disodium octy The present invention provides for novel formulations of lacrylamide/acrylates/butyl aminoethyl methacrylate eyeshadoW products by incorporating bioactive glass into a copolymer, cocoamphodiacetate, tocopheryl acetate, isopro combination of any of the above-listed ingredients. pyl titanium triisostrearate, lecithin, triethylamine, 2-olea Generally, eyeliner and eyebroW pencil products comprise mido-l,3-octadecanediol and propylparaben. talc, mica, polyethylene, ?uorethylene, magnesium stearate Mascara products may also include one or more of the 20 and coloring agents. folloWing: mica, TEA-stearate, glyceryl stearate, tricontanyl Common formulations of eyeliner and eyebroW pencil PVP, silk poWder, diglycol/CHDM/lsophthalates/ sip products comprise cyclomethicone, synthetic beesWax, copolymer, PTFE, stearate, sorbitan laurate, polysorbate 20, arachidyl behenate, microcrystalline Wax, quatemium-l8 acacia, acrylates copolymer, alcohol denatured, aminom hectorite, mineral oil, propylene carbonate, methylparaben, ethyl propandiol, ammonium acrylates copolymer, ammo 25 propylparaben and BHT. nium hydroxide, ammonium lanolate, ascorbyl palmitate, Eyeliner and eyebroW pencil products may also include benZyl alcohol, BHA, butyl stearate, C9-ll isoparaf?n, one or more of the folloWing: PPG-2 myristyl ether propi candelilla Wax, carmine, cetyl alcohol, cetyl stearate, chro onate ceresin, castor oil, vegetable oil, lanolin, aluminum mium hydroxide green, citric acid, cyclomethicone, ethylpa poWder, bronZe poWder, copper poWder, Zinc oxide, alumi raben, fragrance, glycerin, glyceryl rosinate, hydgroplex 30 num poWder, ammonium hydroxide, ascorbic acid, ascorbyl Hhg Whn, hydrolyZed keratin, hydroxyethylcellulose, imi palmitate, benZyldimethylstearylammonium hectorite, dazolidinyl urea, iron oxides, kaolin, magnesium aluminum BHA, bismuth oxychloride, butyl stearate, butylene glycol, silicate, methyl ethyl propyl butylparabens/phenoxyethanol, butylparaben, candelilla Wax, caprylic/capric acid triglycer MlPA-lanolate, MlPA-oleate, nnoxynol-lO, oleic acid, oleyl ide, carmine, carnauba cetyl alcohol, carnauba Wax, ceresin, alcohol, PEG- 100 stearate, pentaerythrityl tetrastearate, phe 35 cerotic acid, cetyl alcohol, cetyl esters, cetyl palmitate, noxyethanol, polybutene, polyethylene, polyquatemium l0, chromium hydroxide green, chromium oxide greens, citric polyvinyl alcohol, potassium Ocotxynol- l 2, phosphate, pro acid, diaZolidinyl urea, dimethicone, ferric ammonium fer pylene carbonate, propylene glycol, propyl, quatemium-l5, rocyanide, ?sh glycerides, glycerin, hydrogenated castor oil, quaternium-l8, hectorite, quatemium-22, SD alcohol 40-B, hydrogenated coco-glycerides, hydrogenated cottonseed oil, silica, silk poWder, sodium dehydroacetate, sodium laureth 40 hydrogenated ?sh oil, hydrogenated palm glycerides, hydro sulfate, sodium lauryl sulfate, sodium polymethacrylate, genated vegetable oil, hydroxyethylcellulose, hydroxylated sorbitan sesquioleate, talc, titanium dioxide, triclosan, trim lanolin, ipphilic glyceryl monooleate, iron oxides, isopropyl ethylsiloxysilicate, trisodium EDTA, ultramarines and xan Cl2-l5-pareth-9 carboxylate, japan Wax, lipophilic glyceryl than gum. monostearate, manganese violet, mellisic acid, methyl pol The present invention provides for novel formulations of 45 ysiloxane, mica, myricyl alcohol, oleostearine, oZokerite, mascara products by incorporating bioactive glass into a para?in, parahydroxybenZoate ester, PEG-8, polyethylene, combination of any of the above-listed ingredients. polysorbate 60, PPG-l5, PPG-5 eteth-20, PVP laureth-4, Generally, eyeshadoW products comprise talc, mica, poly quatemium-l8 bentonite, saturated fatty acid glycerides, ethylene ?uorethylene, magnesium stearate and coloring silica, sorbitan stearate, soybean phospholipid soybean leci agents. 50 thin, stearic acid, stearyl heptanoate, styrene/acrylates Common formulations of eyeshadoW products comprise copolymerm, talc, talloW glyceride, titanium dioxide, toco cyclomethicone, talc, boron nitride, trimethylsiloxysilicate, pheryl acetate, tristearin, ultramarines, various mineral, vita polyethylene, synthetic Wax, microcrystalline Wax, Zinc min, Water, Zinc stearate and various vegetable and plant stearate, kaolin, dimethicone, retinyl palmitate, tocopheryl extracts. acetate, aloe extract, silk poWder, silica PTFE, dehydroace 55 The present invention provides for novel formulations of tic acid, methylparaben, propylparaben, ethylparaben and eyeliner and eyebroW pencil products by incorporating bio diaZolidinyl urea. active glass into a combination of any of the above-listed Eyeshadow products may also include one or more of the ingredients. folloWing: ascorbyl palmitate, beesWax, benZyldimethyl Generally, blush products comprise talc, a preservative, stearylammonium hectorite, BHT, bismuth oxychloride, 60 an emollient, and coloring agents. Cl2-Cl5 alkyl benZoate, calcium silicate, candelilla Wax, Common formulations of blush products comprise dime caprylic/capric acid tryglyceride, camauba Wax, chromium thicone, octyl palmitate, talc, nylon-l2, neopentyl glycol hydroxide green, chromium oxide greens iron oxides, citric diisooctanoate, tribehenin, isostearyl behenate, boron acid, coco caprylate caprate, D1 tocopherol, hydrogenated nitride, acrylates copolymer, tocopherol, retinyl palmitate, oil, hydroxylated lanolin, imidaZolidinyl urea, isopropyl 65 methoxypropylgluconamide, chitin extract, sodium hyalur triisostearoyl titanate, lauroyl lysine, lauryl lysine, lecithin, onate, hydrolyZed glucosaminoglycans, lecithin, candelilla lipophilic glyceryl monostearate, magnesium carbonate, Wax, soy amino acids, mimosa Wax, pentahydrosqualene, US 7,250,174 B2 23 24 sorbitan trioleate, Water, propylene glycol, silica, phenoxy philic glyceryl monostearate, magnesium aluminum silicate, ethanol, titanium butylparaben, isopropylparaben, isobu magnesium carbonate, magnesium sulfate, methicone, tylparaben, BHA, lauryl lysine and methyldihydroias methyl glucose sesquistearate, methyl polysiloxane, mica, monate. mineral oil, myristyl lactate, octamethyl cyclotetrasiloxane, Blush products may also include one or more of the octyl methoxycinamate, octyl palmitate, octyl salicylate, following: acetylated lanolin alcohol, allantoin, ascorbyl octyl stearate, octyldodecanol, octyldodecy neopentanoate, palmitate, barium sulfate, BHT, bismuth oxychloride, octyldodecyl stearoyl stearate, oZokerite, panthenol, pectin, butylparaben, Cl2-l 5, alkyl benZoate, calcium silicate, cam PEG-100 stearate, PEG-2 stearate, PEG-20 sorbitan bees phor, carbomer, carmine, cethyl acetate, clove oil, coco Wax, PEG-32, PEG-6, PEG-8, petrolatum, phenyl dimethi caprylate caprate, diaZolidinyl urea, ethylparaben, eucalyp cone, polyethylene, polyglyceryl-4 isostearate, polyglyc tus oil, ferric ammonium ferrocyanide, ferric ferrocyanidea, eryl-6, ricinoleate, polyisobutene, polysorbate 60, propylene fragrance, imidaZolidinyl urea, iron oxides, kaolin, manga glycol, PVP, quatemium-l8 hectorite, SD alcohol 40 b, silk nese violet, menthol, methylparaben, mica, midaZolidinyl poWder, sodium chloride, sodium dehydroacetate, sodium urea, mineral oil, oat ?our, octyldodecyl stearoyl stearate, hyaluronate, sodium lauroyl sarcosinate, sorbic acid, sorbi panthenol, polyethylene, polyoxymethylene urea, polysor tan sesquioleate, stearic acid, stearoxytrimethylsilane, bate 20, polysorbate 80, quaternium-l5, sodium dehydroac stearyl alcohol, stearyl stearoyl stearate, t-butyl hydro etate, tetrasodium edtapropylparaben, tin oxide, titanium quinone, tetrasodium EDTA, titanium dioxide, tocopheryl dioxide, triethanolamine, trimethylsiloxysilicate, trioctan linoleate, tricontanyl PVP, triethanolamine, trihydroxys ion, ultramarines, various coloring agents, various plant tearin, trimethylsiloxysilicate, trisodium EDTA, tristearin, extracts, Zinc stearate, hydrogenated coco-glycerides, octyl 20 ultramarine blue, va/vinyl butyl benZoate, xanthum gum and hydroxystearate, ultramarines and various coloring agents. various coloring agents. The present invention provides for novel formulations of The present invention provides for novel formulations of blush products by incorporating bioactive glass into a com concealer and foundation products by incorporating bioac bination of any of the above-listed ingredients. tive glass into a combination of any of the above-listed Generally, concealer and foundation products comprise 25 ingredients. isoeicosane, camauba, polyglyceryl-3 diisostearate, silica, Generally, face poWder products comprise talc, a preser titanium oxide and coloring agents. vative, calcium stearate, and coloring agents. Common formulations of concealer and foundation prod Common formulations of face poWder products comprise ucts comprise Water, butylene glycol, dimethicone, isos talc, mineral oil, Zinc stearate, kaolin, aluminum starch tearyl alcohol, synthetic Wax, cyclomethicone, PEG-20 30 octenylsuccinate, acrylates copolymer, silk poWder, silica, methyl glucose sesquistearate, sodium stearate, tribehenin, propylparaben, methylparaben, calcium silicate, imidaZo polymethyl methacrylate, , hydrolyzed veg lidinyl urea, iron dioxides and ultramarines. etable protein, silica, talc, microcrystalline Wax, dimethi Face poWder products may also include one or more of the cone copolyol, polyglyceryl-6-polyricinoleate, aluminum folloWing: acetylated lanolin alcohol, ascorbyl palmitate, stearate, boron nitride, dimethiconol, diisostearyl malate, 35 beesWax, BHT, bismuth oxychloride, camphor, caprylic/ casein, carrageenan, tocopheryl acetate, retinyl palmitate, capric triglyceride, carmine, clove oil, cyclomethicon, dex aloe extract, ascorbic acids, menthol, calcium chloride, trin, diaZolidinyl urea, dimethicone, ethylene/acrylic acid nylon-l2, per?uoropolymethylisopropyl ether, methylpara copolymer, ethylparaben, eucalyptus oil, fragrance, glyceryl ben, propylparaben and phenoxyethanol. rosinate, hydrogentated lecithin, isopropyl palmitate, lauroyl Concealer and foundation products may also include one 40 lysine, lecithin, magnesium stearate, magnesium sulfate, or more of the folloWing: paraf?n, pentaerythrityl tetrastear manganese violet, menthol, methicone, methyl-ethyl-pro ate, octyl hydroxystearate, ceteareth-20, setereth-2, DMDM pyl-ibutylparabens/phenoxyethanol, mica, nylon-l2, oat hydantoin, quatemium-l5, dextrin, calcium silicate, Zinc ?our, octyl palmitate, octyldodecanol stearoyl stearate, stearate, octyldodecyl myristate, tridecyl trimellitate, bis octyldodecyl myristate, panthenol, phenoxyethanol, phenyl digly-ceryl caprylate/caprate/isostearate/stea, glyceryl rosi 45 trimethicone, polysorbate 20, propylene glycol, quaternium nate, acetylated glycol stearate, acetylated lanolin, acety l5, quatemium- l 8 hectorite, retinyl palmitate, sodium dehy lated lanolin alcohol, acrylates copolymer, alcohol droacetate, sodium hydrogenated talloW glutamate, sorbitan denatured, alkyl octanoate, allantoin, aluminum hydroxide, sesquioleate, sorbitan trioleate, titanium dioxide, tocopheryl aluminum starch octenylsuccinate, aminoethylpropanol, acetate, triclosan, tridecyl trimellitate, various coloring arachidyl behenate, ascorbyl palmitate, barium sulfate, bees 50 agents, various plant extracts, Water, aloe extract and allon Wax, bentonite, benZoic acid, BHA, BHT, bisabolol, bisa toin. codyl, bismuth oxychloride, butylparaben, Cl2-l5 alcohols The present invention provides for novel formulations of octanoate, Cl2-l5 alkyl benZoate, calcium aluminum boro face poWder products by incorporating bioactive glass into silicate, candelilla Wax, caprylic/capric triglyceride, car a combination of any of the above-listed ingredients. nauba, castor oil, cellulose gum, cetearyl alcohol, cetearyl 55 Generally, lipstick and lip gloss products comprise castor octanoate, cethyl acetate, cetyl alcohol, cetyl dimethicone oil, caprylic/capric triglycerides, stearic acid, lanolin, poly copolyol, cocoyl sarcosine, diaZolidinyl urea, dicaprylate/ butene, mineral oil, kanolin, silica, BHT, and coloring dicaprate, dioctyl adipate, dipropylene glycol, disodium agents. EDTA, disopropyl dimer dilinoleate, ethylene brassylate, Common formulations of lipstick and lip gloss products ethylene/methacrylate copolymer, ethylene/vinyl acetate 60 comprise trictyldodecyl citrate, isotridecyl isononanoate, copolymer, fragrance, glycerin, glyceryl stearate, hexyl lau Cl0-20 cholesterol/lanosterol esters, synthetic beesWax, rate, hydrogenated coco-glycerides, hydrogenated poly para?in, cetyl alcohol, candelilla Wax, aloe extract, retinyl isobutane, imidaZolidinyl urea, iron oxides, isocetyl stearate, palmitate, tocopheryl acetate, ascorbyl palmitate, sodium isododecane, isooctahexacontane, isopropyl isostearate, iso hyaluronate, PEG-20 sorbitan beesWax, quatemium-l8 hec propyl palmitate, isopropyl titanium triisostearate, isostearyl 65 torite, benZoic acid, BHA, methylparaben, propylparaben, neopentanoate, isostearyl palmitate, kaolin, lanolin, lanolin titanium dioxide, mica, iron dioxides and various coloring alcohol, lanolin oil, laureth-7, lauroyl lysine, lecithin, lipo agents. US 7,250,174 B2 25 Lipstick and lip gloss products may also include one or more of the following: acetylated lanolin, acrylates copoly -continued mer, allantoin, ascorbyl palmitate, beeswax, bis-diglyceryl polyacyladipate-2, bismuth oxychloride, butylparaben, C10 INGREDIENTS Wt % A Wt % B Wt % C 30 cholesterol/lanosterol esters, carnauba, castor oil, cethyl Methyl Paraben 0.1 0.1 0.1 acetate, cetyl dimethicone copolyol, cetyl octanoate, citric Propyl Paraben 0.2 0.2 0.2 acid, cocoa butter, coconut oil, cyclomethicone, cyclopen Schott Glass 45s5 (<4 11 ave. part. size) 0.1 0.1 0.1 tasiloxane, cyclotetrasiloxane, diisopropyl, dimer dili Part C noleate, dimethicone, trissostearyl citrate, Dl-tocopherol, Talc USP 10.0 i i drometriZole, D-tocopherol, ethylcellulose, fragrance, glyc Bioglass 45s @ 1.6 p i 10.0 i eryl oleate, grapeseed oil, hexyl laurate, hydrogenated poly Bioglass 58s @ 0.77 p i i 10.0 isobutene, hydrogenated soy glyceride, hydrogenated veg 100.0 100.0 100.0 etable oil, hydrolyZed collagen, hydrolyZed glucosaminoglycans, isocetyl stearate, isododecane, isopro pyl myristate, isostearyl palmitate, lanolin, magnesium Observations: ascorbyl phosphate, menthol, methicone, methyl glucose 1) The Talc Formula did not set as well/quickly as either sesquistearate, microcrystalline wax, mineral oil, myristyl glass. lactate, neopentyl glycol dicoctanoate, octyl hydroxystear 2) The 58s glass formula set up somewhat faster and ate, octyl methoxycinnamate, octyl palmitate, octyldode appeared to make a smoother product as compared to the canol, oleyl alcohol, oxybenZone, oZokerite, padimate, PEG 20 45s glass formula. 20 sorbitan beeswax, pentaerythrityl tetrabehenate, 3) The Talc formula showed more feathering (bleeding) at 1 pentaerythrityl tetraisostearate, petrolatum, phytosterol/oc hr. tyldodecyl lauroyl glutamate, polybutene, polyethelene, Generally, lip treatment products comprise moisturizers, polyethylene, polyglyceryl-2 diisostearate, polyglyceryl-3 healants and protectants such as petrolatum jelly. 25 diisostearate, polyglyceryl-4 isostearate, polymethysilses Common formulations of lip treatment products comprise quioxane, PPG 51/smdi copolymer, propyl gallate, propy white petrolatum, ethylhexyl P-methoxycinnamate, camuba, lene glycol, PVP/hexadecene copolymer, sesame oil, shellac hydroxylated milk glycerides, nylon-12, paraf?n, tocopheryl wax, silica, sodium hyaluronate, sodium lactate, sodium PCA, sodium phosphate, sodium saccharin, sorbic acid, acetate, bisabolol, retinyl palmitate, panthenol, lecithin, stearic, soya stearol, Zinc sulfate, sodium saccaharin, various squalane, stearic acid, stearyl dimethicone, sucrose acetate 30 isobutyrate, T-butyl hydroquinone, tocopheryl acetate, tri natural and arti?cial ?avorings and various plant extracts. hydroxystearin, triisostearyl citrate, trilsostearin, trimethyl Lip treatment products may also include one or more of siloxysilicate, urea, various natural and arti?cial ?avorings, the following: 2-ethylhexyl salicylate, 2-octyldodecanol, allantoin, aloe extract, alum, arachadyl propionate, beeswax, various vitamin agents, water, wheat germ oil, caprylic/ benZoic acid, benZophenone-3, BHT, bisacodyl, borage seed capric triglyceride, ceresin, tri?uoromethyl C1-4 alkyl dime 35 thicone, arachidyl propionate, phenyl trimethicon and BHT. oil, camphor, carnuba wax, castor oil, cetyl alcohol, cetyl esters, cocoa butter, corn oil, dimethicone, dimethicone, The present invention provides for novel formulations of dipentaerythrityl hexacaprate/hexacaprylate, fragrance, lipstick and lipgloss products by incorporating bioactive hydrogenated castor oil, isopropyl lanolate, kukui nut oil, glass, into a combination of any of the above-listed ingre 40 lanolin, menthol, methylparaben, microcrystalline wax, dients. mineral oil, mixed wax, octadecene/ma copolymer, octyl Example 4 below provides an exemplary embodiments of methoxycinamate, octyl palmitate, oxybenZone , oZokerite, lipstick formulations incorporating bioactiv glass. padimate, para?in, petrolatum, phenol, polybutene, polyphenylmethylsiloxane 556, polythylene, propylparaben, EXAMPLE 4 45 puri?ed water, saccharin, salicylic acid, SD alcohol 36, stearyl alcohol, sun?ower seed oil, talc, tridecyl stearate, Lipstick with Bioglass tridecyl trimellitate, triisostearin esters, various coloring agents, wax paraf?n and white wax. Formulas CPD3-33 A, B, C The present invention provides for novel formulations of 50 lip treatment products by incorporating bioactive glass into a combination of any of the above-listed ingredients. Generally, lipliner products comprise a wax product, a preservative, mineral oil, stearic acid and coloring agents. INGREDIENTS wt % A wt % B wt % C Common formulations of lipliner products comprise cas Part A 55 tor oil, isopropyl palmitate, lanolin, beeswax, candelilla wax, meadowfoam seed oil, fragrance, sesame oil, poly Red 7 Ca Lake 3.0 3.0 3.0 Red 6 Ba Lake 1.0 1.0 1.0 butene, oZokerite, dioctyldodecyl ?uoroheptyl citrate, car Red 33 Al Lake 1.0 1.0 1.0 nuba wax, para?in, hydrogenated soy glyceride, propylene Castor Oil 15.0 15.0 15.0 glycol, stearic acid, sodium saccharin, propylparaben, pro Part B 60 pyl gallate and citric acid. Castor Oil 30.6 30.6 30.6 Lipliner products may also include one or more of the Carnauba Wax 2.0 2.0 2.0 following: aloe extract, BHA, bismuth oxychloride, bronZe Candellila Wax 7.0 7.0 7.0 powder, butylparaben, carmine, castor oil, ceresin, copper Ozokerite Wax 2.0 2.0 2.0 Microcrystalline Wax 3.0 3.0 3.0 powder, cyclomethicone, disostearyl dimer dilinoleate, Jojoba Oil 25.0 25.0 25.0 65 hydrated silica, hydrogenated castor oil, hydrogenated cot Vitamin E 15.0 15.0 15.0 tonseed oil, hydrogenated vegetable oil, iron oxides, man ganese violet methylparaben, mica, PEG-6 beeswax, poly US 7,250,174 B2 27 28 butene, quatemium-18 bentonite, retinyl palmitate, sodium EXAMPLE 5 saccharin, synthetic Wax, titanium dioxide, tocopheryl acetate, various coloring agents, various natural and arti?cial Composition of Anhydrous Nail-Strengthening Gel ?avorings, zinc oxide, asorbyl palmitate, saturated fatty acid I glycerides, caprylic/capric acid triglycerides, glyceryl tri palmitate, parahydroxybenzoate ester, soybean phospho lipid, soybean lecithin and lipophilic glyceryl monostearate. The present invention provides for novel formulations of INGREDIENTS Wt % lip liner products by incorporating bioactive glass into a Jojoba Glaze 80.0 combination of any of the above-listed ingredients. Schott Glass Bioactive Glass (<4 u ave. part. size) 20.0

Generally, nail polish products comprise nitrocellulose, a 100.0 lacquer dissolved in solvents such as acetone or ethyl alcohol and coloring agents. Common formulations of nail polish products comprise EXAMPLE 6 ethyl acetate, butyl acetate, isopropyl alcohol, nitrocellulose, glyceryl tribenzoate, acetyl tributyl citrate, stearalkonium Composition of Anhydrous Nail-Strengthening Gel bentonite, stearalkonium hectorite, glyceryl triacetate, cam II phor, SD alcohol 40, citric acid, malic acid, phosphoric acid, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 hydroxyben and tin 20 oxide. INGREDIENTS Wt % Nail polish products may also include one or more of the folloWing: acrylates copolymer, algae extract, aluminum, Jojoba Glaze 90.0 Schott Glass Bioactive Glass (<4 u ave. part. size) 10.0 amyul acetate, benzophenone-l, biotin, bismuth oxychlo 25 ride, chromium hydroxide green, chromium oxide greens, 100.0 diacetone alcohol, dibutyl phthalate, dimethicone copolyol, dipropylene glycol dibenzoate, ethyl tosylamide, etocrylene, ferric ammonium ferrocyanide, ferric ferrocyanide, ?ber EXAMPLE 7 glass, fragrance, glycois copolymer, guanine, hydrated 30 silica, iron oxides, isobutyl acetate, manganese violet, Composition of Nail Gel (Anhydrous With methyl acetate, mica, N-butyl alcohol, oxidized polyethyl Bioactive Glass) ene, panthenol, phthalic anhydride, phthalic anhydride/glyc erin/glycidyl decandate cop, phthalic anhydride/trimellitic anhydride/glycols copolymer, polyester resin, polyethylene 35 terephithlate, propyl acetate, retinyl palmitate, silica, silver, INGREDIENTS Wt % styrene/acrylates copolymer, sucrose acetate isobutyrate, Glycerin 90.50 styrene/acrylates/acrylonitrile copolymer, tetrabutyl phenyl Pemulen ® TR-2 0.45 Schott Glass Bioactive (<4 u ave. part. size) 9.05 hydroxybenzoate, titanium dioxide, tocopheryl acetate, 40 tosylamide/epoxy resin, tosylamide/formaldehyde resin, 100.00 tribenzoin, trimellitic anhydride, ultramarines, various col oring agents, stearalkonium hectorite, dimethicone copolyol, acrylate copolymer, dipropylene glycol diben EXAMPLE 8 zoate, tribenzoin, biotin, panthenol, retinyl palmitate, toco 45 pheryl acetate, aluminum poWder, bismuth oxychloride, Composition of Skin and Nail Treatment polyester resin, sucrose acetate isobutyrate, diacetone alco (Anhydrous With Sol-gel-derived Bioactive Glass) hol, benzophenone-l, guanine, toluene, tosylamide/formal dehyde resin, dibutyl phthalate, tetrabutyl phenyl hydroxy benzoate, titanium dioxide, iron dioxides, mica, ferric 50 ammonium ferrocyanide, calcium pantothenate, heptane, INGREDIENTS Wt % etocrylene, acetyl tributy citrate, hydrolyzed keratin and various coloring agents. Jojoba Glaze 91.5 Brown Iron Oxide 0.5 The present invention provides for novel formulations of Titanium Dioxide 0.5 nail polish products by incorporating bioactive glass into a 55 Talc - USP 2.5 combination of any of the above-listed ingredients. Schott Glass sol-gel-derived bioactive glass 5.0

Bioactive glass and sol-gel derived bioactive glass reacts 100.0 With aqueous ?uids to form a solution that is rich in inorganic elements, such as calcium, phosphorous, sodium and silicon. These inorganic elements can precipitate on 60 Generally, nail polish remover products comprise acetone nails to form a mineralogical layer (i.e., hydroxyapatite). or ethyl acetate. Common formulations of nail polish remover products This mineralogical layer is expected to add strength to comprise ethyl acetate, alcohol, Water, propylene carbonate, nails. dimethyl glutarate, dimethyl succinate, dimethyl adipate, Examples 5-8 beloW provide exemplary embodiments of 65 gelatin, glycerin, diglycerol, fragrance, isopropanol, propyl nail care formulations incorporating bioactive glass, includ acetate, benzophenone-l, castor oil and various coloring ing sol-gel-derived bioactive glass. agents. US 7,250,174 B2 29 30 Nail polish remover products may also include one or The antimicrobial and anti-in?ammatory properties of more of the following: acetone, citric acid, denatonium bioactive glass are particularly useful in acne prevention and benZoate, PEG-75 lanolin oil, mineral oil, panthenol and treatment products. Bioactive glass can be used in topical tocopheryl acetate. acne creams to reduce in?ammation, While also killing the Bioactive glass may be incorporated into a combination of bacteria and micro-organisms that cause acne. any of the above-listed ingredients. Facial Cleansing, Toning, Exfoliating and Makeup Removal Tampon, Maxipad and Pantiliner Products Products The present invention includes novel formulations Which The present invention includes novel formulations Which incorporate bioactive glass into various brands of tampon, incorporate bioactive glass into various brands of facial maxipad and pantiliner products such as the products mar cleansing, toning, exfoliating products and makeup removal keted under the brand names AlWays, Carefree, Kotex, o.b., products such as the products marketed under the brand Playtex, Tampax, and products produced by high-end and names Aapri, Albolene, Almay, Alpha Hydrox, Ambi, Aqua generic manufacturers. Glycolic, Aquanil Lotion, Ar‘tra, Aveeno, Basis, Biore, Generally, tampon products comprise cotton and/or rayon Bodycology, Bonnie Bell, Brite-Life, Bur‘ts’s Bees, overWrap and cotton cord. Camocare, Cetaphil, Clean & Clear, Clairol, Clearasil, Tampon products may also include one or more of the Clearly Natural, Cover Girl, Curad, Dickinson’s, DML, following: polyethylene/polyester cover, polysorbate-20, Earth Science, Freeman, Garden Botanika, lonax, Jason, fragrance, and a plastic or cardboard applicator. Jergens, Johnson & Johnson, Keri, Kiss My Face, La Bella, Generally, maxipad and pantiliner products comprise cel L’Oreal, Maybelline, Moisturel, Neutrogena, Nivea, lulose, plastic and adhesive strips. Maxipad and pantiliner NoxZema, Oil of Olay, Oxy, Phisoderm, Plenitude, Pond’s, products may also include a fragrance. Propa pH, Purpose, Reviva, Revlon, RoC, Sea BreeZe, The present invention provides for novel formulations of Seban, St. Ives SWiss Formula, Stiefel, Stridex, Suave, tampon, maxipad and pantiliner products by incorporating T-Zone, Ten-O-Six, Vegee Tonic, and products produced by bioactive glass into a combination of any of the above-listed 25 high-end and generic manufacturers. ingredients. Generally, facial cleansing, toning, or exfoliating products The antimicrobial and hygroscopic effects of bioactive or makeup removal products comprise camphor, Water, glass are particularly useful in tampon, maxipad, and pant menthol, stearic acid, calcium hydroxide, ammonium iliner products to reduce bacteria and odor. hydroxide and an exfoliant such as alpha or beta hydroxy Acne Prevention and Treatment Products 30 acid, retinoic acid, aZelaic acid or adapelene. The present invention includes novel formulations Which Common formulations of facial cleansing, toning, exfo incorporate bioactive glass into various brands of acne liating products and makeup removal products comprise prevention and treatment products such as the products Water, glycerin, sodium laureth sulfate, cocamidopropyl marketed under the brand names Acne Aid, Aconmel, betaine, tocopheryl acetate, panthenol, methyl lactate, cary Aveeno, Biore, Burt’s Bees, Clean & Clear, Clear Logix, 35 lates/steareth-20, methacrylate copolymer, xanthan gum, Clearasil, Desert Essence, Exact, Fostex, Garden Botanika, microcrystalline Wax, sodium magnesium, silicate, sodium Hyland’s Homeopathic, lonax, Jason, Johnson & Johnson, hydroxide, fragrance, DMDM hydantoin, iodopropynl butyl Kiss My Face, Liquimat, Neutrogena, NoxZema, Orange carbamate, various vitamin, mineral, fruit and vegetable Daily, Oxy, Pamoxyl, Pemox, Pond’s, ReZamid, Sal Ac, extracts and various coloring agents. Salicylic Acid, Sastid, Sebasorb, Stiefel, Stridex, Suave, 40 Facial cleansing, toning, and exfoliating products and Sulforcin, Sulfur Soap, Sulpho-Lac, T-Zone, Zirh, and prod makeup removal products may also include one or more of ucts produced by high-end and generic manufacturers. the folloWing: l-hexadecanol, iodopropyl butylcarbamate, Generally, acne prevention and treatment products com acrylate crosspolymer, acrylates/Cl0-30 alkyl, allantoin, prise the active ingredient benZoyl peroxide or salicylic acid. ammonium hydroxide, beesWax, benZophenone-4, benZyl Common formulations of acne prevention and treatment 45 alcohol, beta carotene, BHT, boric acid, butylene glycol, products comprise active ingredients consisting of a com butylparaben, camphor, caprylic/capric triglyceride, car bination of resorcinol, sulfur and alcohol or benZoyl perox bomer, ceresin, ceteareth-20, cetearyl alcohol, cetearyl ide. isononanoate, cetyl alcohol, cetyl hydroxyethylcellulose, Acne prevention and treatment products may also include cetyl octanoate, chlorhexidrine digluconate, chromium one or more of the folloWing inactive ingredients: alcohol, 50 hydroxide green, citric acid, cocamide mea, cocamidopropyl attapulgite, bentonite, butylparaben, carbomer, citric acid, phosphatidyl pg-dimonium chloride, cocamidopropylamine dioctyl sodium sulfosuccinate, disodium EDTA, edetate oxide, colloidal oatmeal, corn germ oil, dea-cetyl phosphate, disodium, EDTA, fragrance, glycerin, hydroxyethylcellu diaZolidinyl urea, dicaprylate/dicaprate, dimethicone, diso lose, hydroxypropyl methylcellulose, iron oxides, isopropyl dium EDTA, disodium laureth sulfosuccinate, disodium myristate, kaolin, lauramide dea, methylparaben, parachlo 55 lauroamphodiacetate, disodium oleamido PEG-2 sulfosuc rometaxylenol, PEG-8 laurate, potassium hydroxide, propy cinate, disodium ricinoleamido mea-sulfosuccinate, edetate lene glycol, propylparaben, salicylic acid, simethicone, disodium, EDTA, ethoxydiglycol, ethylparaben, gelatin, sodium bisul?te, sodium borohydride, sodium chloride, glyceryl laurate, glyceryl polymethacrylate, glyceryl stear sodium cocoate, sodium hydroxide, sodium polynapthalene ate, glycol DS, hexylene glycol, hydroxycetyl hydroxyethyl sulfonate, sodium talloWate, talc, titanium dioxide, triso 60 dimonium chloride, hydroxypropyl guar hydroxypropyltri dium hedta, various plant and mineral extracts, Water, xan monium chloride, hydroxypropylcellulose, imidaZolidinyl than gum, Zinc oxide, aluminum hydroxide, glyceryl stearate urea, iron oxides, isocetyl alcohol, isopropyl myristate, SE and PEG-l2. isopropyl palmitate, lactic acid, lanolin oil, laureth-4, lau The present invention provides for novel formulations of reth-9, lauric acid, lauryl phosphate, lauryl polyglucose, acne prevention and treatment products by incorporating 65 magnesium aluminum silicate, menthol, methyl gluceth 20, bioactive glass into a combination of any of the above-listed methylchloroisothiaZolinone, methyldibromo glutaronitirle, ingredients. methylisothiaZolinone, methylparaben, mineral oil, myristic US 7,250,174 B2 31 32 acid, octyl hydroxystearate, olive oil, palmitic acid, paraf?n, Lift, Formula 405, Fougera, Freeman, Fruit of the Earth, PEG-10 hydrogenated castor oil, PEG-10 soya sterol, PEG Galderma, Garden Botanika, Gold Bond, Golden Sun, Good 100 stearate, PEG-120 glucose dioleate, PEG-120 methyl Sense, Health?oW, Hydrox-C, Jamieson & Co., J. C. Bril glucose dioleate, PEG-150 distearate, PEG-2 stearate, PEG lantine, Jason, Jean Nate, Jergens, Jockey Club, KC & 20, PEG-200 glyceryl talloWate, PEG-3 distearate, PEG-7 Company, Keri, Kerodex 51, Kiss My Face, La Bella, glyceryl cocoate, PEG-8, PEG-80 sorbitan laurate, PEG-9 Lac-Hydrin Five, LactiCare, Lady Esther, Lander, Lanolar, tridecyl ether, pentasodium penetate, petrolatum, PG-acetate Lantiseptic, Little Forest, Lubrex, Lubriderm, MG-217, phosphate, phenoxyethanol, phenylethyl alcohol, poloxamer Moisturel, Nate’ Naturals, Naturade, Naturalife, Nature’s 184, polydecene, polyol alkoxy esters, polyoxyethylene 15 Apothecary, Natures Family, Nature’s Gate, Neutrogena, cocoamine phosphate/oleate comp, polyquatemium-10, Nivea, Noxzema, Nutraderm, Nutra-E, Nutraderm, Nutra polyquatemium-24, polyquaternium-7 capryloyl salicylic plu, Oilatum Ad, Oil of Olay, Optimum Series, Orange acid, polysorbate 20, polysorbate 60, polysorbate 80, potas Daily, Pacquin, Palmer’s, Pen-Kera, Perfect Solutions, Petal sium hydroxide, potassium myristate, potassium palmitate, Fresh, Plenitude, Pond’s, Porcelana, Prax, Pretty Feet & potassium sorbate, potassium stearate, PPG-10 butanediol, Hands, Proteque, Purpose, Queen Helene, Revlon, Rex Eme, PPG-10 methyl glucose ether, PPG-12 buteth-16, PPG-15 RoC, Rose Milk, Sarah Michaels, Sama, Sea Breeze, SFC, stearyl ether, propylene glycol, propylparaben, quaternium Seba Nil, Shepard’s, Shikai, Simply Be Well, Soft Sense, 15, saf?oWer oil, salicylic acid, sesame oil, simethicone, State of Mind, St. Ives SWiss Formula, Stik, Stretch Mark, sodium borate, sodium C12-15 alcohol ethoxycarboxylate, Suave, Sudden Change, Sundance, SWeen, The Healing sodium chloride, sodium cocoate, sodium cocoyl glutamate, Garden, Theraplex, Triple Lanolin, University Medical, sodium cocoyl isethionate, sodium cocoyl isethionate, 20 U-Lactin, Ultra Mide 25, Vanicream, Vaseline, Vas Pet, Vital sodium dodecylbenzenesulfonate, sodium isethionate, Care, Vitec, Wibi, Wild Yam Complex, Woltra, Xpressions, sodium isostearoyl lactylate, sodium lactate, sodium lauro Yardley’s of London, Zim’s Crack Creme, and products amphoacetate, sodium lauroyl sarcosinate, sodium lauryl produced by high-end and generic manufacturers. sulfate, sodium lauryl sulfoacetate, sodium myristoyl sarco Bioactive glass is particularly useful in these products sinate, sodium palm kemelate, sodium PCA, sodium stear 25 since it possesses anti-in?ammatory and antimicrobial prop ate, sodium sul?te, sodium talloWate, sodium trideceth sul erties. The mild abrasive and high pH in certain formulations fate, sodium cocoyl isethionate, stearamidopropyl generate an exfoliant effect on the skin to remove Wrinkles. pg-dimonium chloride phosphate, steareth-2, steareth-21, In addition, these formulations Which incorporate bioactive stearic acid, stearyl alcohol, sucrose laurate, talc, tea-stear glass may be used to hide shadoWs created by Wrinkles. ate, tetrasodium EDTA, tetrasodium etibronate, titanium 30 Skin formulations comprising bioactive glass also provide dioxide, triclocarban, pentasodium pentetate, triclosan, tri a protective HCA layer on the corneal layer of the skin. In ethanolamine, trisodium hedta, tromethamine, sodium cetyl addition, the anti-in?ammatory action of bioactive glass sulfate, oleyl betaine, laureth-3, self-emulsifying Wax, coco reduces redness and irritation While the anti-microbial action amphocarboxyglycinate, lauramide DEA, lauramide MEA, disinfects. linoleamide DEA, polyethylene, lauryl methyl gluceth-10 35 Generally, facial moisturizing, anti-Wrinkle, and eye care dihydroxypropyldimonium chloride, sodium lauroamphodi products or hand and body lotion products comprise an acetate and decy glucoside. emollient, a preservative and collagen. The present invention provides for novel formulations of Common formulations of facial moisturizing, anti facial cleansing, toning, and exfoliating products and Wrinkle, and eye care products and hand and body lotion makeup removal products by incorporating bioactive glass 40 products comprise Water, glycerin, stearic acid, aloe gel, into a combination of any of the above-listed ingredients. glycol stearate, soya sterol, lecithin, dimethicone, glyceryl The anti-in?ammatory and antimicrobial effects of bio stearate, cetyl alcohol, magnesium aluminum silicate, fra active glass are particularly useful in facial cleansing, ton grance, carbomer, stearamide AMP, methylparaben, DMDM ing, and exfoliating products and makeup removal products hydantoin, iodopropynl, butycarbamate, disodium EDTA, to reduce bacteria and in?ammation. Additionally, the abra 45 butylene glycol, titanium dioxide, various mineral, fruit, sive quality of bioactive glass is useful in exfoliation. vegetable, and vitamin extracts and various coloring agents. Facial moisturizing, anti-Wrinkle, and eye care products Facial Moisturizing Anti-Wrinkle, Eye Treatment and Hand and hand and body lotion products may also include one or and Body Lotion Products more of the folloWing: 1-hexadecanol, acemannan hydrogel, The present invention includes novel formulations Which 50 acetylated lanolin alcohol, acrylates copolymer, acrylates/ incorporate bioactive glass into various brands of facial C10-30 alkyl acrylate crosspolymer, acrylates/carbamate moisturizing, anti-Wrinkle, anti-aging, eye treatment and copolymer, alantoin octyl dimenthyl paba, alcohol, allanto hand and body lotion products such as the products mar intetra EDTA, alpha lipoic acid, aluminum starch octenyl keted under the brand names Acid Mantle, A-Derma, Abra, succinate, ammonium glycolate, ammonium hydroxide, Alba Botanica, Albolene, Almay, Ala Derm, Allercreme, 55 ammonium lactate, apricot kernel oil, ascorbic acid polypep Aloe Vera 80, Alpha Hydrox, Alpha Keri, AmLactin, Aqua tide (vitamin c), ascorbyl palmitate, avobenzone, beesWax, Care, Aqua Glycolic, Aqua Lactin, Aquanil, Asorbase, Arthi benzophenone-4, benzyl alcohol, BHT, bisaboloi, blyceryl Care, Atrac-Tran, Aveeno, Avon, Baby Magic, Baker Cum stearate, boric acid, butyrolactone, C10-30 cholesterol/ mins, Balm Barr, Basis, Beauty Without Crvetty, Beta Care, lanosterol esters, C12-15 alkyl benzoate, C13-14isopara?'1n, Biore, Bodycology, Brite-Life, Burt’s Bees, Calgon, 60 calcium chloride, calcium hydroxide, calcium sulfate, cam Camocare Gold, Ca-Rezz, Carmol, Carrington, CB1, phor, caprylic acid, castor oil, ceramide 3, ceresin, ceteareth Cetaphil, Chamberlain, Clairol, Clean & Clear, Complex 15, 20, cetearyl alcohol, cetearyl octanoate, ceteth-24, cetrimo Coral Springs, Corn Huskers, Curel, Cutar, Cutemol, Der nium chloride, cetyl acetate, cetyl dimethicone, cetyl esters, mal Therapy, Dermacerin, Dermasil, Dermatone, Dermo cetyl octanoate, cetyl palmitate, cetyl ricinoleate, chloride, van, DiaDermal, DiabetiDerm, Dixie Health, DML, Doak, 65 chlorphenesin, cholecalciferol, cholesteryl isostearate, DPM, Earthly Elements, Earth Science, Earth Therapeutics, choleth-24, citric acid, coco caprylate caprate, cocoa butter, Elta, Epilyt, Esoterica, Estar, Eucerin, Evian, Exorex, Face cocobetaine, colloidal oatmeal, copolymer, cyclomethicone, US 7,250,174 B2 33 34 cyclopentasiloxane, dea-cetyl phosphate, dea-oleth-3 phos Examples 9 and 10 beloW provide exemplary embodi phate, derrnasterone (bioactive multi Wild yam species com ments of skin lotion/makeup base and cream foundation plex), diaZolidinyl urea, dicaprylate/dicaprate, dicaprylyl makeup formulations incorporating bioactive glass, includ ether, dicaprylyl maleate, diisopropyl sebacate, dioctanoate, ing sol-gel-derived bioactive glass. dioctyl succinate, dipropylene glycol, distearlydimonium 5 chloride, distearyldimonium, emulsi?ers, ethoxydiglycol, EXAMPLE 9 ethylene brassylate, ethylhexyl P-methoxycinnamate, glyc erin, eucalyptol, eucalyptus oil, fumaric acid, gelatin, glu Composition of Skin Lotion/makeup cose, glyceryl dilaurate, glycolic acid, glycoproteins, glysine, GMS/PEG 100 stearate, guar gum, hexyl laurate, Base With Sol-gel-derived Bioactive Glass hyaluronic acid, hydrogenated castor oil, hydrogenated lanolin, hydrogenated polyisobutane, hydrolyZed animal protein, hydroxyethylcellulose, imidaZolidinyl urea, isocetyl stearate, isodecyl oleate, isohexadecane, isopropyl isostear INGREDIENTS Wt % ate, isopropyl myristate, isopropyl palmitate, isostearic acid, isostearyl alcohol, isostearyl benZoate, isotearyl neopentan Mineral Oil (70ssu) 20.0 PolaWax ® 5.0 date, kaolin (natural clay), lactic acid, lanolin, diaZolidinyl Glycerin 2.0 urea, laureth-23, laureth-4, laureth-7, lauroyl lysine, linolea Deionized Water 65.4 midopropyl pg-dimonium chloride phosphate, linseed oil, Jaguar C-14S 0.5 magnesium ascorbyl phosphate, magnesium sulfate, malic Phenobact 1.0 Fragrance (High End Botanicals AFF #ACR2492019E) 0.1 acid, menthol, menthyl anthranilate, menthyl lactate, meth Citric Acid monohydrate powder 2.0 oxypropylgluconamide, methyl gluceth-20, methylcellu Schott Glass sol-gel-derived bioactive glass 4.0 lose, methylchloroisothiaZolinone, methylisothiaZol, meth 100.0 ylisothiaZolinone, mineral oil, mink oil, monoglyceride 25 citrate, myristyl lactate, myristyl myristate, neopentyl glycol dicaprylate/dicaprate, nylon-12, octyl hydroxystearate, octyl methoxycinamate, PEG-8 beeswax, phenylbenZimidaZole EXAMPLE 10 sulfonic acid, octyl methoxycinnamate, octyl palmitate, octyl salicylate, octyldodecanol, octyldodecyl myristate, 30 Cream Foundation Makeup With Bioglass octyldodecyl neopentanotate, oleyl sarcosin, oxybenZone, palm oil, palmitic acid, PEG 100 stearate, PEG-10 soya Formulas CPD3-34 A, B, C sterol, PEG-100 stearate, PEG-15 cocamine, PEG-4 dilau rate, PEG-40 stearate, PEG-5 glyceryl stearate, PEG-50 stearate, PEG-8 distearate, PEG-8 stearate, petrolatum, PG 35 dioctanoate, phenol, phenoxyethanol, phenylcarbinol, phe nyldimethicone, phospholipids, polyacrylamide, polyglyc INGREDIENTS Wt % A Wt % B Wt % C eryl-3 methyl glucose distearate, polyglyceryl-4 isostearate, polyglycerylmethacrylate, polyoxyl 40 stearate, polysorbate Part A 20, polysorbate 40, polysorbate 60, potassium hydroxide, 40 Crodafos CES 3.0 3.0 3.0 potassium sorbate, potassium stearate, progesterone USP, Volpo 10 0.8 0.8 0.8 Volpo 3 0.6 0.6 0.6 propylene glycol, PVM/MA decadiene crosspolymer, PVP/ Jojoba Oil 10.0 10.0 10.0 eicosene copolymer, PVP/hexadecene copolymer, pyridox Cyclomethicone D5 5.0 5.0 5.0 ine HCL (vitamin B6), quatemium-15, resorcinol, retinyl Part B palmitate, saccharide isomerate, salicylic acid, SD alcohol 45 Deionized Water 59.9 59.9 59.9 40-b, shea butter, silk amino acid, sodium benZoate, sodium NaOH 0.1 0.1 0.1 borate, sodium calcium alginate, sodium carbomer, sodium Volpo 10 0.1 0.1 0.1 chloride, sodium DNA, sodium hyaluronate, sodium isos TiO2 7.0 7.0 7.0 tearoyl lactylate, sodium lauryl sulfate, sodium PCA, YelloW Iron Oxide 0.8 0.8 0.8 Red Iron Oxide 0.3 0.3 0.3 sodium pyruvate, sodium stearate, sorbic acid, sorbitan 50 50/50 BlacldBroWn Iron Oxide Blend 0.1 0.1 0.1 laurate, sorbitan stearate, sorbitol, soybean oil, special pet Part C rolatum fraction, squalane, steapyrium chloride, stearamide dea, stearamidopropyl PG-dimonium chloride phosphate, Propylene Glycol 3.0 3.0 3.0 Jaguar 13S 0.3 0.3 0.3 steareth-2, steareth-21, stearoxytrimethylsilane, stearyl alco Part D hol, tea, tea-acrylates/c10-30 alkyl acrylate crosspolymer, 55 tea-carbomer 941, TEA-stearate, tetrasodium EDTA, trans Talc USP 8.0 i i vector-delivery system (lipo copolymer complex), tri citrate, Bioglass 45s @ 1.6 u i 8.0 i Bioglass 58s @ 0.77 p i 8.0 tricaprin, tridecyl stearate, tridecyl trimellitate, triethanola Part E mine, triisocetyl citrate, trilaurin, trisodium EDTA, trola mine, urea, Wool Wax, alcohol, collagen, elastin, propylpa 60 Germaben II 1.0 1.0 1.0 raben, PEG-40, sodium cetearyl sulfate, stearyl alcohol, quaterinium-22, sodium hydroxide and silica. 100.0 100.0 100.0 The present invention provides for novel formulations of facial moisturizing, anti-Wrinkle, and eye care products and Observations: Both 34 B and 34 C have more even hand and body lotion products by incorporating bioactive 65 application than 34 A (the talc formulation) and both feel glass into a combination of any of the above-listed ingredi much less oily than 34 A after drying. 34 C is less oily than ents. 34 B. US 7,250,174 B2 35 36 Foot Care Products nol-HC, Solarcaine, Sting Kill, Tecnu, Tegrin, Tinactin, The present invention includes novel formulations Which Unguentine, and products produced by high-end and generic incorporate bioactive glass into various brands of foot care manufacturers. products including products directed to treating athlete’s Generally, anti-itch products comprise the active ingredi foot, fungal conditions and odor, as Well as foot pumice ent benZocaine, novacaine or bacitracin. products such as the products marketed under the brand Common formulations of anti-itch products comprise names Absorbine Jr., A?ate, Aloe Vesta, Alpha Hydrox, BFI, active ingredients consisting of a combination of camphor, BaZa, Blis-to-Sol, Brite-Life, Carrington, Cruex, Desenex, benZocaine, pramoxine hydrochloride, Zinc acetate or Desert Essence, Dr. Scholl’s, Earth Therapeutics, Fougera, hydrocortisone. Freeman, Fungi Care, Fungiclear, FungiCure, Funginail, Anti-itch products may also include one or more of the Fungi Nail, Fungus Stop, Gold Bond, Health at Home, folloWing inactive ingredients: l-hexadecanol, 5-chloro-2 Johnson’s, LA Cross, Lamisil, Lotrimin, Mavis, Micatin, methyl-4-isothiaZolin-3-one (and) 2-met, acetic acid, adhe MiconaZole, Neutrogena, NP-27, Odor-Eaters, Orly, Out sives, alcohol, aloe vera, aluminum sulfate, ammonia, ben groW, Parex, Pinaud, Podiacin, Pretty Feet & Hands, Quin Zalkonium chloride, benZyl alcohol, bisabolol, butylene sana, St. Ives SWiss Formula, SWeen, Tetterine, Tinactin, glycol, calamine, calcium acetate, carbomer, ceresin, cet Ting, TingAF, Trim, Triple Care, Vaseline, Zeasorb, and eareth-20, cetearyl alcohol, ceteth-2, cetyl alcohol, cetyl products produced by high-end and generic manufacturers. palmitate, chlorothymol, citric acid, coal tar solution, dia Foot care formulations comprising bioactive glass are Zolidinyl urea, dimethicone, dioctyl sodium sulfosuccinate, anti-microbial and create a soothing effect. The anti-micro diphenhydramine HCl, disodium EDTA, distearlydimonium bial effect of bioactive glass includes antifugal properties 20 chloride, edetate disodium, ethoxydiglycol, fragrance, glyc making bioactive glass particularly Well-suited for foot care erin, glyceryl stearate SE, glyceryl tribehenate, hydroxypro products. In addition, the hygroscopic properties of bioac pyl methylcellulose, hydroxypropylcellulose, iodopropyl tive glass help to reduce foot moisture. Bioactive glass also butylcarbamate, isobutane (propellant), isopropanol, isopro can be used to create or be incorporated into a foot pumice. pyl alcohol, isopropyl myristate, isopropyl palmitate, isos For example, poWders may be sintered by any acceptable 25 tearyl neopentanoate, karaya, laneth-l6, lanolin, laureth-23, method to form a porous solid material for use in a foot lidocaine hydrochloride, maltodextrin, menthol, menthol, pumice. isopropyl alcohol, methyl gluceth-20, , Generally, foot care products comprise the active ingre methylparaben, mineral oil, oatmeal ?our, octoxynol-9, dient allylamine, aZole, griseofulvin, oxiconaZole or tolnaf olive oil, panthenol, PEG-2 oleate, petrolatum, polyethylene tate. 30 glycol, polysorbate 40, potassium hydroxide, potato dextrin, Common formulations of foot care products comprise PPG-l trideceth-6, propylene glycol, propylparaben, SD active ingredients consisting of a combination of tolnaftate, alcohol 38-b, SD alcohol 40, sodium acrylates copolymer, Zinc undecylenate, miconaZole, nitrate, corn starch, Zinc sodium borate, sodium cetearyl sulfate, sodium chloride, oxide, kaolin and benZethonium chloride. sodium citrate, sodium lauryl sulfate, steareth-2, steareth-2l, Foot care products may also include one or more of the 35 stearic acid, stearyl alcohol, styrene/acrylates copolymer, folloWing inactive ingredients: acetone, acrylate copolymer, sulfated castor oil, thymol, titanium dioxide, tocopheryl aldioxa, behenoxy dimethicone, calendula, carbohydrate acetate, triethanolamine, various coloring agents, Water, acrylic copolymer, ceteareth-6, chloroxylenol, diaZolidinyl White petrolatum, White Wax, Zinc oxide, Zinc pyrithione, urea, edetate disodium, fragrance, imidurea, iodine, isobu para?in, yelloW Wax, maltodextrin, and various fruit, veg tane, isopropyl myristate, menthol, microporous cellulose, 40 etable, mineral and vitamin extracts. monobasic sodium phosphate, stearamidoethyl diethy The present invention provides for novel formulations of lamine, myristyl myristate, polysorbate 60, polysorbate 80, anti-itch products by incorporating bioactive glass into a potassium iodide, quatemium, SD alcohol 40, sodium bicar combination of any of the above-listed ingredients. bonate, stearalkonium hectorite, stearamidoethyl diethy lamine, stearic acid, stearyl alcohol, talc, thymol, triglyceryl 45 Antibacterial, Antiseptic, Antibiotic and First Aid Products diisostearate, WormWood oil, xanthan gum, Water, salicylic The present invention includes novel formulations Which acid, methyl salicylate, bentonite, camphor, benZethonium incorporate bioactive glass into various brands of antibac chloride, terbina?ne hydrochloride, benZyl alcohol, cetyl terial, antiseptic, antibiotic and ?rst aid products such as the alcohol, cetyl palmitate, sodium hydroxide, sorbitan products marketed under the brand names Absorbine, B-D, monostearate, starch, magnesium stearate and various 50 Baciguent, Bactine, Bag Balm, Ben Gay, Betadine, Betasept, herbal, plant and mineral extracts. BFI, Blue Star, Boil Ease, Brite-Life, Campho-Phenique, The present invention provides for novel formulations of CarraklenZ, Clinipad, Clocream, Dermoplast, Dyna-hex, foot care products by incorporating bioactive glass into a Family Medic, Flex-All, Fougera, Glover’s, Gold Bond, combination of any of the above-listed ingredients. Good Sense, Hibiclens, Hibistat, Humco, Iodex, Johnson & 55 Johnson, Lanabiotic, Lanacort, Lander, Lanocane, Lavocal, Anti-itch Products Medi-Quik, Mentholatum, Mineral Ice, Myciguent, Myci The present invention includes novel formulations Which tracin, Neosporin, Nexcare, Polysporin, Resinol, Sayman, incorporate bioactive glass into various brands of anti-itch Sensogard, Spectrocin, Sportscreme, Stopain, SWan, Top products such as the products marketed under the brand Care, Unguentine, V1cks, Zephiran Chloride, and products names A&D Ointment, After Bite, Americaine, Aquaphor, 60 produced by high-end and generic manufacturers. Arctic Spray, Aveeno, Baciguent, Bactine, Benadryl, Beta Generally, antibacterial, antiseptic, antibiotic and ?rst aid dine, Blue Star, Boil Ease, Caladryl, Caldecort, Campho products comprise alcohol, hydrogen peroxide, povo-iodine, Phenique, Chiggerex, Cortaid, CortiZone, Dermarest, Der phenol or resorcinol. moplast, Exorex, Foille, Gold Bond, Good Sense, Humco, Common formulations of antibacterial, antiseptic, antibi Itch-X, Ivarest, Ivy Block, Ivy-Dry, KeriCort-lO, Lanabi 65 otic, and ?rst aid products comprise active ingredients otic, Lanacane, Lanacort, Lotrimin, Medi-Quik, Micatin, consisting of a combination of polymyxin B sulfate, baci Mycitracin, Neosporin, Nupercainal, Polysporin, Rhuli, Sar tracin Zinc, neomycin and pramoxine hydrochloride.