US008551508B2

(12) United States Patent (10) Patent No.: US 8,551,508 B2 Lee et al. (45) Date of Patent: Oct. 8, 2013

(54) COSMETIC, PERSONAL CARE, CLEANING 6,224,888 B1 5/2001 Vatter et al. AGENT, AND NUTRITIONAL SUPPLEMENT 4. R ck $398, ity, al...... 433/217.1 a O. ca. COMPOSITIONS AND METHODS OF 7.857.046 B2 12/2010 Lovell et al. MAKING AND USING SAME 2002/0114768 A1 8/2002 Stoor et al. 2004/0228905 A1 * 1 1/2004 Greenspan et al...... 424,445 (75) Inventors: Sean Lee, Karlsruhe (DE); Susanna Kessler, Ergolding (DE); Oliver FOREIGN PATENT DOCUMENTS Forberich, Oberursel (DE); Claire CN 1290.158 A 4/2001 Buchwar, Wiesbaden (DE); David C. JP 2001-516709 10, 2001 Greenspan, Gainesville, FL (US) JP 2001-52.5779 12/2001 WO 96.10985 4f1996 (73) Assignee: Schott AG, Mainz (DE) WO 97.27148 7/1997 WO 99.13852 3, 1999 (*) Notice: Subject to any disclaimer, the term of this WO 99.37287 7, 1999 WO WO9937287 * 7/1999 patent is extended or adjusted under 35 WO OOf 15167 3, 2000 U.S.C. 154(b) by 919 days. WO OO/42977 T 2000 WO 00,76486 12/2000 (21) Appl. No.: 11/775,615 WO 01.03650 1, 2001 WO O 1/72145 10, 2001 (22) Filed: Jul. 10, 2007 WO O 1/72262 10, 2001 OTHER PUBLICATIONS (65) Prior Publication Data US 2007/0275O21 A1 Nov. 29, 2007 Fechner, J., “Bioactive Glasses as a Potential New Class of Anti Oxidative Ingredients for Personal Care Products.” International Journal for Applied Science 131: Apr. 1-5, 2005. Related U.S. Application Data S. Lee et al., "Bioactive Glasses: A Potential New Class of Active Ingredients for Personal Care Products”. International Journal for (60) Division of application No. 09/818,466, filed on Mar. Applied Science 129: Sep. 1-7, 2003. 27, 2001, now Pat. No. 7,250,174, which is a Schott VitryXX(R) Bioactive Glass Material Data, pp. 1-2, Jun. 2010. continuation-in-part of application No. 09/456,196, Schott VitryXX(R) Bioactive Glass for Skin Care Product Information, filed on Dec. 7, 1999, now abandoned, and a pp. 1-2, Jun. 2010. continuation-in-part of application No. 09/456,195, Schott VitryXX(R) Bioactive Glass Summary of Tox Data-Highly biocompatible and skin-friendly, p. 1, Jun. 2010. filed on Dec. 7, 1999, now abandoned. Original and Translation of Chinese Office Action issued for Chinese Provisional application No. 60/192.216, filed on Mar. Application No. 200480024141.1, dated Jun. 10, 2011. (60) Larry L. Hench and Jon K. West, “Biological Applications of Bioac 27, 2000, provisional application No. 60/197,162, tive Glasses”. Life Chemistry Reports 13: 187-241, 1996. filed on Apr. 14, 2000. Kokubo, T. et al., Solutions able to reproduce in vivo Surface-struc ture changes in bioactive glass-ceramic A-W. J. Biomed Mater. Res. (51) Int. C. 24: 721-734, 1990. A6 IK 8/02 (2006.01) Nikko Chemicals Kabushi Kaisha, Nihon Surfactant Kogyo Kabushi (52) U.S. C. Kaisha and Toshoku Pigment Kabushiki Kaisha, “ Hand USPC ...... 424/401 book. pp. 657-658 (Nov. 1, 1996) and an English translation. (58) Field of Classification Search None * cited by examiner See application file for complete search history. Primary Examiner — Anand Desai Assistant Examiner — Melissa Mercier (56) References Cited (74) Attorney, Agent, or Firm — Pearl Cohen Zedek Latzer, U.S. PATENT DOCUMENTS LLP 4,103,002 A 7, 1978 Hench et al. (57) ABSTRACT 4,159,358 A 6, 1979 Hench et al. 4,171,544. A 10, 1979 Hench et al. The present invention involves new cosmetic, personal care, 4,189,325 A 2f1980 Barrett et al. cleaning agent, biocidal agent, functional food, and nutri 4,234,972 A 11, 1980 Hench et al. tional Supplement compositions. These new compositions 4,775,656 A 10, 1988 Harada et al. incorporate bioactive glass into cosmetics, personal care 4,814,165 A 3/1989 Berg et al. 5,074,916 A 12/1991 Hench et al. items, cleaning agents, biocidal agents, functional foods, and 5,204,106 A 4/1993 Schepers et al. nutritional Supplements. The present invention also involves 5,290,544 A 3, 1994 Shimono et al. methods of making and methods of using Such compositions. 5,766,611 A 6, 1998 Shimono et al. 5,834,008 A * 1 1/1998 Greenspan et al...... 424/443 12 Claims, No Drawings US 8,551,508 B2 1. 2 COSMETIC, PERSONAL CARE, CLEANING described by Larry L. Hench and Jon K. West in “Biological AGENT, AND NUTRITIONAL SUPPLEMENT Applications of Bioactive Glasses' Life Chemistry Reports, COMPOSITIONS AND METHODS OF 1996, Vol. 13, pp. 187-241, the contents of which are incor MAKING AND USING SAME porated herein by reference.

RELATED APPLICATIONS DETAILED DESCRIPTION OF THE INVENTION This application is a divisional of U.S. application Ser. No. Bioactive glass is a sodium-calcium-phospho-silicate 09/818,466, filed Mar. 27, 2001 which claims priority from glass. As used herein, the term “bioactive glass may refer to U.S. Provisional Application No. 60/192.216, filed Mar. 27, 10 particulate melt-derived and/or sol-gel derived bioactive 2000 and U.S. Provisional Application No. 60/197,162, filed glass. In addition, the term “bioactive glass' may be used to Apr. 14, 2000. This application is also a continuation-in-part refer to an aqueous extract of particulate melt-derived an/or of U.S. application Ser. No. 09/456,196, filed Dec. 7, 1999, sol-gel derived bioactive glass. and U.S. application Ser. No. 09/456,195, filed Dec. 7, 1999. The present invention utilizes bioactive glass preferably The disclosures of each of these applications are incorporated 15 between 40 and 96% by weight of silicon dioxide oxide herein by reference. (SiO), between about 0 and 35% by weight of sodium oxide (NaO), between about 4 and 46% by weight calcium oxide FIELD OF THE INVENTION (CaO), and between about 1 and 15% by weight phosphorus The present invention involves new cosmetic, personal oxide (POs). As referred herein, bioactive glasses are typi care, cleaning agent, biocidal agent, functional food, and cally silicon dioxide based compositions capable of forming nutritional Supplement compositions. These new composi hydroxycarbonate apatite (HCA). More preferably, the glass tions incorporate bioactive glass into cosmetics, cleaning includes between 40 and 60% by weight of silicon dioxide agents, personal care products, biocidal agents, functional oxide (SiO), between about 5-30% by weight of sodium foods and nutritional Supplements. The present invention also 25 oxide (NaO), between about 10 and 35% by weight calcium involves methods of making and methods of using Such com oxide (CaO), and between about 1 and 12% by weight phos positions. phorus oxide (POs). The oxides can be present as solid Solutions or mixed oxides, or as mixtures of oxides. BACKGROUND OF THE INVENTION CaF, B.O.s, Al-O, MgO and KO may be included in the 30 composition in addition to silicon, sodium, phosphorus and Preservatives are necessary and important ingredients that calcium oxides. The preferred range for BO is between 0 ensure the stability and safety of different products. Many and 10% by weight. The preferred range for KO is between problems exist with respect to known preservatives. Many 0 and 8% by weight. The preferred range for MgO is between have unwanted effects on the products they are in or on the 0 and 5% by weight. person or thing for which the products are used. Many are 35 Typically, bioactive glasses have the following composi relatively expensive and have no beneficial effects besides preservation. Many, in fact, are not efficacious as preserva tion by weight percentage: tives. Many have effects on the products texture or taste that make them undesirable. Better preservatives are needed. There has also been a great need for ingredients that can be 40 Component Wt. Percent used safely and beneficially in products that have antibacte SiO2 40-90 rial, antifungal, antiviral, ion releasing, anti-inflammatory CaO 4-45 and/or pH properties in the products themselves and/or on the NaO O-3S person or thing for which the product issued. Ingredients that POs 2-16 can express one or more of these properties are needed. 45 CaF2 O-2S B2O3 O-4 KO O-8 SUMMARY OF THE INVENTION MgO O-5 Applicants have found that bioactive glass when used in a wide variety of cosmetics provides exceptional qualities to 50 A more preferred composition by weight percentage for the cosmetic including a beneficial preservative effect. Appli bioactive glass is as follows: cants also have found that bioactive glass preserves a variety ofstandardhousehold and industrial cleaning agents. Further, certain bioactive glass compositions provide excellent clean Component Wt. Percent ing properties and greatly enhance the cleaning properties of 55 standard household and industrial cleaning agents. In addi SiO, 40-68 tion, applicants have found that certain bioactive glass com CaO S-30 positions are useful as a functional food and nutritional Na2O 1O-35 Supplement or used in Such. Moreover, certain bioactive glass POs 1-12 compositions act as an excellent preservative for food. 60 In addition, the compositions of this invention can be for The present invention includes formulations which may mulated as disclosed herein to have enhanced and beneficial comprise metal ions such as AgNO, CuO, and ZnO, or other properties that include antibacterial, antiviral, antifungal, ion antimicrobial salts, including but not limited to, silver, copper releasing, anti-inflammatory and pH effects. As used herein and Zinc ions. These metals may be in nitrate or acetate form. “bioactive glass” is an inorganic glass material having an 65 The preferred range for these salts is between 0 and 15% by oxide of silicon as its major component. The use of bioactive weight. The present invention also includes formulations glass for unrelated purposes such as orthopedic repair is which do not comprise metal ions. US 8,551,508 B2 3 4 The most preferred glass is Bioglass(RTM (a trademark of porosity of the glass is between about 0 and 85%, preferably University of Florida), which has a composition including between about 30 and 80%, and more preferably between about 45% by weight silicon dioxide, about 24.5% by weight about 40 and 60%. Porous bioactive glass can be prepared, for Sodium oxide, about 6% by weight phosphorus oxide, and example, by incorporating a leachable Substance into the about 24.5% by weight calcium oxide. Another preferred bioactive glass composition, and leaching the Substance out material is hydroxyapatite. Another preferred material for of the glass. Suitable leachable substances are well known to several applications are the porous sol-gel glasses. those of skill in the art, and include, for example, sodium Particulate, non-interlinked bioactive glass is preferred for chloride and other water-soluble salts. The particle size of the many embodiments of the present invention. That is, the glass leachable Substance is roughly the size of the resulting pore. is in the form of small, discrete particles, rather than a fused 10 The relative amount and size of the leachable substance gives matrix of particles or a mesh or fabric (woven or non-woven) rise to the degree of porosity. Also, as described herein, poros of glass fibers. Note that under some conditions the discrete ity can be achieved using sintering and/or by controlling the particles of the present invention may tend to cling together treatment cycle of glass gels to control the pores and inter because of electrostatic or other forces but are still considered pores of the material. to be non-interlinked. Preferably the particle size is less than 15 In addition, anti-microbial and anti-inflammatory compo about 90 microns; more preferably, less than about 20 sitions derived from aqueous extracts of bioactive glass can microns; even more preferably, less than about 5 microns, and be formed by placing bioactive glass in an aqueous solution, most preferably, less than about 2 microns, as measured by allowing the glass to dissolve over a suitable period of time, SEM or laser light scattering techniques, although different for example, a week or more, and filtering out the dissolved uses may advantageously use different particle sizes. glass particles. The solvent can also be evaporated to provide The preferred particle size range for the bioactive glass is a solid material with anti-microbial properties. These com site and use dependent. Particle sizes less than about 1000 positions can be used in situations where elimination, reduc microns and greater than about 2 microns can also be used. tion, or prevention of microbes, including but not limited to Particles of such a small size range generally provide for the bacteria, viruses, and fungi would be advantageous, for advantages of the present invention without eliciting undesir 25 example, in cosmetic formulations, cleaning agent formula able immune responses. tions, functional foods and as a preservative for foods. Without being bound to a particular theory, it is believed The glass composition can be prepared in several ways to that there is a complex relationship between the type of ion provide melt-derived glass, sol-gel derived glass and sintered being released from the glass, the amount of that ion, the rate glass particles. The sintered particles may be in sol-gel at which release occurs, the pH of the Surrounding environ 30 derived, unreacted, or pre-reacted melt-derived form. The ment, and the resulting anti-microbial or anti-inflammatory glass composition is preferably melt-derived. Melt derived response. This effect is observed with respect to the particles glass is generally prepared by mixing grains of oxides or of bioactive glass themselves and also in the aqueous solu carbonates, melting and homogenizing the mixtures at high tions derived from the glass particles. Accordingly, in the temperatures, typically between about 1250 and 1400°C. The compositions and uses described below, particulate and/or 35 molten glass can be flitted and milled to produce a small bioactive glass Solutions derived from the particles may be particulate material. used. In each preparation, it is preferred to use reagent grade Large particles of bioactive glass do not have appreciable glass, especially when the glass is used to prepare materials antimicrobial properties. However, small particles of bioac which ultimately may be administered topically. Bioactive tive glass and highly porous bioactive glass do have appre 40 glass particles may be prepared using the melt-derived and ciable antimicrobial properties. Bioactive glass has bacteri grinding process described previously in U.S. Pat. No. 5,204. cidal properties and is effective against, for example, Staph. 106, the disclosure of which is incorporated herein by refer aureus, Staph. epidermidis, and various streptococci. These ence. Where particular particle size ranges are desired, sifting bacteria may be found in and on the skin. These antimicrobial may be used to obtain Such particles. For optimum sterility, properties are enhanced in an aqueous environment. While 45 glass particles may be ultrasonically cleaned, packaged in not being bound by a specific mechanism of action, it is Syringes and sterilized with gamma radiation. believed that this action is a result, inter alia, of the greatly The particulate biologically active material used in the increased bioactivity of the small particulates, which leads to present invention may be prepared according to the methods an increased pH of the Surrounding environment. The com of the art such as taught in U.S. Pat. Nos. 4,159,358; 4,234, bined properties of being both broadly bactericidal while at 50 972; 4,103,002: 4,189,325; 134,171,544; 4,775,646; 4,857, the same time maintaining tissue biocompatibility make a 046 and 5,074,916. For example, the raw materials (e.g., variety of formulations comprising Small particles of bioac SiO, CaO, Na-O and POs) are mixed in a Nalgene(RTM tive glass resistant to microbial contamination and especially plastic container on a ball mill for four hours. The mix is then suitable for formulations which will contact the skin. melted in a platinum crucible at 1350° C. and homogenized The antimicrobial action increases with decreasing particle 55 for 24 hours. The molten glass is poured into distilled, deion size. The preferred particle size depends, in part, on the ized water to produce a glass frit. Alternatively, ribbons may expected microbial challenge and the desired purity of the be prepared by pouring the glass over moving rollers. The frit formulation comprising bioactive glass For example, formu or ribbons may be ground, for example, by one of several lations having bioactive glass particles averaging 20 microns means. In one method the frit or ribbons are ground in a ordinarily is Sufficient. However, for a longer lasting preser 60 mortar and pestle and passed through ASTM sieves to pro Vative effect or to maintain a higher degree of purity, particles duce the required particle size range. Alternatively, the frit or averaging less than five microns as measured by SEM or laser ribbons may be ground using a ball-milling or jet milling light scattering techniques may be used. When highly porous process. bioactive glass is used in place of or in addition to Small Bioactive glass may be derived using a drying step, which particles of bioactive glass, the pore size is between about 0 65 may include near-equilibrium drying. Near-equilibrium dry and 500 um, preferably between about 10 and 150 um, and ing in place of or in addition to drying under dry conditions more preferably, between about 50 and 100 um. The degree of provides for much larger average pore size in the final com US 8,551,508 B2 5 6 position at a given level of SiO. In addition near-equilibrium The sol-gel-derived bioactive glass readily reacts with drying results in a higher rate of resorption as compared to aqueous solutions because of the high SSA (i.e., there is a traditionally prepared sol-gel bioactive glass materials. For tremendous amount of Surface area where glass/solution example, in-vivo testing of one has shown that more than 50% reactions can take place). When immersed in an aqueous of sol-gel material made in this manner resorbed at eight Solution, the sol-gel-derived bioactive glass begins to react, weeks. Comparable prior 4555 melt derived bioactive releasing soluble silica, calcium and phosphate anions. Once glasses, do not resorb at all by eight weeks. Indeed, it has been the concentration of calcium and phosphate anions is Suggested that glasses including more than 55% silicon diox increased to the saturation limit for HAp, a mineralogical, ide are not bioactive. HAp-rich layer will form on the surfaces that comprise the As used herein, near-equilibrium drying is drying under the 10 sol-gel-derived bioactive glass, and Surrounding Surfaces (i.e., hard and soft human tissues). conditions near the two phase boundaries in the phase dia For example, a reaction mixture including tetraethoxysi gram at a temperature and pressure Sufficient to yield a bio lane (TEOS), triethylphosphate (TEP), and calcium nitrate active glass with large pore structure, i.e., a pore structure can be used to make sol-gel bioactive glasses. Alkoxides of Sufficient to yield a bioactive glass. For example, near-equi 15 calcium, titanium, Zirconium, magnesium, aluminum, iron librium drying may be drying under the conditions near the and potassium also can be used. Other appropriate ingredients line for water as illustrated in conventional phase diagrams will also be apparent to those of ordinary skill in the art. In (or other liquids Such as methanol, ethanol, acetone, liquid addition, aerogels may be used. When an aerogel is used, (CO, benzene and so on). By manipulating the sealing of the increased pressure is used instead of near-equilibrium drying designed drying chamber to adjust the extent of the drying to achieve larger pore size and greater resorbability. condition away from the equilibrium line and relative humid Sol-gel processing which uses a near-equilibrium drying ity (from environmental humidity to 98%), the duration of step yields larger pore size in the final product and permits near-equilibrium drying, and the temperature at which the development of HCA very rapidly for both high and low drying is conducted, one can drastically alter pore size of silicon dioxide content gels. Indeed, these compositions form resultant bioactive glass. For example, increasing the sealing 25 HCA more rapidly than other gels when exposed to SBF of the drying chamber during drying typically results in an (Simulated Body Fluid, Kokubo, T. et al., J. Biomed. Mater. increase in relative humidity and pore diameter. Near-equi Res., 24, 721-34, 1990) or physiological fluids. The near librium drying temperature can also be varied, for example, equilibrium drying technique also provides for more homo with water drying. When using liquids other than water, Such geneous gels which can be heated to higher temperatures as those referred to above, one may obtain a faster drying or 30 while retaining large pore diameter. This permits much better increase the pore size range of the gel to a large extent. control of the final product e.g. resorbability, homogeneity A sol-gel process is any process that includes the use of a and physical structure. For example, sol-gel compositions sol-gel in the preparation of bioactive glass. Sol-gel derived derived without using near-equilibrium drying techniques are glass is generally prepared by synthesizing an inorganic net not able to provide adequate resorbability at higher levels of work by mixing metal alkoxides in solution, followed by 35 silicon dioxide. In contrast, the near-equilibrium drying tech hydrolysis, gelation, and low temperature (around 200-900 nique provides gels having excellent resorbability even when C.) firing to produce a glass. Sol-gel derived glasses produced high amounts of silicon dioxide are included. Such sol-gel this way are known to have an initial high specific Surface area glasses are also more homogeneous than other Sol-gel glasses (SSA) compared with either melt-derived glass or porous and calcium is distributed uniformly. melt derived glass. The resulting material contains nanom 40 This drying technique can be used to prepare all types of eter-sized porosity and has a SSA ranging from 50-400 m/g. sol-gel bioactive glasses. For example, the technique can be The Sol-gel derived glass does not contain Sodium. Thus, used to prepare frit, ribbons, monoliths, powders, coatings, when this material comes into contact with an aqueous solu fibers, mats, weaves and composites. tion, the dissolution mechanisms are different from those Frit can be ground to very broad ranges of particle size Such associated with non-sol-gel-derived bioactive glass. 45 as from about 2 Lum up to 1 mm for any purpose. The monolith Typically, Sol-gel-derived bioactive glasses have the fol can be formed to complex shapes such as various implants. lowing composition by weight percentage: 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 applications, 50 drug delivery, treating tooth hypersensitivity as well as the Component Wt. Percent remineralization of tooth structure, burn healing and wound SiO2 49-90 healing. CaO 5-42 While not being bound to any particular theory, it is POs 1-12 believed that the near-equilibrium drying step reduces capil 55 lary force inside the pore structure of the gel which results in A more preferred composition for Sol-gel-derived bioac large pore size. Gels are networks of Small colloid particles. tive glasses comprises the following composition by weight The networks includes voids which become pores and pore percentage: channels in the final glass composition. It is believed that the moisture of the near-equilibrium drying step enhances the 60 reaction at the neck between two particles in the network and the strength of the neck and “backbone' of the gel structure Component Wt. Percent which reduces shrinkage of the drying structure and ulti mately results in gels with large pores. SiO, 49-72 CaO 5-35 On the other hand, due to the liquid tension, the pressure POs S-9 65 difference between the different size of pores and channels is: US 8,551,508 B2 7 8 where, Y is liquid tension, 0 is contact angle and ris the radius In one embodiment the cosmetic formulation comprises a of pores and pore channels. During drying, the pressure dif protic solvent. In another embodiment the cosmetic formula ference, AP, will pull the network tight enabling pore collapse tion contains bioactive glass which has components within and gel shrinkage as liquid evaporates. It is believed that the following ranges on a % weight basis: 40-60% SiO, near-equilibrium drying allows the liquid inside the pore 5 10-30% CaO; 10-35% NaO; 2-8% P.O; 0-25% CaF: structure to evaporate under the condition of near equilibrium 0-10% B.O.; 0-8% KO; and 0-5% MgO. at a range of temperatures. This keeps liquid vapor pressure Cosmetic formulations in accordance with the present inside the channels and pores at high heating conditions invention can be well preserved using bioactive glass, without which resists the shrinkage and collapse of the gel structure having to add skin-irritating cytotoxic and possibly allergen and results in large pore sizes. 10 producing chemical preservatives to the preparation. Further Bioactive glass, Sol-gel derived bioactive glass and/or more, an additional nurturing effect may beachieved through aqueous extracts of bioactive glass may be incorporated into the antimicrobial and inflammation-inhibiting effect of bio various cosmetic, cleaning agent, functional foods, nutri active glass. The anti-inflammatory effects of bioactive glass tional Supplements and other products as described below. make it particularly useful in skin care formulations by pro Cosmetics 15 moting reductions in irritation, itching, redness and rashes. General Inspecial cases it might be desirable to add the preservative The present invention provides novel cosmetics composi in accordance with the present invention to preparations tions comprising bioactive glass. While current manufactur which have been preserved using standard preservatives in ing processes generally control microbial contamination order to achieve Synergetic effects. when the products are in sealed containers, after unsealing the 20 Bioactive glass has the ability to react with aqueous solu package, bacteria, fungi and/or mold may contaminate the tions (i.e., human perspiration, humidity, body fluids) to elicit cosmetics. Often, various antibacterial agents are added to the biological effects such as anti-microbial/antibacterial behav cosmetics to minimize this process. These antibacterial ior, UV screening, anti-inflammatory behavior, mineralogical agents, however, often create negative effects such as skin film forming, and therapeutic release of inorganic ions. These irritation for the cosmetic user. 25 effects are considered advantageous for many cosmetic appli A goal of the present invention is to produce cosmetic cations, and several examples of cosmetic formulations that formulations which, in contrast to presently available cosmet can be used to include bioactive glass and/or sol-gel-derived ics, exhibit an ability to withstand microbial contamination bioactive glass within a cosmetic product are described without creating negative effects such as skin irritation. herein. In one embodiment of the present invention, bioactive 30 Bioactive glass forms a hydroxy carbonate layer (HCA) on glass may be included in cosmetic formulations to minimize protein-containing Surfaces such as hair, skin, nails and teeth. microbial contamination, including contamination by bacte This HCA layer can desensitize teeth, harden/thicken nails, ria, fungi and/or mold. The cosmetic compositions can protect skin and modify hair texture. include the aqueous extracts of bioactive glass and/or par Bioactive glass and/or sol-gel-derived bioactive glass may ticles of bioactive glass. 35 be effective at absorbing and scattering visible and UV light, In one embodiment the cosmetic formulation comprises making these materials attractive for soft focus and Sun particulate bioactive glass having an average particle size less Screening applications. than 10 microns. In another embodiment particulate bioactive In one embodiment cosmetic products comprise sol-gel glass having an average particle size less than 5 microns, and derived bioactive glass. The sol-gel-derived bioactive glass is preferably less than 2 microns is used. Preferred cosmetic 40 extremely porous, and thus effective at Scattering visible and preparations are especially creams, make-up compounds, lip UV light. The scatter of visible light is important for soft sticks, and salves since the micro-biocidal effect of focus cosmetic products, which are intended to scatter light bioactive glass is further enhanced by the moisture contained from the skin in Such a way that skin wrinkles become less in these preparations. However, bioactive glass can be added visible to the human eye. Further, the scatter of UV light is to virtually any cosmetic presently available to improve its 45 important for products. Thus, the sol-gel-derived resistance to contamination. Accordingly, the cosmetic may bioactive glass is effective at scattering UV light in the UVA be liquid based, or alternatively, other than liquid based. and UVB regions of the solar spectrum and provides a soft Cosmetic formulations may include, for example, creams, focusing effect. lotions, , make-up compounds and tinctures. Further, the sol-gel-derived bioactive glass reacts with In one embodiment the invention provides bioactive glass 50 aqueous solutions to form a solution that becomes concen for use as a preservative of perishable goods. The perishable trated in calcium, phosphate anions and soluble silica. When goods may be, for example, cosmetic and/or pharmaceutical this solution becomes Saturated, it can form a mineralogical, preparations. In another embodiment the present invention HAp-rich layer on the to Surrounding human tissue. Thus, the provides a preservative which itself contains bioactive glass. sol-gel-derived bioactive glass is expected to be effective in The preservative which contains bioactive glass may be 55 soft focus products because it is effective at scattering visible added to or included in cosmetic formulations. light, and the precipitation of the mineralogical layer could A cosmetic formulation in accordance with the present act as a skin-tightening agent that would further aid in hiding invention may contain an amount of bioactive glass up to 95% skin wrinkles. of the total weight of the cosmetic formulation, especially up It should also be noted that in addition to bioactive glass, to 70%, more especially up to 50%, or 40%, and even more 60 antibiotics may also be added to cosmetic formulations. The preferably up to 30% of the weight of the cosmetic formula addition of antibiotics to cosmetic products which include tion. Upper limits of 7% of the weight or 5% of the weight are bioactive glass is particularly useful in formulations which preferred for some formulations, whereby 3% of the weight is require topical application. especially preferred in some formulations. Lower limits are Methods of Making 0.01% of the weight, especially 0.1% of the weight, whereby 65 The present invention also provides a method of making 0.5% of the weight and 1% of the weight are especially cosmetic compositions comprising bioactive glass. An effec preferred as the lowest effective amounts. tive antimicrobial amount of the bioactive glass is added to or US 8,551,508 B2 10 included in a cosmetic formulation. An "effective, antimicro drous liquids. Thus, bioactive glass and/or sol-gel-derived bial amount of bioactive glass” refers to a sufficient amount of bioactive glass may be formulated in liquids, pastes, gels or bioactive glass having an appropriate particle size to effec creams that are anhydrous, but water-soluble (or water per tively prevent or control microbial contamination. The meable). In this instance, the bioactive glass remains un amount and particle size of bioactive glass to include in a reacted while immersed in the anhydrous liquid, paste, gel or cosmetic formulation will vary depending on the desired cream, but would be activated when applied to the human length and degree of purity as well as the anticipated micro body and allowed to react with perspiration, humidity, and/or bial challenge. An “effective antimicrobial amount of bioac other aqueous-containing bodily liquids. tive glass also may refer to a Sufficient amount of an aqueous extract of bioactive glass to effectively prevent or control 10 In one embodiment, bioactive glass and/or sol-gel-derived microbial contamination. An "effective antimicrobial bioactive glass for cosmetic products are used in a dispensing amount of bioactive glass may also refer to a combination of system containing two separate vessels (i.e., similar to the particulate bioactive glass and aqueous extract of bioactive dispensing system used for an epoxy). The bioactive glass glass to effectively prevent or control microbial contamina and/or sol-gel-derived bioactive glass may be could be for tion. 15 mulated in an anhydrous liquid, paste, cream or gel within one Bioactive glass may be added to or included in cosmetic vessel, while an aqueous liquid, past, cream or gel may be formulations using, for example, techniques or combinations contained within the second vessel. of techniques such as general mixing with slow medium, moderate, or even vigorous agitation. Sufficient agitation In another embodiment bioactive glass and/or sol-gel-de should be provided to achieve relative homogeneity. Prefer rived bioactive glass are mixed with an anhydrous liquid, ably, mixing and agitation will avoid excessive aeration and paste cream or gel that evaporated or is metabolized into the will have a low sheer rate. In addition, antifloculants may be skin after being applied to the body. The anhydrous liquid, used to keep the particles from clumping together. Other paste, cream or gel protects the bioactive glass while in the methods or combinations of methods of blending, dispersing, cosmetic package, yet disappears once applied to the body, mixing, combining and/or emulsifying may be utilized. Agi 25 thus allowing the bioactive glass to react with perspiration, tation may be achieved, for example, with Standard mixing humidity, and/or other aqueous-containing body liquids. devices. General mixing and blending may be achieved, for example, with an impeller. In yet another embodiment, the desirable characteristics It has been unexpectedly discovered that for many cos associated with bioactive glass and/or sol-gel-derived bioac metic base formulations, bioactive glass is easier to homoge 30 tive glass are achieved by utilizing an aqueous extract of neously mix than other common inorganic powders, such as derived from bioactive glass. The bioactive glass and/or sol and powder, for example. gel-derived bioactive glass may be reacted with an aqueous Bioactive glass may be added to or included in virtually any Solution until the solution became saturated with calcium, known cosmetic formulation. Applicants anticipate as well phosphate anions and soluble silica. This solution could then that bioactive glass will be suitable for inclusion in any as yet 35 be filtered, buffered to an appropriate pH, and then added to to be developed cosmetic formulation. In one embodiment cosmetic formulations to develop cosmetic products in accor the bioactive glass may be particulate. In another embodi dance with the present invention. In this embodiment, the ment the bioactive glass may be an aqueous solution derived formulation may contain aqueous cosmetic ingredients, since from particulate bioactive glass. In still another embodiment there would be no solid bioactive glass or sol-gel-derived the bioactive glass may be a combination of particulate bio 40 active glass and an aqueous solution derived from bioactive bioactive glass available for reaction. glass. In many cosmetic applications it is desired that the product Applicants have unexpectedly discovered that bioactive have pH value of between 5 and 8. Maintaining this pH level glass mixed with oil forms a cream. Likewise, bioactive glass with bioactive glass in an aqueous Suspension, however, is mixed with water unexpectedly forms a cream. The cream 45 difficult as the glass will continuously react in solution, resulting from mixing bioactive glass with either oil or water increasing the pH value. Applicants have discovered that as possesses a consistent homogenized texture particularly Suit little as 1% citric acid can effectively buffer bioactive glass able for cosmetic formulations. toward more neutral pH values over a long period in an Applicants have unexpectedly discovered that a combina aqueous suspension. This is to be contrasted with the effect of tion of bioactive glass with standard skin creams give the skin 50 adding a standard buffer, such as HCL-based buffers to the a pleasant-non-oily feeling and look when compared with the same Suspension, which do not maintain pH levels for Suit same cream applied without the added bioactive glass. With able periods of time. Thus, citric acid is one preferred method out being bound to any mechanism, it is believed that the of buffering aqueous based solutions with bioactive glass. bioactive glass has an affinity for oils as well as water and Bioactive glass is especially useful in an aqueous containing protenaceous matter, which is consistent with the unexpected 55 formulation when the formulation is appropriately buffered to effect observed by which bioactive glass and oil form a ensure that the pH remains near-neutral and when the bioac Smooth, homogeneous cream consistency. Thus bioactive tive glass is coated with a hydrophobic material that prevents glass is Suitable as an effective treatment for oily/fatty skin. Bioactive glass and Sol-gel derived bioactive glass exhibit the glass from reacting while in formulation. many desirable characteristics that would improve cosmetic 60 In another embodiment the bioactive glass and/or Sol-gel products. However, the difficulty lies in formulating the cos derived bioactive glass can be formulated into a dry form metic products in Such a way that the bioactive glass and/or incorporating other ingredients, for example colorants and sol-gel-derived bioactive glass remain unreacted (passive) fragrances, and packaged in Small packets or caches for single while packaged, and then become reactive (active) when use cosmetic products for skin, hair or nail applications, for applied onto the human body. 65 example. The dry form may be a powder. Bioactive glass and sol-gel-derived bioactive glass react The following raw materials listed in Table 1 were mixed with aqueous Solutions, but are inert when immersed in anhy with bioactive glass and produced stable compositions. US 8,551,508 B2 11 12 TABLE I TABLE II-continued

Raw Materials Combined with Bioactive Glass Raw Materials Combined with Sol-Gel-Derived Bioactive Glass Raw Material Raw Material

Incromectant AQ Crodafos SG Promyristyl PM-3 Glycerox 767 Dermo DPG-2B Cocamide DEA Transcutol CG Jojoba Oil Crodafos N3N Incromectant AQ Triethanolamine 10 Foamtaine CABG (45%) Promyristyl PM-3 Mineral Oil Abil EM-90 Incrodet TD7C Dermo DPG-2B Polyderm PPI SiWI Transutol CG PEG2 Oleamine Octyl Methoxycinnamate Crodafos CAP 15 Crodafos N3N Plantaren APB Triethanolamine Polyderm PPISIWS Menthyl Anthranilate Finsolv TN Mineral Oil Crodasinic O Incrodet TD7C Dermo B-246 Polyderm PPI SiWI GE 12O2 PEG2 Oleamine Crovol A-40 Crodafos CAP Crowo A-70 Plantaren APB GESF 96.350 cps Probutyl 14 Polyderm PPISIWS Foamtaine CABG Finsolv TN Dermol MS Crodasinic O PPG 10 Cetyl ether 25 Dermo B-246 PEG 7 Glyceryl Cocoate GE 12O2 d-Limonene Crovol A-40 Oleth-3 Crowo A-70 Stepancquat ML GE SF 96 (350 cps) Ammonium Lauryl Sulfate Probutyl 14 Incromectant LQ 30 Tergitol NP-9 Coco Hydroxy Sultaine Crodesta SL-40*** Bioactive glass, including sol-gel derived bioactive glass POE20 Sorbitan monooleate may be combined with anhydrous cosmetic ingredients to Propylene Glycol created Stable, non-irritating cosmetic formulations. A list of Ethanol 35 Na Laureth-2 Sulfate exemplary anhydrous ingredients is provided in Table III. Sorbitan Isostearate Glycerin TABLE III Procetyl AWS Crodafos SG Anhydrous Cosmetic Ingredients Combined with Bioactive Glass Glycerox 767 Cocamide DEA 40 Cosmetically acceptable Glycols - including, Jojoba Oil but not limited to the following: Abil EM-90 Glycerin Propylene Glycol The following raw materials listed in Table 2 were mixed Butylene Glycol 45 Hexylene Glycol with Sol-gel-derived bioactive glass and produced stable 2-methylpropane diol compositions. Cosmetically acceptable Alcohols - including, but not limited to the following: TABLE II Ethanol Raw Materials Combined with Sol-Gel-Derived Bioactive Glass 50 Sopropano Raw Material Dermol MS oleyl alcohol PPG 10 Cetyl ether Cosmetically acceptable Esters - including, PEG7 Glyceryl Cocoate but not limited to the following: d-Limonene 55 Oleth-3 sopropyl Myristate Stepancquat ML sopropyl Palmitate Ammonium Lauryl Sulfate ojoba Oil Incromectant LQ Glyceryl tri caprate caprylate Tergitol NP-9 Propylene glycol di caprate? caprylate Coco Hydroxy Sultaine Sorbitan Esters Crodesta SL-40 60 Diesters of diacids POE20 Sorbitan monooleate Cosmetically acceptable Ethoxylated Materials - including, Propylene Glycol but not limited to the following: Ethanol Na Laureth-2 Sulfate Ethoxylated y Alcohols Sorbitan Isostearate Ethoxylated Fa y Acids Glycerin 65 Ethoxylated Sor bitan Esters Procetyl AWS Ethoxylated Glycerides US 8,551,508 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 Cosmetically acceptable Propoxylated Materials - including, but not limited to the following: 5 Sorbitan Esters Diesters of diacids Propoxylated Fatty Alcohols Cosmetically acceptable Ethoxylated Materials - including, Propoxylated Fatty Acids but not limited to the following: Esters of Propoxylated Fatty Alcohols Ethoxylated Propoxylates hoxylated Fatty Alcohols Cosmetically acceptable anhydrous ionic Surfactants - including, 10 hoxylated Fatty Acids but not limited to the following: hoxylated Sorbitan Esters hoxylated Glycerides Phosphate esters osmetically acceptable Propoxylated Materials - including, Sulfaters bl not limited to the following: Carboxylates Fatty amine salts Propoxylated Fatty Alcohols Quaternary nitrogen salts 15 Propoxylated Fatty Acids Cosmetically acceptable mineral, vegetable and sters of Propoxylated Fatty Alcohols animal derived oils and fats. hoxylated Propoxylates Cosmetically acceptable silicones including, Cosmetically acceptable anhydrous ionic Surfactants - including, but not limited to the following: but not limited to the following: Dimethicone Phosphate esters Simethicone Sulfaters Cyclomethicone Carboxylates Dimethicone ethoxylates and propoxylates Fatty amine salts Cosmetically acceptable fluorocarbons and derivatives - including, Quaternary nitrogen salts but not limited to the following: Cosmetically acceptable mineral, vegetable 25 and animal derived oils and fats. Zonyls Cosmetically acceptable silicones including, Fluorcarbon alcohols but not limited to the following: Cosmetically acceptable aerosol propellants - including, but not limited to the following: Dimethicone Simethicone Propane 30 Cyclomethicone Butane Dimethicone ethoxylates and propoxylates Pentane Cosmetically acceptable fluorocarbons and derivatives - including, Sobutane but not limited to the following: HFC, CFC, HCFC Zonyls Fluorcarbon alcohols Bioactive glass, including sol-gel derived bioactive glass 35 Cosmetically acceptable amides - including, may be combined with anhydrous and hydrous cosmetic but not limited to the following: ingredients to created stable, non-irritating cosmetic formu 8. y acid diethanolamides lations. Anhydrous and hydrous cosmetic ingredients may be 8. y acid monoethanolamides used in a two-compartment dispensing system. A list of exem 8. y acid dimethylamnopropylamides plary anhydrous and hydrous cosmetic ingredients is pro 40 Cosmetically acceptable Polymers - including, vided in Table IV. but not limited to the following: Polyalkenes TABLE IV Polyoxethylenes Polyoxypropylenes Anhydrous and Hydrous Ingredients Which May Be Used in a 45 Polyamides Two-Compartment Dispensing System Polyesters Polyurethanes Cosmetically acceptable Glycols - including, Cellulosics and derivatives but not limited to the following: Polyacrylics Polymethacrylics Glycerin 50 Polysiloxanes Propylene Glycol Butylene Glycol Cosmetically acceptable copolymers Hexylene Glycol Cosmetically acceptable cosmetic formulation bases - including, 2-methylpropane diol but not limited to the following: Cosmetically acceptable Alcohols - including, Emulsifying Waxes but not limited to the following: 55 Lubrajels Ethanol Zilgels Sopropano oioba Glaze Absorption Bases

Cosmetically acceptable Esters - including, 60 Bioactive glass, including sol-gel derived bioactive glass but not limited to the following: also may be combined with cosmetic ingredients which sopropyl Myristate evaporate shortly after being applied to the skin. Such com sopropyl Palmitate ojoba Oil binations may used to create stable, non-irritating cosmetic Glyceryl tri caprate? caprylate 65 formulations. A list of exemplary cosmetic ingredients which Propylene glycol di caprate? caprylate may evaporate after being applied to the skin is provided in Table V. US 8,551,508 B2 15 16 TABLEV Earth, Good Sense, Hawaiian Tropic, Kiss My Face, Neutro gena, and products produced by high-end and generic manu Evaporating Ingredients facturers. Cosmetically acceptable Alcohols - including, Generally, pigmentation products comprise the active ingre but not limited to the following: dient dehydroxyacetone (DHA). Common formulations of pigmentation products comprise Ethanol water, glycerin, dihydroxyacetone, octyl palmitate, butylene Sopropano n-propanol glycol, cetyl alcohol, PPG-20 methylglucose ether distear Cosmetically acceptable Esters - including, ate, stearyl alcohol, acrylates/C10-30 alkyl acrylate cross but not limited to the following: 10 polymer, aloegel, cocoa butter, DEA-cetyl phosphate, dime Ethyl acetate thicone, disodium EDTA, DMDM hydantoin, eucalyptus oil, Butyl acetate fragrance, glyceryl Stearate, iodopropyl butylcarbamate, Cosmetically acceptable Ethoxylated Materials - including, lanolin, magnesium aluminum silicate, PEG-100 Stearate, but not limited to the following: polysorbate 60, sodium metabisulfite, sorbic acid, steareth Ethoxydiglycol 15 20, Xanthan gum and various vitamin, mineral, fruit and plant Cosmetically acceptable silicones - including, eXtractS. but not limited to the following: Pigmentation products may also include one or more of the Cyclomethicone following: isoceteth-3 acetate, Sorbitan isostearate, Dimethicone polyduaternium-37, glycereth-7 triacetate, dicaprylate/dica Cosmetically acceptable ketones - including, prate, PPG-1 trideceth-6, bisabolol, PEG-20 methylglucose but not limited to the following: sesquistearate, caprylic/capric triglyceride, unasaponifables, benzyl alcohol, butylparaben, C12-15 alcohol benzoate, Acetone Methyl Ethyl Ketone caprylic/capric, triglyceride, caramel, carbamate/acrylate Cosmetically acceptable Aliphatic compounds - including, copolymer, carbomer, ceteareth-20, ceteth-10, ceteth-2, cetyl but not limited to the following: 25 hydroxyethylcellulose, citric acid, diazolidinyl urea, dim ethyl isosorbide, dipropylene glycol, disodium EDTA, emul n-alkanes Sifying wax, ethoxydiglycol, ethylparaben, imidazolidinyl branched alkanes Permethyls urea, isoceteth-20, isopropyl palmitate, melanin, methylglu Aerosol propellant gases ceth-20, methylparaben, octyl methoxycinamate, panthenol, Cosmetically acceptable fluorocarbons, chlorofluoro carbons, 30 PEG-7 glyceryl cocoate, petrolatum, phenoxyethanol, poly hydrofluoro carbons and hydrochlorofluoro carbons - including, dimethylsiloxane-PPG ether/IPDI copolymer, polysorbate but not limited to the following: 20, polysorbate 80, propylene glycol, propylparaben, sili Aerosol propellant gases cone, sodium PCA, Sorbitol, Steareth-2, Stearic acid, toco pheryl acetate, triethanolaminel and witch hazel. 35 The present invention provides for novel formulations of One aspect of the present invention will be more clearly pigmentation products by incorporating bioactive glass into a understood with reference to the following non-limiting combination of any of the above-listed ingredients. In addi examples of cosmetic and personal care products and formu tion, bioactive glass itself can act as a pigment. Also, bioactive lations which are suitable for use with bioactive glass. glass can be doped with various metals, including but not Categories of Cosmetics and Personal Care Health Products 40 limited to iron, cobalt, and/or manganese, to produce a The present invention will produce novel formulations of a desired pigmentation. variety of cosmetic and personal care products including but Sun Care Products not limited to: pigmentation and Sun care products; diaper, The present invention includes novel formulations which baby wipe and hand wipe, baby powder and and incorporate bioactive glass into various brands of Sun care diaper rash products; nursing pads (for bras); makeup prod 45 products, such as the products marketed under the brand ucts; tampon, maxipad and pantiliner products; acne preven names A-FIL, Alba Botanica, Aloe Vera 80, Ambrelle, Bain tion and treatment products; cleansing, toning and de Soleil, Banana Boat, Biosun, Blue Lizard, Brite-Life, Bull exfoliating products and makeup removal products; facial Frog, . DuraScreen, Elta Block, Esoterica, Flents, moisturizing, anti-wrinkle, eye treatment, hand and Fruit of the Earth, Good Sense, Hawaiian Tropic, Jason, Kiss body lotion products; foot care products; anti-itch products; 50 My Face, L.A. Tan, Lily of the Desert, Native Tan, Nature's anti-bacterial, antiseptic, antibiotic and first aid products; Gate, , No Ad, Off, Panama Jack, PreSun, Sea & bath and shower Soap in bar, liquid and gel form and bath salt Ski, Shade Sunblock, Sol Bar, Sunbrellas, Sun Splash, Ti products; and hair detangling products; hair Screen, Water Babies, and products produced by high-end mousse, and products; antiperspirant and and generic manufacturers. deodorant products in powder, creme, roll-on, aerosol and 55 Pigmentation and Sun care formulations comprising bioac Stick form; aftershave and lotion products; shaving tive glass provide enhanced UV protection as compared to products in creme, gel, powder and Soap forms; depilatory, formulations not comprising bioactive glass. While not being epilatory and hair bleaching products in creme, wax and bound by any specific theory, the high and irregular surface powder forms; products; mouthwash and mouth area of particulate bioactive glass is thought to contribute to rinse products; wig and toupee powder products; shoulder 60 this enhanced UV protection. In addition, the reactive glass pads; freckle coating products, eye drop products; and contact surface provides a protective HCA layer to offer additional lens treatment products. UV protection, Moreover, these formulations help to mitigate Pigmentation Products the effects of Sun allergies by releasing soluble calcium. The present invention includes novel formulations which Bioactive glass begins to absorb UV light at wavelengths incorporate bioactive glass into various brands of pigmenta 65 below 380 nm, and 0% transmittance was observed through a tion products, such as the products marketed under the brand polished, 5 mm glass blank for UV light with a wavelength names Bain de Soleil, Banana Boat, Coppertone, Fruit of the below 280 nm. Thus, bioactive glass should be an excellent US 8,551,508 B2 17 18 sunblock for the UVB (270-320 nm) region, and a moderately Example 1 good sunblock for the UVA (320-400 nm) region of solar radiation. Composition of Sunscreen Gel with Bioactive Glass The sun-blocking, effectiveness of bioactive glass should improve as a function of time, after it is applied to human skin. Bioactive glass is expected to react with human perspiration to form a porous, mineralogical, HAp-rich precipitate at the glass Surface. This porous, Surface precipitate is expected to INGREDIENTS wt % scatter Solar radiation, thus improving the Sun-blocking char Jojoba Glaze 82.5 10 Octyl Methoxycinnamate 7.5 acteristics of the bioactive glass with reaction time. Thus, Benzophenone-3 S.O bioactive glass is considered an active Sunscreen ingredient Schott Glass Bioactive Glass (<4Lave. part. size) S.O that would improve over time as perspiration from the skin would activate the scattering characteristics that are associ ated with the HAp-rich surface precipitate. 15 The transmittance through a 5 mm thick, polished sample of bioactive glass that was reacted with tris-buffered saline Example 2 solution to form a surface precipitate of HAp was tested. The transmittance through the pre-reacted bioactive glass was Composition of Sunscreen Gel with Sol-Gel-Derived found to be less than that through the un-reacted bioactive Bioactive Glass glass at any wavelength from 280 to 600 nm. Thus, the HAp layer formed by pre-reaction appears to scatter UV and vis ible light, and the bioactive glass should be more effective at blocking UV radiation once it begins to react with human INGREDIENTS wt % perspiration on the skin. 25 Generally, Sun care products comprise the active ingredient Jojoba Glaze 82.5 Octyl Methoxycinnamate 7.5 , titanium oxide, Zinc oxide, , or Benzophenone-3 S.O . Schott Glass sol-gel-derived bioactive glass S.O Common formulations of Sun care products comprise octyl methoxycinnamate, , , benzalko 30 nium chloride, water, PVP/eicosenecopolymer, dioctylphos phate, triethanolamine, cetyl alcohol, retinyl palmitate, oat extract, tocopherol acetate, panthenol, dimethicone, trimeth Example 3 ylsiloxysilicate, bisabolo, disodium EDTA, sorbitan isostear ate, butylene glycol, phenoxyethanol, carbomer, Xanthan 35 Composition of Sunscreen Gel Formulas CPD3-32, gum and diasolidinyl urea. J, K, N, O, R, S Sun care products may also include one or more of the following: PVP/hexadecene, , 2-ethyl hexyl salicylate, acrylates/C10-30 alkyl acrylate crosspoly 40 mer, acrylates/octylacrylamide copolymer, aloe extract, alu Sunscreen Base Formula minum stearate, avobenzone (parsol 1789), barium sulfate, benzophenone-3, benzyl alcohol, butylcarbamate, C12-15 INGREDIENTS % alkyl benzoate, ceteareth-20, cetearyl alcohol, cetyl palmi Jojoba Glaze 87.5 tate, cyclomethicone, DEA-cetyl phosphate, DMDM hydan 45 Octyl Methoxycinnamate 7.5 toin, edetate disodium, elastin, emulsifying wax NF, ethyl Benzophenone 3 S.O hexyl P-methoxycinnamate, fluoroalkyldimethicone, fragrance, glyceryl monostearate-450, glyceryl Stearate SE, 1OOO hydrolyzed collagen, hydroxypropyl cellulose, imidazolidi nyl urea, iodopropynyl, isohexadecane, isopropyl palmitate 50 Formulas to be tested (palm oil), jojoba oil, menthyl anthranilate, methylparaben, CPD3-32 J=Sunscreen Base Formula (above), SPF-15 mineral oil, octadecene/MA copolymer, , octyl CPD3-32 K=Jojoba Glaze, SPF-0 palmitate, octyldodecy neopentanoate, oxybenzone, paraffin, CPD3-32 N=Sunscreen Base Formula+2% 45s, d50=11.6. petrolatum, phenethyl alcohol, phenylbenzimidazole Sul CPD3-32 O=Sunscreen Base Formula+2% 58s, d50–0.77u 55 CPD3-32 R=Sunscreen Base Formula+4% 45s, d50=11.6. fonic acid, polyglyceryl-3 distearate, PPG-12/SMDI copoly CPD3-32 S=Sunscreen Base Formula-i-4% 58s, d50–0.77u mer, PPG-15 stearyl ether, proplyene glycol, propylparaben, Diaper, Baby Wipe and Handwipe, Baby Powder and Body PVP/hexadecene, SD alcohol 40, shea butter, silica, Sorbitan Powder Products, and Diaper Rash Products sesquioleate, Sorbitol, Stearic acid, Stearoxytrimethylsilane, The present invention includes novel formulations which stearyl alcohol, titanium dioxide, tribehenin, trifluoromethyl 60 incorporate bioactive glass into various brands of diaper, C1-4 and Zinc oxide. baby wipe and hand wipe, baby powder and body powder The present invention provides for novel formulations of products such as the products marketed under the brand Sun care products by incorporating bioactive glass into a names A&D, Aloe Vesta, Alpharma, Ammens, Aveeno, Baby combination of any of the above-listed ingredients. Examples Magic, Balmax, Borofax, Boudreaux’s, Brite-Life, Burt's 1-3 below provide exemplary embodiments of sun care for 65 Bees, Caldesene, Calmoseptine, Cashmere Bouquet, mulations incorporating bioactive glass, including sol-gel Cetaphil, Chubbs, Clinipad, Comfort Bath, Cottonelle, Des derived bioactive glass. itin, Diaparene, Diaper Doubler, Diaper Guard, Dr. Smith's, US 8,551,508 B2 19 20 Drypers, Flander's, Fougera, Gerber, Gold Bond, Goodnites, Generally, diaper rash products comprise Zinc oxide and Good Sense, G&W. Huggies, Johnson & Johnson, Kid Fresh, fish or cod liver oil. Kleenex, Little Bottoms, Little Forest, Luvs, Mexsana, Common formulations of diaper rash products comprise Nature Boy & Girl, Neutrogena, Nice N Clean, Paladin, petrolatum, lanolin, cod liver oil, fragrance, mineral oil, Pampers, Phisoderm, Playtex, Pull Ups, Pure N Gentle, 5 microcrystalline wax and paraffin. Purell, Shower to Shower, Smiles, Suave, Sween, Tom's of Diaper rash products may also include one or more of the Maine, Tushies, , Wash-Up, Weleda, Wet Ones, and following: balsam, benzoic acid, water, bismuth Submitrate, products produced by high-end and generic manufacturers. borax, silicone, methylparaben, talc, trihydroxy Stearin, bis The anti-inflammatory, antimicrobial, and hygroscopic abolol, polyparaben and imidazolidinyl urea. properties of bioactive glass are particularly useful in diapers, 10 The present invention provides for novel formulations of baby powders, body powders, diaper rash products and moist diaper rash products by incorporating bioactive glass into a towelettes to reduce inflammation, rash and odors. In addi combination of any of the above-listed ingredients. tion, bioactive glass can reduce the acidity of urine and is The antimicrobial, anti-inflammatory, and hygoscopic activated by the aqueous nature of urine. properties of bioactive glass are particularly useful in diaper Generally, diaper products comprise synthetic or natural 15 rash products to reduce inflammation, rash and odors. absorbent materials which absorb moisture, synthetic mate Nursing Pads (for Bras) rials which prevent leakage, and fragrance and/or antibacte Bioactive glass may also be incorporated into various rial agents. brands of nursing pad (for bras), including nursing pads mar The present invention provides for novel formulations of keted under the brand names Curity, Healthflow, Gerber, diaper products by incorporating bioactive glass into a com Johnson's, Evenflo, Omron, and products produced by high bination of any of the above-listed ingredients. In addition, end and generic manufacturers. bioactive glass may be used in so-called adult brand diaper The antimicrobial and anti-inflammatory effects of a bio products. active glass are particularly useful in nursing pads (bras) to Generally, baby wipe or hand wipe products comprise the reduce inflammation, rash and odors. active ingredient disodium cocoamphodiacetae, a protectant 25 Makeup Products Such as silicon oil, mineral oil, fatty acids, fatty alcohols or The present invention includes novel formulations which plant oils, and a Such as aloegel, propylene glycol incorporate bioactive glass into various brands of makeup and PEG-60. products including mascara, eyeshadow, eyeliner and eye Common formulations of baby and hand wipe products brow pencil, blush, , , lip comprise water, propylene glycol, PEG-75 lanolin, cocoam 30 Stick, , lip treatment, lipliner, and nail phodiacetate, polysorbate 20, methylparaben, 2-bromo-2-ni polish remover products Such as the products marketed under tropane-1,3-diol, propylparaben, aloeveragel and fragrance. the brand names , Alpha Hydrox, Aromatherapaes, Baby and handwipe products may also include one or more Bari, Black Radiance, Blistex, Bonnie Bell, Brite-Life, Burt’s of the following: cocamidopropyl PG-dimonium chloride Bees, Caboodles, Carmex, Chap-et, ChapStick, Chatterm, phosphate, acrylates/C10-30 alkyl acrylate crosspolymer, 35 Clinipad, Coty, Cover Girl, Curity, , Dermatone, Gar acetamidopropyl trimonium chloride, acrylates copolymer, den Botanika, Herpecin-L, Jane, Jason, Kid Care, L'Oreal, alkyl polyglycoside, aminomethyl propanol, benzalkonium Liquimat, Loud Music, M Professional, , Maybel chloride, benzoic acid, C12-15 alkyl benzoate, citric acid, line, Milani, Natural Ice, Neutrogena, Noxzema, Ocusoft, Oil diazolidinyl urea, dimethicone, disodium EDTA, disodium of Olay, Orly, Petersons, Purpose, , Sally Hansen, phosphate, DMDH hydantoin, ethyl alcohol, glycerin, iso 40 Savex, Softlips, Stay Free, Tampax, United Colors of Benet propyl myristate, malic acid, nonoxynol 9, oleth-20, phos ton Cosmetics, Ultimates, Vaseline, Viractin, Wet 'n' Wild, phate, phospholipid CDM, phospholipid EFA, polyamino Woltra, Zilactin, and products produced by high-end and propyl biguanide, potassium laureth phosphate, potassium generic manufacturers. sorbate, retinyl palmitate, SD alcohol 40, simethicone, The anti-inflammatory and antimicrobial effects of bioac Sodium benzoate, sodium nonoxynol-9, Sorbic acid, tetraso 45 tive glass are particularly useful in makeup products to reduce dium EDTA, tocopherolacetate and various vitaminand plant bacteria and inflammation. eXtractS. Generally, mascara products comprise talc, a wax product, The present invention provides for novel formulations of a preservative and coloring agents. baby and handwipe products by incorporating bioactive glass Common formulations of mascara products comprise into a combination of any of the above-listed ingredients. 50 water, beeswax, cyclopentasilosane, glyceryl Stearate, PPG Generally, baby powder and body powder products com 17 copolymer, carnuba wax, Stearic acid, paraffin, butylene prise talc and/or corn starch, Zinc oxide and fragrance. glycol, EDTA, polyethylene, nylon-12, polymethyl Common formulations of baby powder and body powder methacrylate, PVP copolymer, PVP silica, triethanolamine, products comprise corn Starch or talc, Sodium bicarbonate, synthetic wax, hydrolyzed corn starch, panthenol, dimethi aloe Vera gel, tricalcium phosphate and fragrance. 55 conol, isoceteth-20, hydroxyethyl cellulose, diazolidyl urea, Baby powder and body powder products may also include methylparaben, simethicone, butylparaben, disodium octy one or more of the following: tricalcium phosphate, bentonite lacrylamide/acrylates/butyl aminoethyl methacrylate (natural clay), kaolin clay, polysaccharides, purified rice bran copolymer, cocoamphodiacetate, tocopheryl acetate, isopro flour, silica, Zinc oxide, hydroxyquinoline, 8-hydroxyquino pyl titanium triisostrearate, lecithin, triethylamine, 2-olea line sulfate, isostearic acid, PPG-20, methyl glucose ether, 60 mido-1,3-octadecanediol and propylparaben. magnesium carbonate, Zinc Stearate, camphor, benzalkonium Mascara products may also include one or more of the chloride and various fruit, mineral, vitamin and herbal following: mica, TEA-stearate, glyceryl Stearate, tricontanyl eXtractS. PVP, silk powder, diglycol/CHDM/lsophthalates/sip copoly The present invention provides for novel formulations of mer, PTFE, stearate, sorbitan laurate, polysorbate 20, acacia, baby powder and body powder products by incorporating 65 acrylates copolymer, alcohol denatured, aminomethyl pro bioactive glass into a combination of any of the above-listed pandiol, ammonium acrylates copolymer, ammonium ingredients. hydroxide, ammonium lanolate, ascorbyl palmitate, benzyl US 8,551,508 B2 21 22 alcohol, BHA, butyl stearate. C9-11 isoparaffin, candelilla onate ceresin, castor oil, vegetable oil, lanolin, aluminum wax, carmine, cetyl alcohol, cetyl Stearate, chromium powder, bronze powder, copper powder, Zinc oxide, alumi hydroxide green, citric acid, cyclomethicone, ethylparaben, num powder, ammonium hydroxide, ascorbic acid, ascorbyl fragrance, glycerin, glyceryl rosinate, hydgroplex Hhg Whn, palmitate, benzyldimethylstearylammonium hectorite. BHA, hydrolyzed keratin, hydroxyethylcellulose, imidazolidinyl bismuth oxychloride, butyl stearate, butylene glycol, butylpa urea, iron oxides, kaolin, magnesium aluminum silicate, raben, candelilla wax, caprylic/capric acid triglyceride, car methyl ethyl propyl butylparabens/phenoxyethanol, MIPA mine, carnaubacetyl alcohol, carnauba wax, ceresin, cerotic lanolate, MIPA-oleate, nnoxynol-10, oleic acid, oleyl alco acid, cetyl alcohol, cetyl esters, cetyl palmitate, chromium hol, PEG-100 stearate, pentaerythrity1 tetrastearate, phe hydroxide green, chromium oxide greens, citric acid, diaZo noxyethanol, polybutene, polyethylene, polyduaternium 10, 10 polyvinyl alcohol, potassium Ocotxynol-12, phosphate, pro lidinyl urea, dimethicone, ferric ammonium ferrocyamide, pylene carbonate, propylene glycol, propyl, quaternium-15. fish glycerides, glycerin, hydrogenated castor oil, hydroge quaternium-18, hectorite, quaternium-22, SD alcohol 40-B, nated coco-glycerides, hydrogenated cottonseed oil, hydro silica, silk powder, sodium dehydroacetate, sodium laureth genated fish oil, hydrogenated palm glycerides, hydrogenated Sulfate, Sodium lauryl Sulfate, sodium polymethacrylate, Sor 15 vegetable oil, hydroxyethylcellulose, hydroxylated lanolin, bitan sesquioleate, talc, titanium dioxide, triclosan, trimeth ipphilic glyceryl monooleate, iron oxides, isopropyl C12-15 ylsiloxysilicate, trisodium EDTA, ultramarines and Xanthan pareth-9 carboxylate, japan wax, lipophilic glyceryl gun. monostearate, manganese violet, mellisic acid, methyl pol The present invention provides for novel formulations of ysiloxane, mica, myricyl alcohol, oleoStearine, oZokerite, mascaraproducts by incorporating bioactive glass into a com paraffin, parahydroxybenzoate ester, PEG-8, polyethylene, bination of any of the above-listed ingredients. polysorbate 60, PPG-15, PPG-5 eteth-20, PVP laureth-4, Generally, eyeshadow products comprise talc, mica, poly quaternium-18 bentonite, Saturated fatty acid glycerides, ethylene fluorethylene, magnesium Stearate and coloring silica, Sorbitan Stearate, soybean phospholipid soybean leci agents. thin, Stearic acid, Stearyl heptanoate, styrenefacrylates Common formulations of eyeshadow products comprise 25 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, dehydroacetic The present invention provides for novel formulations of acid, methylparaben, propylparaben, ethylparaben and dia 30 eyeliner and eyebrow pencil products by incorporating bio Zolidinyl 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, an stearylammonium hectorite, BHT, bismuth oxychloride, emollient, and coloring agents. C12-C15 alkyl benzoate, calcium silicate, candelilla wax, 35 Common formulations of blush products comprise dime caprylic?capric acid try glyceride, carnauba wax, chromium thicone, octyl palmitate, talc, nylon-12, neopentyl glycol hydroxide green, chromium oxide greens iron oxides, citric disooctanoate, tribehenin, isostearyl behenate, boron nitride, acid, coco caprylate caprate, D1 tocopherol, hydrogenated acrylates copolymer, tocopherol, retinyl palmitate, methox oil, hydroxylated lanolin, imidazolidinyl urea, isopropyl tri ypropylgluconamide, chitin extract, sodium hyaluronate, SoStearoyltitanate, lauroyl lysine, lauryl lysine, lecithin, lipo 40 hydrolyzed glucosaminoglycans, lecithin, candelilla wax, philic glyceryl monostearate, magnesium carbonate, manga soy amino acids, mimosa wax, pentahydrosqualene, Sorbitan nese violet, methyl polysiloxane, mica, mineral oil, trioleate, water, propylene glycol, silica, phenoxyethanol, octyldodecyl Stearoyl Stearate, paraffin, parahydroxyben titanium butylparaben, isopropylparaben, isobutylparaben, Zoate ester, polymethyl methacrylate, polyvinylidene copoly BHA, lauryl lysine and methyldihydroiasmonate. mer, propylene carbonate, quaternium-15, Saturated fatty 45 Blush products may also include one or more of the fol acid glycerides, Sodium dehydroacetate, soybean phospho lowing: acetylated lanolin alcohol, allantoin, ascorbyl palmi lipid soybean lecithin, Stearic acid, titanium dioxide, trilaurin, tate, barium sulfate, BHT, bismuth oxychloride, butylpara trioctanion, ultramarines, Zinc oxides, iron oxides, ferric fer ben, C12-15, alkyl benzoate, calcium silicate, camphor, rocyamide, ferric ammonium ferrocyamide, carmine, polyg carbomer, carmine, cethyl acetate, clove oil, coco caprylate lyceryl-3 diisoStearate, hydrogenated coco-glycerides, ethyl 50 caprate, diazolidinyl urea, ethylparaben, eucalyptus oil, ferric ene/methacrylate copolymer, nylon-12, pentahydrosqualene, ammonium ferrocyamide, ferric ferrocyamidea, fragrance, acrylates copolymer, polyglycery-4 isostearate, laurylmethi imidazolidinyl urea, iron oxides, kaolin, manganese violet, cone copolyol, perfluoropolymethyliospropeth phosphate, menthol, methylparaben, mica, midazolidinyl urea, mineral butylparaben, phenoxyethanol and various coloring agents. oil, oat flour, octyldodecyl Stearoyl Stearate, panthenol, poly The present invention provides for novel formulations of 55 ethylene, polyoxymethylene urea, polysorbate 20, polysor eyeshadow products by incorporating bioactive glass into a bate 80, quaternium-15, Sodium dehydroacetate, tetrasodium combination of any of the above-listed ingredients. edtapropylparaben, tin oxide, titanium dioxide, triethanola Generally, eyeliner and eyebrow pencil products comprise mine, trimethylsiloxysilicate, trioctanion, ultramarines, Vari talc, mica, polyethylene, fluorethylene, magnesium Stearate ous coloring agents, various plant extracts, Zinc Stearate, and coloring agents. 60 hydrogenated coco-glycerides, octyl hydroxyStearate, ultra Common formulations of eyeliner and eyebrow pencil marines and various coloring agents. products comprise cyclomethicone, synthetic beeswax, The present invention provides for novel formulations of arachidyl behenate, microcrystalline wax, quaternium-18 blush products by incorporating bioactive glass into a com hectorite, mineral oil, propylene carbonate, methylparaben, bination of any of the above-listed ingredients. propylparaben and BHT. 65 Generally, concealer and foundation products comprise Eyeliner and eyebrow pencil products may also include isoeicosane, carnauba, polyglyceryl-3 diisoStearate, silica, one or more of the following: PPG-2 myristyl ether propi titanium oxide and coloring agents. US 8,551,508 B2 23 24 Common formulations of concealer and foundation prod Common formulations of face powder products comprise ucts comprise water, butylene glycol, dimethicone, isostearyl talc, mineral oil, Zinc Stearate, kaolin, aluminum starch octe alcohol, synthetic wax, cyclomethicone, PEG-20 methylglu nylsuccinate, acrylates copolymer, silk powder, silica, propy cose sesquistearate, Sodium Stearate, tribehenin, polymethyl lparaben, methylparaben, calcium silicate, imidazolidinyl methacrylate, Salicylic acid, hydrolyzed vegetable protein, urea, iron dioxides and ultramarines. silica, talc, microcrystalline wax, dimethicone copolyol. Face powder products may also include one or more of the polyglyceryl-6-polyricinoleate, aluminum Stearate, boron following: acetylated lanolin alcohol, ascorbyl palmitate, nitride, dimethiconol. diisoStearyl malate, casein, carrag beeswax, BHT, bismuth oxychloride, camphor, caprylic/ca eenan, tocopheryl acetate, retinyl palmitate, aloe extract, pric triglyceride, carmine, clove oil, cyclomethicon, dextrin, 10 diazolidinyl urea, dimethicone, ethylene? acrylic acid copoly ascorbic acids, menthol, calcium chloride, nylon-12, perfluo mer, ethylparaben, eucalyptus oil, fragrance, glyceryl rosi ropolymethylisopropyl ether, methylparaben, propylparaben nate, hydrogentated lecithin, isopropyl palmitate, lauroyl and phenoxyethanol. lysine, lecithin, magnesium Stearate, magnesium sulfate, Concealer and foundation products may also include one manganese violet, menthol, methicone, methyl-ethyl-propyl or more of the following: paraffin, pentaerythrity1 tetrastear 15 ibutylparabens/phenoxyethanol, mica, nylon-12, oat flour, ate, octyl hydroxystearate, ceteareth-20, setereth-2, DMDM octyl palmitate, octyldodecanol Stearoyl Stearate, octyldode hydantoin, quaternium-15, dextrin, calcium silicate, Zinc cyl myristate, panthenol, phenoxyethanol, phenyl trimethi stearate, octyldodecyl myristate, tridecyl trimelitate, bis cone, polysorbate 20, propylene glycol, quaternium-15. digly-ceryl caprylate/capratefisostearate/stea, glyceryl rosi quaternium-18 hectorite, retinyl palmitate, Sodium dehy nate, acetylated glycol Stearate, acetylated lanolin, acetylated droacetate, sodium hydrogenated tallow glutamate, Sorbitan lanolin alcohol, acrylates copolymer, alcohol denatured, sesquioleate, Sorbitan trioleate, titanium dioxide, tocopheryl alkyl octanoate, allantoin, aluminum hydroxide, aluminum acetate, triclosan, tridecyl trimellitate, various coloring starch octenylsuccinate, aminoethylpropanol, arachidyl agents, various plant extracts, water, aloe extract and allon behenate, ascorbyl palmitate, barium Sulfate, beeswax, ben toin. tonite, benzoic acid, BHA, BHT, bisabolol, bisacodyl, bis 25 The present invention provides for novel formulations of muth oxychloride, butylparaben, C12-15 alcohols octanoate, face powder products by incorporating bioactive glass into a C12-15 alkylbenzoate, calcium aluminum borosilicate, can combination of any of the above-listed ingredients. delilla wax, caprylic/capric triglyceride, carnauba, castor oil, Generally, and lip gloss products comprise castor cellulose gum, cetearyl alcohol, cetearyl octanoate, cethyl oil, caprylic/capric triglycerides, Stearic acid, lanolin, poly acetate, cetyl alcohol, cetyl dimethicone copolyol, cocoyl 30 butene, mineral oil, kanolin, silica, BHT, and coloring agents. sarcosine, diazolidinyl urea, dicaprylate/dicaprate, dioctyl Common formulations of lipstick and lip gloss products adipate, dipropylene glycol, disodium EDTA, disopropyl comprise trictyldodecyl citrate, isotridecyl isononanoate, dimer dilinoleate, ethylene brassylate, ethylene/methacrylate C10-20 cholesterol/lanosterol esters, synthetic beeswax, par copolymer, ethylene/vinyl acetate copolymer, fragrance, affin, cetyl alcohol, candelilla wax, aloe extract, retinyl glycerin, glyceryl Stearate, hexyl laurate, hydrogenated coco 35 palmitate, tocopheryl acetate, ascorbyl palmitate, sodium glycerides, hydrogenated polyisobutane, imidazolidinyl hyaluronate, PEG-20 sorbitan beeswax, quaternium-18 hec urea, iron oxides, isocetyl Stearate, isododecane, isooctahexa torite, benzoic acid, BHA, methylparaben, propylparaben, contane, isopropyl isostearate, isopropyl palmitate, isopropyl titanium dioxide, mica, iron dioxides and various coloring titanium trisoStearate, isoStearyl neopentanoate, isostearyl agents. palmitate, kaolin, lanolin, lanolinalcohol, lanolin oil, laureth 40 Lipstick and lip gloss products may also include one or 7, lauroyl lysine, lecithin, lipophilic glyceryl monostearate, more of the following: acetylated lanolin, acrylates copoly magnesium aluminum silicate, magnesium carbonate, mag mer, allantoin, ascorbyl palmitate, beeswax, bis-diglyceryl nesium sulfate, methicone, methyl glucose sesquistearate, polyacyladipate-2, bismuth oxychloride, butylparaben, C10 methyl polysiloxane, mica, mineral oil, myristyl lactate, 30 cholesterol/lanosterol esters, carnauba, castor oil, cethyl octamethylcyclotetrasiloxane, octyl methoxycinamate, octyl 45 acetate, cetyl dimethicone copolyol, cetyl octanoate, citric palmitate, octyl salicylate, octyl Stearate, octyldodecanol, acid, cocoa butter, coconut oil, cyclomethicone, cyclopenta octyldodecy neopentanoate, octyldodecyl Stearoyl Stearate, siloxane, cyclotetrasiloxane, diisopropyl, dimer dilinoleate, ozokerite, panthenol, pectin, PEG-100 stearate, PEG-2 stear dimethicone, trissostearyl citrate, D1-tocopherol, drometri ate, PEG-20 sorbitan beeswax, PEG-32, PEG-6, PEG-8, pet Zole, D-tocopherol, ethylcellulose, fragrance, glyceryl oleate, rolatum, phenyl dimethicone, polyethylene, polyglyceryl-4 50 grapeseed oil, hexyl laurate, hydrogenated polyisobutene, isostearate, polyglyceryl-6, ricinoleate, polyisobutene, hydrogenated Soy glyceride, hydrogenated vegetable oil, polysorbate 60, propylene glycol, PVP quaternium-18 hec hydrolyzed collagen, hydrolyzed glucosaminoglycans, iso torite, SD alcohol 40b, silk powder, sodium chloride, sodium cetyl Stearate, isododecane, isopropyl myristate, isostearyl dehydroacetate, Sodium hyaluronate, sodium lauroyl sarco palmitate, lanolin, magnesium ascorbyl phosphate, menthol, sinate, Sorbic acid, Sorbitan sesquioleate, Stearic acid, Stear 55 methicone, methyl glucose sesquistearate, microcrystalline oxytrimethylsilane, Stearyl alcohol, Stearyl Stearoyl Stearate, wax, mineral oil, myristyl lactate, neopentyl glycol dicoc t-butyl hydroquinone, tetrasodium EDTA, titanium dioxide, tanoate, octyl hydroxy Stearate, octyl methoxycinnamate, tocopheryllinoleate, tricontanyl PVP triethanolamine, trihy octyl palmitate, octyldodecanol, oleyl alcohol, oxybenzone, droxystearin, trimethylsiloxysilicate, trisodium EDTA, ozokerite, padimate, PEG-20 sorbitan beeswax, pentaeryth tristearin, ultramarine blue, va/vinylbutylbenzoate, xanthum 60 rity1 tetrabehenate, pentaerythrityl tetraisostearate, petrola gum and various coloring agents. tum, phytosterol/octyldodecyl lauroyl glutamate, poly The present invention provides for novel formulations of butene, polyethelene, polyethylene, polyglyceryl-2 concealer and foundation products by incorporating bioactive disoStearate, polyglyceryl-3 diisoStearate, polyglyceryl-4 glass into a combination of any of the above-listed ingredi isostearate, polymethysilses quioxane, PPG 51/smdi copoly entS. 65 mer, propyl gallate, propylene glycol, PVP/hexadecene Generally, face powder products comprise talc, a preserva copolymer, seasame oil, shellac wax, silica, Sodium hyalur tive, calcium Stearate, and coloring agents. onate, sodium lactate, sodium PCA, Sodium phosphate, US 8,551,508 B2 25 26 Sodium saccharin, Sorbic acid, squalane, Stearic acid, Stearyl menthol, methylparaben, microcrystalline wax, mineral oil, dimethicone, Sucrose acetate isobutyrate, T-butyl hydro mixed wax, octadecene/ma copolymer, octyl methoxyci quinone, tocopheryl acetate, trihydroxy Stearin, triisoStearyl namate, octyl palmitate, oxybenzone, oZokerite, padimate, citrate, trilso stearin, trimethylsiloxysilicate, urea, various paraffin, petrolatum, phenol, polybutene, polyphenylmethyl natural and artificial flavorings, various vitamin agents, siloxane 556, polythylene, propylparaben, purified water, water, wheat germ oil, caprylic/capric triglyceride, ceresin, saccharin, Salicylic acid, SD alcohol 36, Stearyl alcohol, Sun trifluoromethyl C1-4 alkyl dimethicone, arachidyl propi flower seed oil, talc, tridecyl stearate, tridecyl trimellitate, onate, phenyl trimethicon and BHT. triisoStearin esters, various coloring agents, wax paraffin and The present invention provides for novel formulations of white wax. 10 The present invention provides for novel formulations of lipstick and lipgloss products by incorporating bioactive lip treatment products by incorporating bioactive glass into a glass, into a combination of any of the above-listed ingredi combination of any of the above-listed ingredients. entS. Generally, lipliner products comprise a wax product, a Example 4 below provides an exemplary embodiments of lipstick formulations incorporating bioactive glass. preservative, mineral oil, Stearic acid and coloring agents. 15 Common formulations of lipliner products comprise castor oil, isopropyl palmitate, lanolin, beeswax, candelilla wax, Example 4 meadowfoam seed oil, fragrance, Sesame oil, polybutene, oZokerite, dioctyldodecyl fluoroheptyl citrate, carnuba wax, Lipstick with Bioglass Formulas CPD3-33 A, B, C paraffin, hydrogenated Soy glyceride, propylene glycol, Stearic acid, Sodium saccharin, propylparaben, propyl gallate and citric acid. Lipliner products may also include one or more of the following: aloe extract, BHA, bismuth oxychloride, bronze INGREDIENTS wt %. A wt % B wt % C powder, butylparaben, carmine, castor oil, ceresin, copper PartA powder, cyclomethicone, disoStearyl dimer dilinoleate, 25 hydrated silica, hydrogenated castor oil, hydrogenated cot Red 7 Ca Lake 3.0 3.0 3.0 tonseed oil, hydrogenated vegetable oil, iron oxides, manga Red 6 Ba Lake 1.O 1.O 1.O Red 33 Al Lake 1.O 1.O 1.O nese violet methylparaben, mica, PEG-6 beeswax, poly Castor Oil 1S.O 1S.O 1S.O butene, quaternium-18 bentonite, retinyl palmitate, sodium Part B saccharin, synthetic wax, titanium dioxide, tocopheryl 30 acetate, various coloring agents, various natural and artificial Castor Oil 30.6 30.6 30.6 flavorings, Zinc oxide, asorbyl palmitate, Saturated fatty acid Carnauba Wax 2.0 2.0 2.0 glycerides, caprylic/capric acid triglycerides, glyceryl tri Candellila Wax 7.0 7.0 7.0 Ozokerite Wax 2.0 2.0 2.0 palmitate, parahydroxybenzoate ester, soybean phospho Microcrystalline Wax 3.0 3.0 3.0 lipid, soybean lecithin and lipophilic glyceryl monostearate. Jojoba Oil 2SO 2S.O 2S.O 35 The present invention provides for novel formulations of Vitamin E 1S.O 1S.O 1S.O products by incorporating bioactive glass into a com Methyl Paraben O.1 O.1 O.1 bination of any of the above-listed ingredients. Propyl Paraben O.2 O.2 O.2 Generally, nail polish products comprise nitrocellulose, a Schott Glass 45s5 (<4Lave. part. size) O.1 O.1 O.1 lacquer dissolved in solvents such as acetone or ethyl alcohol Part C and coloring agents. 40 Tac USP 1O.O Common formulations of nail polish products comprise Bioglass 45 S (c) 1.6 L 1O.O ethyl acetate, butyl acetate, isopropyl alcohol, nitrocellulose, Bioglass 58s (a) 0.77. 1O.O glyceryl tribenzoate, acetyl tributyl citrate, Stearalkonium bentonite, Stearalkonium hectorite, glyceryl triacetate, cam 1OOO 1OO.O 1OO.O phor, SD alcohol 40, citric acid, malic acid, phosphoric acid, 45 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 hydroxyben and tin Observations: oxide. 1) The Talc Formula did not set as well/quickly as eitherglass. Nail polish products may also include one or more of the 2) The 58s glass formula set up somewhat faster and appeared following: acrylates copolymer, algae extract, aluminum, to make a smoother product as compared to the 45s glass amyul acetate, benzophenone-1, biotin, bismuth oxychloride, formula. 50 chromium hydroxide green, chromium oxide greens, diac 3) The Talc formula showed more feathering (bleeding) at 1 etone alcohol, dibutyl phthalate, dimethicone copolyol. hr. dipropylene glycol dibenzoate, ethyl tosylamide, etocrylene, Generally, lip treatment products comprise , ferric ammonium ferrocyamide, ferric ferrocyamide, fiber healants and protectants such as petrolatum jelly. glass, fragrance, glycols copolymer, guanine, hydrated silica, Common formulations of lip treatment products comprise iron oxides, isobutyl acetate, manganese violet, methyl white petrolatum, ethylhexyl P-methoxycinnamate, carnuba, 55 acetate, mica, N-butyl alcohol, oxidized polyethylene, pan hydroxylated milk glycerides, nylon-12, paraffin, tocopheryl thenol, phthalic anhydride, phthalic anhydride/glycerin/gly acetate, bisabolol, retinyl palmitate, panthenol, lecithin, cidyl decandate cop, phthalic anhydride/trimellitic anhy Stearic, soya Stearol, Zinc sulfate, Sodium saccaharin, various dride/glycols copolymer, polyester resin, polyethylene natural and artificial flavorings and various plant extracts. terephithlate, propyl acetate, retinyl palmitate, silica, silver, Lip treatment products may also include one or more of the 60 styrenefacrylates copolymer, Sucrose acetate isobutyrate, Sty following: 2-ethylhexyl salicylate, 2-octyldodecanol, allan renefacrylates/acrylonitrile copolymer, tetrabutyl phenyl toin, aloe extract, alum, arachadyl propionate, beeswax, ben hydroxybenzoate, titanium dioxide, tocopheryl acetate, tosy Zoic acid, benzophenone-3, BHT, bisacodyl, borage seed oil, lamide/epoxy resin, tosylamide/formaldehyde resin, triben camphor, carnuba wax, castor oil, cetyl alcohol, cetyl esters, Zoin, trimellitic anhydride, ultramarines, various coloring cocoa butter, corn oil, dimethicone, dimethicone, dipen 65 agents, Stearalkonium hectorite, dimethicone copolyol, acry taerythrityl hexacaprate/hexacaprylate, fragrance, hydroge late copolymer, dipropylene glycol dibenzoate, tribenzoin, nated castor oil, isopropyl lanolate, kukui nut oil, lanolin, biotin, panthenol, retinyl palmitate, tocopheryl acetate, alu US 8,551,508 B2 27 28 minum powder, bismuth oxychloride, polyester resin, Example 8 Sucrose acetate isobutyrate, diacetone alcohol, benzophe none-1, guanine, toluene, tosylamide/formaldehyde resin, Composition of Skin and Nail Treatment dibutyl phthalate, tetrabutyl phenyl hydroxybenzoate, tita nium dioxide, iron dioxides, mica, ferric ammonium ferro- 5 Anhydrous with Sol-Gel-Derived Bioactive Glass cyamide, calcium pantothenate, heptane, etocrylene, acetyl tributy citrate, hydrolyzed keratin and various coloring agents. The present invention provides for novel formulations of nail polish products by incorporating bioactive glass into a 10 INGREDIENTS wt % combination of any of the above-listed ingredients. Jojoba Glaze 91.5 Bioactive glass and Sol-gel derived bioactive glass reacts with Brown Iron Oxide O.S aqueous fluids to form a solution that is rich in inorganic Titanium Dioxide O.S Tac - USP 2.5 elements, such as calcium, phosphorous, sodium and silicon. Schott Glass sol-gel-derived bioactive glass S.O These inorganic elements can precipitate on nails to form a 15 mineralogical layer (i.e., hydroxyapatite). This mineralogical layer is expected to add strength to nails. Examples 5-8 below provide exemplary embodiments of Generally, nail polish remover products comprise acetone nail care formulations incorporating bioactive glass, includ o or ethyl acetate. ing sol-gel-derived bioactive glass. Common formulations of nail polish remover products comprise ethyl acetate, alcohol, water, propylene carbonate, Example 5 dimethyl glutarate, dimethyl Succinate, dimethyl adipate, gelatin, glycerin, diglycerol, fragrance, isopropanol, propyl Composition of Anhydrous Nail-Strengthening Gel I 25 acetate, benzophenone-1, castor oil and various coloring agents. Nail polish remover products may also include one or more of the following: acetone, citric acid, denatonium benzoate, INGREDIENTS wt % PEG-75 lanolin oil, mineral oil, panthenol and tocopheryl 30 acetate. Jojoba Glaze 80.0 Bioactive glass may be incorporated into a combination of Schott Glass Bioactive Glass (<4 ave, part, size) 20.0 any of the above-listed ingredients. 1OO.O Tampon, Maxipad and Pantiliner Products The present invention includes novel formulations which 35 incorporate bioactive glass into various brands of tampon, maxipad and pantiliner products such as the products mar Example 6 keted under the brand names Always, Carefree, Kotex, o.b. Playtex, Tampax, and products produced by high-end and Composition of Anhydrous Nail-Strengthening Gel generic manufacturers. II 40 Generally, tampon products comprise cotton and/or rayon overwrap and cotton cord. Tampon products may also include one or more of the following: polyethylene/polyester cover, polysorbate-20, fra grance, and a plastic or cardboard applicator. INGREDIENTS wt % 45 Generally, maxipad and pantiliner products comprise cel Jojoba Glaze 90.0 lulose, plastic and adhesive strips. Maxipad and pantiliner Schott Glass Bioactive Glass (<4Lave. part. size) 1O.O products may also include a fragrance. The present invention provides for novel formulations of 1OO.O tampon, maxipad and pantiliner products by incorporating 50 bioactive glass into a combination of any of the above-listed ingredients. Example 7 The antimicrobial and hygroscopic effects of bioactive glass are particularly useful in tampon, maxipad, and pant Composition of Nail Gel iliner products to reduce bacteria and odor. 55 Acne Prevention and Treatment Products Anhydrous with Bioactive Glass The present invention includes novel formulations which incorporate bioactive glass into various brands of acne pre vention and treatment products such as the products marketed under the brand names Acne Aid, Aconmel, Aveeno, Biore, 60 Burt’s Bees, Clean & Clear, Clear Logix, , Desert INGREDIENTS wt % Essence. Exact, Fostex, Garden Botanika, Hyland's Homeo Glycerin 90.50 pathic, Tonax, Jason, Johnson & Johnson, Kiss My Face, Pemulen (RTR-2 O.45 Liquimat, Neutrogena, Noxzema, Orange Daily, Oxy. Pam Schott Glass Bioactive (<4Lave. part. size) 9. OS oxyl, Pernox, Ponds, Rezamid, Sal Ac, Salicylic Acid, Sas 100.00 65 tid, Sebasorb, Stiefel, Stridex, Suave, Sulforcin, Sulfur Soap, Sulpho-Lac, T-Zone, Zirh, and products produced by high end and generic manufacturers. US 8,551,508 B2 29 30 Generally, acne prevention and treatment products com ben, camphor, caprylic/capric triglyceride, carbomer, cer prise the active ingredient benzoyl peroxide or salicylic acid. esin, ceteareth-20, cetearyl alcohol, cetearyl isononanoate, Common formulations of acne prevention and treatment cetyl alcohol, cetyl hydroxyethylcellulose, cetyl octanoate, products comprise active ingredients consisting of a combi chlorhexidrine digluconate, chromium hydroxide green, cit nation of resorcinol, Sulfur and alcohol or benzoyl peroxide. ric acid, cocamide mea, cocamidopropyl phosphatidyl pg Acne prevention and treatment products may also include dimonium chloride, cocamidopropylamine oxide, colloidal one or more of the following inactive ingredients: alcohol, oatmeal, corn germ oil, dea-cetyl phosphate, diazolidinyl attapulgite, bentonite, butylparaben, carbomer, citric acid, urea, dicaprylate/dicaprate, dimethicone, disodium EDTA, dioctylsodium sulfosuccinate, disodium EDTA, edetate diso disodium laureth SulfoSuccinate, disodium lauroamphodiac dium, EDTA, fragrance, glycerin, hydroxyethylcellulose, 10 etate, disodium oleamido PEG-2 sulfosuccinate, disodium hydroxypropyl methylcellulose, iron oxides, isopropyl ricinoleamido mea-sulfoSuccinate, edetate disodium, EDTA, myristate, kaolin, lauramide dea, methylparaben, parachlo ethoxydiglycol, ethylparaben, gelatin, glyceryl laurate, glyc rometaxylenol, PEG-8 laurate, potassium hydroxide, propy eryl polymethacrylate, glyceryl Stearate, glycol DS, hexylene lene glycol, propylparaben, Salicylic acid, simethicone, glycol, hydroxycetyl hydroxyethyl dimonium chloride, sodium bisulfite, sodium borohydride, sodium chloride, 15 hydroxypropyl guar hydroxypropyltrimonium chloride, Sodium cocoate, Sodium hydroxide, Sodium polynapthalene hydroxypropylcellulose, imidazolidinyl urea, iron oxides, Sulfonate, Sodium tallowate, talc, titanium dioxide, trisodium isocetyl alcohol, isopropyl myristate, isopropyl palmitate, hedta, various plant and mineral extracts, water, Xanthan gum, lactic acid, lanolin oil, laureth-4, laureth-9, lauric acid, lauryl Zinc oxide, aluminum hydroxide, glyceryl Stearate SE and phosphate, lauryl polyglucose, magnesium aluminum sili PEG-12. cate, menthol, methyl gluceth 20, methylchloroisothiazoli The present invention provides for novel formulations of none, methyldibromo glutaronitirle, methylisothiazolinone, acne prevention and treatment products by incorporating bio methylparaben, mineral oil, myristic acid, octyl hydroxys active glass into a combination of any of the above-listed tearate, olive oil, palmitic acid, paraffin, PEG-10 hydroge ingredients. nated castor oil, PEG-10 soya sterol, PEG-100 stearate, PEG The antimicrobial and anti-inflammatory properties of bio 25 120 glucose dioleate, PEG-120 methyl glucose dioleate, active glass are particularly useful in acne prevention and PEG-150 distearate, PEG-2 stearate, PEG-20, PEG-200 glyc treatment products. Bioactive glass can be used in topical eryl tallowate, PEG-3 distearate, PEG-7 glyceryl cocoate, acne creams to reduce inflammation, while also killing the PEG-8, PEG-80 sorbitan laurate, PEG-9 tridecyl ether, pen bacteria and micro-organisms that cause acne. tasodium penetate, petrolatum, PG-acetate phosphate, phe Facial Cleansing, Toning, Exfoliating and Makeup Removal 30 noxyethanol, phenylethyl alcohol, poloxamer 184, poly Products decene, polyol alkoxy esters, polyoxyethylene 15 cocoamine The present invention includes novel formulations which phosphatefoleate comp, polyduaternium-10, polyduater incorporate bioactive glass into various brands of facial nium-24, polyduaternium-7 capryloyl salicylic acid, polysor cleansing, toning, exfoliating products and makeup removal bate 20, polysorbate 60, polysorbate 80, potassium hydrox products such as the products marketed under the brand 35 ide, potassium myristate, potassium palmitate, potassium names Aapri, Albolene, Almay, Alpha Hydrox, Ambi, Aqua sorbate, potassium stearate, PPG-10 butanediol, PPG-10 Glycolic, Aquanil Lotion, Artra, Aveeno, Basis, Biore, Body methyl glucose ether, PPG-12 buteth-16, PPG-15 stearyl cology, Bonnie Bell, Brite-Life, Burts's Bees, Camocare, ether, propylene glycol, propylparaben, quaternium-15, saf Cetaphil, Clean & Clear, Clairol, Clearasil, Clearly Natural, flower oil, salicylic acid, sesame oil, simethicone, sodium Cover Girl, Curad, Dickinson's, DML, Earth Science, Free 40 borate, sodium C12-15 alcohol ethoxycarboxylate, sodium man, Garden Botanika, Tonax, Jason, Jergens, Johnson & chloride, sodium cocoate, Sodium cocoylglutamate, sodium Johnson, Keri, Kiss My Face, La Bella, L'Oreal, , cocoylisethionate, Sodium cocoylisethionate, sodium dode Moisturel, Neutrogena, , Noxzema, Oil of Olay, Oxy. cylbenzenesulfonate, Sodium isethionate, Sodium isostearoyl Phisoderm, Plenitude, Ponds, Propa pH, Purpose, Reviva, lactylate, Sodium lactate, Sodium lauroamphoacetate, sodium Revlon, RoC, Sea Breeze, Seban, St. Ives Swiss Formula, 45 lauroyl sarcosinate, Sodium lauryl Sulfate, Sodium lauryl Sul Stiefel, Stridex, Suave, T-Zone, Ten-O-Six, Vegee Tonic, and foacetate, Sodium myristoyl sarcosinate, sodium palm kerne products produced by high-end and generic manufacturers. late, Sodium PCA, sodium Stearate, sodium sulfite, sodium Generally, facial cleansing, toning, or exfoliating products tallowate, Sodium trideceth Sulfate, Sodium cocoylisethion or makeup removal products comprise camphor, water, men ate, Stearamidopropyl pg-dimonium chloride phosphate, Ste thol, Stearic acid, calcium hydroxide, ammonium hydroxide 50 areth-2, Steareth-21, Stearic acid, Stearyl alcohol. Sucrose lau and an exfoliant such as alpha or beta hydroxy acid, retinoic rate, talc, tea-Stearate, tetrasodium EDTA, tetrasodium acid, azelaic acid or adapelene. etibronate, titanium dioxide, triclocarban, pentasodium pen Common formulations of facial cleansing, toning, exfoli tetate, triclosan, triethanolamine, trisodium hedta, ating products and makeup removal products comprise water, tromethamine, Sodium cetyl Sulfate, oleyl betaine, laureth-3, glycerin, Sodium laureth Sulfate, cocamidopropyl betaine, 55 self-emulsifying wax, cocoamphocarboxyglycinate, laura tocopheryl acetate, panthenol, methyl lactate, carylates/ste mide DEA, lauramide MEA, linoleamide DEA, polyethyl areth-20, methacrylate copolymer, Xanthan gum, microcrys ene, lauryl methyl gluceth-10 dihydroxypropyldimonium talline wax, sodium magnesium, silicate, sodium hydroxide, chloride, sodium lauroamphodiacetate and decy glucoside. fragrance, DMDM hydantoin, iodopropynlbutyl carbamate, The present invention provides for novel formulations of various vitamin, mineral, fruit and vegetable extracts and 60 facial cleansing, toning, and exfoliating products and makeup various coloring agents. removal products by incorporating bioactive glass into a com Facial cleansing, toning, and exfoliating products and bination of any of the above-listed ingredients. makeup removal products may also include one or more of the The anti-inflammatory and antimicrobial effects of bioac following: 1-hexadecanol, iodopropylbutylcarbamate, acry tive glass are particularly useful in facial cleansing, toning, late crosspolymer, acrylates/C10-30 alkyl, allantoin, ammo 65 and exfoliating products and makeup removal products to nium hydroxide, beeswax, benzophenone-4, benzyl alcohol, reduce bacteria and inflammation. Additionally, the abrasive beta carotene, BHT, boric acid, butylene glycol, butylpara quality of bioactive glass is useful in exfoliation. US 8,551,508 B2 31 32 Facial Moisturizing Anti-Wrinkle, Eye Treatment and Hand more of the following: 1-hexadecanol, acemannan hydrogel, and Body Lotion Products acetylated lanolin alcohol, acrylates copolymer, acrylates/ The present invention includes novel formulations which C10-30 alkyl acrylate crosspolymer, acrylates/carbamate incorporate bioactive glass into various brands of facial mois copolymer, alantoin octyl dimenthyl paba, alcohol, allanto turizing, anti-wrinkle, anti-aging, eye treatment and hand and intetra EDTA, alpha lipoic acid, aluminum starch octenylsuc body lotion products such as the products marketed under the cinate, ammonium glycolate, ammonium hydroxide, ammo brand names Acid Mantle, A-Derma, Abra, Alba Botanica, nium lactate, apricot kernel oil, ascorbic acid polypeptide Albolene, Almay, Ala Derm, Allercreme. Aloe Vera 80, Alpha (vitamin c), ascorbyl palmitate, avobenzone, beeswax, ben Hydrox, Alpha Keri, AmLactin, Aqua Care, Aqua Glycolic, Zophenone-4, benzyl alcohol, BHT, bisaboloi, blyceryl Stear Aqua Lactin, Aquanil, Asorbase, ArthiCare, Atrac-Tran, 10 ate, boric acid, butyrolactone, C10-30 cholesterol/lanosterol Aveeno, Avon, , Baker Cummins, Balm Barr, esters, C12-15 alkyl benzoate, C13-14 isoparaffin, calcium Basis, Beauty Without Crvetty, Beta Care, Biore, Bodycol chloride, calcium hydroxide, calcium sulfate, camphor, ogy, Brite-Life, Burt’s Bees, , Camocare Gold, Ca caprylic acid, castor oil, ceramide 3, ceresin, ceteareth 20, ReZZ, Carmol, Carrington, CBI, Cetaphil, Chamberlain, cetearyl alcohol, cetearyl octanoate, ceteth-24, cetrimonium Clairol, Clean & Clear, Complex 15, Coral Springs, Corn 15 chloride, cetyl acetate, cetyl dimethicone, cetyl esters, cetyl Huskers, Curel, Cutar, Cutemol, Dermal Therapy, Dermac octanoate, cetyl palmitate, cetyl ricinoleate, chloride, chlor erin, Dermasil, Dermatone, Dermovan, DialDermal, Diabeti phenesin, cholecalciferol, cholesteryl isoStearate, choleth-24, Derm, Dixie Health, DML, Doak, DPM, Earthly Elements, citric acid, coco caprylate caprate, cocoa butter, cocobetaine, Earth Science, Earth Therapeutics, Elta, Epilyt, Esoterica, colloidal oatmeal, copolymer, cyclomethicone, cyclopentasi Estar, Eucerin, Evian, Exorex, Face Lift, Formula 405, Foug loxane, dea-cetyl phosphate, dea-oleth-3 phosphate, dermas era, Freeman, Fruit of the Earth, Galderma, Garden Botanika, terone (bioactive multiwildyam species complex), diazolidi Gold Bond, Golden Sun, Good Sense, Healthflow, Hydroxy nyl urea, dicaprylate/dicaprate, dicaprylyl ether, dicaprylyl C, Jamieson & Co., J.C. Brillantine, Jason, Jean Nate, Jer maleate, diisopropyl sebacate, dioctanoate, dioctyl Succinate, gens, Jockey Club, KC & Company, Keri, Kerodex 51, Kiss dipropylene glycol, distearlydimonium chloride, distearyldi My Face, La Bella, Lac-Hydrin Five, LactiCare, Lady Esther, 25 monium, emulsifiers, ethoxydiglycol, ethylene brassylate, Lander, Lanolar, Lantiseptic, Little Forest, Lubrex, Lubrid ethylhexyl P-methoxycinnamate, glycerin, eucalyptol, euca erm, MG-217, Moisturel, Nate Naturals, Naturade, Natural lyptus oil, fumaric acid, gelatin, glucose, glyceryl dilaurate, ife, Nature's Apothecary, Natures Family, Nature's Gate, glycolic acid, glycoproteins, glysine, GMS/PEG 100 stear Neutrogena, Nivea, Noxzema, Nutraderm, Nutra-E, Nutrad ate, guar gum, hexyl laurate, hyaluronic acid, hydrogenated erm, Nutraplu, Oilatum Ad, Oil of Olay, Optimum Series, 30 castor oil, hydrogenated lanolin, hydrogenated polyisobu Orange Daily, Pacquin, Palmers, Pen-Kera, Perfect Solu tane, hydrolyzed animal protein, hydroxyethylcellulose, imi tions, Petal Fresh, Plenitude, Pond's, Porcelana, Prax, Pretty dazolidinyl urea, isocetyl stearate, isodecyl oleate, isohexa Feet & Hands, Proteque, Purpose, Queen Helene, Revlon, decane, isopropyl isostearate, isopropyl myristate, isopropyl Rex Eme, RoC, Rose Milk, Sarah Michaels, Sarna, Sea palmitate, isostearic acid, isostearyl alcohol, isoStearylben Breeze, SFC, Seba Nil, Shepard's, Shikai, Simply Be Well, 35 Zoate, isotearyl neopentandate, kaolin (natural clay), lactic Soft Sense, State of Mind, St. Ives Swiss Formula, Stik, acid, lanolin, diazolidinyl urea, laureth-23, laureth-4, laureth Stretch Mark, Suave, Sudden Change, Sundance, Sween, The 7, lauroyl lysine, linoleamidopropyl pg-dimonium chloride Healing Garden, Theraplex, Triple Lanolin, University Medi phosphate, linseed oil, magnesium ascorbyl phosphate, mag cal, U-Lactin, Ultra Mide 25, Vanicream, Vaseline, Vas Pet, nesium sulfate, malic acid, menthol, menthyl anthranilate, Vital Care, Vitec, Wibi, Wild Yam Complex, Woltra, Xpres 40 menthyl lactate, methoxypropylgluconamide, methyl glu sions, Yardley's of London, Zim’s Crack Creme, and prod ceth-20, methylcellulose, methylchloroisothiazolinone, ucts produced by high-end and generic manufacturers. methylisothiazol, methylisothiazolinone, mineral oil, mink Bioactive glass is particularly useful in these products oil, monoglyceride citrate, myristyl lactate, myristyl since it possesses anti-inflammatory and antimicrobial prop myristate, neopentylglycol dicaprylate/dicaprate, nylon-12, erties. The mild abrasive and high pH in certain formulations 45 octyl hydroxystearate, octyl methoxycinamate, PEG-8 bees generate an exfoliant effect on the skin to remove wrinkles. In wax, phenylbenzimidazole Sulfonic acid, octyl methoxycin addition, these formulations which incorporate bioactive namate, octyl palmitate, octyl salicylate, octyldodecanol, glass may be used to hide shadows created by wrinkles. octyldodecyl myristate, octyldodecyl neopentanotate, oleyl Skin formulations comprising bioactive glass also provide sarcosin, oxybenzone, palm oil, palmitic acid, PEG 100 stear a protective HCA layer on the corneal layer of the skin. In 50 ate, PEG-10 soya sterol, PEG-100 stearate, PEG-15 cocam addition, the anti-inflammatory action of bioactive glass ine, PEG-4 dilaurate, PEG-40 stearate, PEG-5 glyceryl Stear reduces redness and irritation while the anti-microbial action ate, PEG-50 stearate, PEG-8 distearate, PEG-8 stearate, disinfects. petrolatum, PG-dioctanoate, phenol, phenoxyethanol, phe Generally, facial moisturizing, anti-wrinkle, and eye care nylcarbinol, phenyldimethicone, phospholipids, polyacryla products or hand and body lotion products comprise an emol 55 mide, polyglyceryl-3 methyl glucose distearate, polyglyc lient, a preservative and collagen. eryl-4 isostearate, polyglycerylmethacrylate, polyoxyl 40 Common formulations of facial moisturizing, anti stearate, polysorbate 20, polysorbate 40, polysorbate 60, wrinkle, and eye care products and hand and body lotion potassium hydroxide, potassium Sorbate, potassium Stearate, products comprise water, glycerin, Stearic acid, aloegel, gly progesterone USP propylene glycol, PVM/MA decadiene col stearate, soya sterol, lecithin, dimethicone, glyceryl Stear 60 crosspolymer, PVP/eicosene copolymer, PVP/hexadecene ate, cetyl alcohol, magnesium aluminum silicate, fragrance, copolymer, pyridoxine HCL (vitamin B6), quaternium-15, carbomer, stearamide AMP methylparaben, DMDM hydan resorcinol, retinyl palmitate, Saccharide isomerate, salicylic toin, iodopropynl, butycarbamate, disodium EDTA, butylene acid, SD alcohol 40-b, shea butter, silk amino acid, sodium glycol, titanium dioxide, various mineral, fruit, vegetable, benzoate, Sodium borate, sodium calcium alginate, sodium and vitamin extracts and various coloring agents. 65 carbomer, sodium chloride, sodium DNA, sodium hyalur Facial moisturizing, anti-wrinkle, and eye care products onate, Sodium isostearoyl lactylate, Sodium lauryl Sulfate, and hand and body lotion products may also include one or Sodium PCA, sodium pyruvate, Sodium Stearate, Sorbic acid, US 8,551,508 B2 33 Sorbitan laurate, Sorbitan Stearate, Sorbitol, soybean oil, spe -continued cial petrolatum fraction, squalane, Steapyrium chloride, Stearamide dea, Stearamidopropyl PG-dimonium chloride INGREDIENTS wt % A wt % B wt % C phosphate, Steareth-2, Steareth-21, Stearoxytrimethylsilane, Part C stearyl alcohol, tea, tea-acrylates/c10-30 alkyl acrylate cros Propylene Glycol 3.0 3.0 3.0 spolymer, tea-carbomer 941, TEA-stearate, tetrasodium Jaguar 13S O.3 O.3 O.3 EDTA, trans-vector-delivery system (lipo copolymer com Part D plex), tricitrate, tricaprin, tridecyl Stearate, tridecyl trimelli tate, triethanolamine, triisocetyl citrate, trilaurin, trisodium Tac USP 8.O 10 Bioglass 45 S (c) 1.6 L 8.0 EDTA, trolamine, urea, wool wax, alcohol, collagen, elastin, Bioglass 58s (a) 0.77. 8.O propylparaben, PEG-40, sodium cetearyl sulfate, stearyl Part E alcohol, quaterinium-22, Sodium hydroxide and silica. The present invention provides for novel formulations of Germaben II 1.O 1.O 1.O facial moisturizing, anti-wrinkle, and eye care products and hand and body lotion products by incorporating bioactive 15 glass into a combination of any of the above-listed ingredi Observations: Both 34 B and 34 Chave more even appli entS. cation than 34A (the talc formulation) and both feel much less Examples 9 and 10 below provide exemplary embodiments oily than 34A after drying. 34C is less oily than 34 B. of skin lotion/makeup base and cream foundation makeup Foot Care Products formulations incorporating bioactive glass, including sol-gel The present invention includes novel formulations which derived bioactive glass. incorporate bioactive glass into various brands of foot care Example 9 products including products directed to treating athlete's 25 foot, fungal conditions and odor, as well as foot pumice Composition of Skin Lotion/Makeup Base with products such as the products marketed under the brand names Absorbine Jr. Aftate, Aloe Vesta, Alpha Hydrox, BFI, Sol-Gel-Derived Bioactive Glass Baza, Blis-to-Sol, Brite-Life, Carrington, Cruex, Desenex, Desert Essence, Dr. Scholls, Earth Therapeutics, Fougera, 30 Freeman, Fungi Care, Fungiclear, FungiCure, Funginail, Fungi Nail, Fungus Stop, Gold Bond, Health at Home, INGREDIENTS wt % Johnson's, LA Cross, Lamisil, Lotrimin, Mavis, Micatin, Mineral Oil (70ssu) 2O.O Miconazole, Neutrogena, NP-27, Odor-Eaters, Orly, Out Polawax (R) S.O grow, Parex, Pinaud, Podiacin, Pretty Feet & Hands, Quin Glycerin 2.0 35 sana, St. Ives Swiss Formula, Sween, Tetterine, Tinactin, Deionized Water 65.4 Jaguar C-14S O.S Ting, Ting AF, Trim, TripleCare, Vaseline, Zeasorb, and prod Phenobact 1.O ucts produced by high-end and generic manufacturers. Fragrance (High End Botanicals AFF #ACR2492019E) O.1 Foot care formulations comprising bioactive glass are anti Citric Acid monohydrate powder 2.0 microbial and create a soothing effect. The anti-microbial Schott Glass sol-gel-derived bioactive glass 4.0 40 effect of bioactive glass includes antifugal properties making 1OOO bioactive glass particularly well-suited for foot care products. In addition, the hygroscopic properties of bioactive glass help to reduce foot moisture. Bioactive glass also can be used to Example 10 create or be incorporated into a foot pumice. For example, 45 powders may be sintered by any acceptable method to form a Cream Foundation Makeup with Bioglass Formulas porous solid material for use in a foot pumice. CPD3-34 A, B, C Generally, foot care products comprise the active ingredi entallylamine, azole, griseofulvin, oxiconazole or tolnaftate. 50 Common formulations of foot care products comprise active ingredients consisting of a combination of tolnaftate, Zinc undecylenate, miconazole, nitrate, corn starch, Zinc INGREDIENTS wt % A wt % B wt % C oxide, kaolin and benzethonium chloride. PartA Foot care products may also include one or more of the 55 following inactive ingredients: acetone, acrylate copolymer, Crodafos CES 3.0 3.0 3.0 Volpo 10 O.8 O.8 O.8 aldioxa, behenoxy dimethicone, calendula, carbohydrate Volpo 3 O.6 O6 O.6 acrylic copolymer, ceteareth-6, chloroxylenol, diazolidinyl Jojoba Oil 1O.O 1O.O 1O.O urea, edetate disodium, fragrance, imidurea, iodine, isobu Cyclomethicone D5 S.O S.O S.O tane, isopropyl myristate, menthol, microporous cellulose, Part B 60 monobasic sodium phosphate, Stearamidoethyl diethy Deionized Water 59.9 59.9 59.9 lamine, myristyl myristate, polysorbate 60, polysorbate 80, NaOH O.1 O.1 O.1 potassium iodide, quaternium, SD alcohol 40, Sodium bicar Volpo 10 O.1 O.1 O.1 bonate, Stearalkonium hectorite, Stearamidoethyl diethy TiO, 7.0 7.0 7.0 Yellow Iron Oxide O.8 O.8 O.8 lamine, Stearic acid, Stearyl alcohol, talc, thymol, triglyceryl Red Iron Oxide O.3 O.3 O.3 65 disoStearate, wormwood oil, Xanthan gum, water, salicylic 50:50 Black Brown Iron Oxide Blend O.1 O.1 O.1 acid, methyl salicylate, bentonite, camphor, benzethonium chloride, terbinafine hydrochloride, benzyl alcohol, cetyl US 8,551,508 B2 35 36 alcohol, cetyl palmitate, sodium hydroxide, Sorbitan BFI, Blue Star, Boil Ease, Brite-Life, Campho-Phenique, monostearate, starch, magnesium Stearate and various herbal, Carraklenz, Clinipad, Clocream, Dermoplast, Dyna-hex, plant and mineral extracts. Family Medic, Flex-All, Fougera, Glover's, Gold Bond, The present invention provides for novel formulations of Good Sense, Hibiclens, Hibistat, Humco, Iodex, Johnson & foot care products by incorporating bioactive glass into a 5 Johnson, Lanabiotic, Lanacort, Lander, Lanocane, Lavocal, combination of any of the above-listed ingredients. Medi-Quik, Mentholatum, Mineral Ice, Myciguent, Mycitra Anti-Itch Products cin, Neosporin, Nexcare, Polysporin, Resinol, Sayman, Sen The present invention includes novel formulations which Sogard, Spectrocin, Sportscreme, Stopain, Swan, Top Care, incorporate bioactive glass into various brands of anti-itch Unguentine, Vicks, Zephiran Chloride, and products pro products such as the products marketed under the brand 10 names A&D Ointment, After Bite, Americaine, Aquaphor, duced by high-end and generic manufacturers. Arctic Spray, Aveeno, Baciguent, Bactine, Benadryl, Beta Generally, antibacterial, antiseptic, antibiotic and first 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, 15 Common formulations of antibacterial, antiseptic, antibi Itch-X, Ivarest, Ivy Block, Ivy-Dry, KeriCort-10, Lanabiotic, otic, and first aid products comprise active ingredients con Lanacane, Lanacort, Lotrimin, Medi-Quik, Micatin, Mycitra sisting of a combination of polymyxin B sulfate, bacitracin cin, Neosporin, Nupercainal, Polysporin, Rhuli, Samol-HC, Zinc, neomycin and pramoxine hydrochloride. Solarcaine, Sting Kill, Tecnu, Tegrin, Tinactin, Unguentine, Antibacterial, antiseptic, antibiotic, and first aid products and products produced by high-end and generic manufactur may also include one or more of the following inactive ingre CS. dients: bacitracin, benzalkonium chloride, benzoic acid, bis Generally, anti-itch products comprise the active ingredi muth-formiciodide, butylparaben, camphor, cholesterolized ent benzocaine, novacaine or bacitracin. ointment, citric acid, base, dibasic sodium phosphate, edetate Common formulations of anti-itch products comprise disodium, emulsifying wax, isopropyl alcohol, licocaine active ingredients consisting of a combination of camphor, 25 hydrochloride, glycerin, hydrogen peroxide, imidurea, iso benzocaine, pramoxine hydrochloride, Zinc acetate or hydro propyl alcohol, light mineral oil, magnesium carbonate, men cortisone. thol, methylparaben, microcrystalline wax, Octoxynol-9, pet Anti-itch products may also include one or more of the rolatum, phosphoric acid, poloxamer 188, polymyxin B following inactive ingredients: 1-hexadecanol, 5-chloro-2- Sulfate, potassium Sorate, pramoxine HC1, propylene glycol, methyl-4-isothiazolin-3-one (and) 2-met, acetic acid, adhe 30 silica, Sodium benzoate, Sodium lauryl Sulfate, sodium mat sives, alcohol, aloe Vera, aluminum Sulfate, ammonia, benza abisulfite, thymoli, tocopheryl acetate, water, white petrola lkonium chloride, benzyl alcohol, bisabolol, butylene glycol, tum and zinc phenol sulfenate. calamine, calcium acetate, carbomer, ceresin, ceteareth-20, The present invention provides for novel formulations of cetearyl alcohol, ceteth-2, cetyl alcohol, cetylpalmitate, chlo antibacterial, antiseptic, antibiotic, and first aid products by rothymol, citric acid, coal tar Solution, diazolidinyl urea, 35 incorporating bioactive glass into a combination of any of the dimethicone, dioctyl Sodium SulfoSuccinate, diphenhy above-listed ingredients. dramine HCl, disodium EDTA, distearlydimonium chloride, Formulations of particulate bioactive glass yield a compo edetate disodium, ethoxydiglycol, fragrance, glycerin, glyc sition which is capable of dramatically reducing the amount eryl Stearate SE, glyceryl tribehenate, hydroxypropyl meth of time necessary for wound healing to occur and can aug ylcellulose, hydroxypropylcellulose, iodopropyl butylcar 40 ment the natural healing process. The effect of these formu bamate, isobutane (propellant), isopropanol, isopropyl lations is most dramatically illustrated in the immune com alcohol, isopropyl myristate, isopropyl palmitate, isostearyl promised patient whose ability to heal wounds is somewhat neopentanoate, karaya, laneth-16, lanolin, laureth-23, Suppressed. lidocaine hydrochloride, maltodextrin, menthol, menthol, Particulate bioactive glasses which are useful in treating isopropyl alcohol, methyl gluceth-20, methyl salicylate, 45 wounds, burns, and abrasions typically have the following methylparaben, mineral oil, oatmeal flour, octoxynol-9, olive composition by weight percentage: oil, panthenol, PEG-2 oleate, petrolatum, polyethylene gly col, polysorbate 40, potassium hydroxide, potato dextrin, PPG-1 trideceth-6, propylene glycol, propylparaben, SD alcohol 38-b, SD alcohol 40, sodium acrylates copolymer, 50 Component Percent Sodium borate, sodium cetearyl Sulfate, Sodium chloride, SiO2 40-60 Sodium citrate, Sodium lauryl Sulfate, Steareth-2, Steareth-21, CaO 10-30 Stearic acid, Stearyl alcohol, styrenefacrylates copolymer, Sul NaO 1O-35 POs 2-8 fated castor oil, thymol, titanium dioxide, tocopheryl acetate, CaF2 O-2S triethanolamine, various coloring agents, water, white petro 55 B2O3 O-10 latum, white wax, Zinc oxide, Zinc pyrithione, paraffin, yel KO O-8 low wax, maltodextrin, and various fruit, vegetable, mineral MgO O-5 and vitamin extracts. The present invention provides for novel formulations of The preferred composition of the bioactive glass is: anti-itch products by incorporating bioactive glass into a 60 combination of any of the above-listed ingredients. Antibacterial, Antiseptic, Antibiotic and First Aid Products SiO2 45 The present invention includes novel formulations which CaO 24.5 incorporate bioactive glass into various brands of antibacte Na2O 24.5 rial, antiseptic, antibiotic and first aid products such as the 65 POs 6 products marketed under the brand names Absorbine, B-D, Baciguent, Bactine, Bag Balm, Ben Gay, Betadine, Betasept, US 8,551,508 B2 37 38 The preferred particle size range for the bioactive glass is applied to a wound, burn, or abrasion followed by application small and less than 90 microns is recommended. Particle sizes of the bandage. Alternatively, other two part delivery systems less than 10 microns as well as less than 2 microns can also be may be used. used. Particles of Such a small size range generally are effec Soap and Bath Salt Products tive without illiciting any undesirable immune response. The present invention includes novel formulations which Topical antibiotics are antibiotics suitable for skin treat incorporate bioactive glass into various brands of bath and ment. Examples of Such antibiotics include: chlorampheni shower Soap in bar, liquid, gel form and bath salts such as the col, chlortetracycline, clyndamycin, clioquinol, erythromy products marketed under the brand names Abra, Alba cin, framycetin, gramicidin, fusidic acid, gentamicin, Botanica, Albolene, Aloe Vera 80, Alpha Hydrox, Aroma, 10 Aura Cacia, Aussie, Aveeno, Baby Magic, Balmex, Bare mafenide, mupiroicin, neomycin, polymyxin B, bacitracin, Elegance, Basis, Body & Earth, Bodycology, Bubble Factory, silver sulfadiazine, tetracycline and chlortetracycline. Those Burt’s Bees, Calgon, Camay, Capri, Caress, Carrington, of ordinary skill in the art will appreciate that there are other Cashmere Bouquet, Cetaphil, Clairol, Clearasil, Clearly appropriate topical antibiotics Such as those listed in Natural, , Conti Castile, Cuticura, Dermalab, Desert U.S.P.D., for example. 15 Essence, , Dove, Earth Therapeutics, Eucerin, Exorex, The bioactive glass and topical antibiotic can be combined Fa, Fels Naptha. Formula 405, Gillette, Grandpa's, Humco, in any pharmaceutically acceptable carrier to facilitate appli , Ivory, Jason, Jean Nate, Jergens, Johnson & cation to a wound, burn, or abrasion. These compositions can Johnson, Johnson's, Keri, Kirks Castile, Kiss My Face, Lava, be combined with an ointment, white petrolatum, mineral oil Lever 2000, LifeBuoy, Lindora, Lowila, Lubriderm, Lux, and other substances known to those of ordinary skill in the Masada, Moisturel, Nate Naturals, Naturade, Nature's Gate, art. Neutrogena, Nivea, No Rinse, Noxzema, Oil of Olay, Oila These bioactive glass and topical antibiotic compositions tum, Packer's, , PanOxyl Bar, Phisoderm, Polytar, may also be combined with other wound, burn and abrasion Purell, Pure & Natural, Pure Pleasure, Purpose, Revlon, Safe treatments or dressings such as collagen, fibrin, fibronectin, guard, San Francisco Soap, Sarah Michaels, Sayman, Shield, Vitamin E. gauze, cotton, cellulosic, synthetic wound or burn 25 Shikai, Simply Be Well, , Stiefel, St. Ives Swiss dressings and other wound or burn dressingS/treatments Formula, State of Mind, Suave, Summer's Eve, Sween, The known to those of ordinary skill in the art. Dressings of Healing Garden, Toms of Maine, Tone, Ultra Swim, Vase fiberglass and fiberglass made from fibers of bioactive glass line, Vel Beauty Bar, Village Naturals, White Rain, Yardley's can also be used. of London, Zest, and products produced by high-end and Bioactive glass may also be used to a skin grafting particu 30 generic manufacturers. The anti-microbial properties of bioactive glass are par late bioactive glass may be added to the graft before it is ticularly useful in soap formulations. In addition, since soap placed in its intended location. The graft may also be further making is generally an anhydrous process, creating Such for treated with a topical antibiotic prior to placement. The appli mulations is a relatively straightforward process. Bioactive cation of bioglass to grafts is intended to increase the likeli 35 glass having certain particle sizes, create an abrasive effect hood that the graft will “take and incorporate in the hostbed. and are particularly well-suited for certain hand Soaps (i.e., While not being bound to any particular theory or mecha “Lava'). In addition, bioactive glass may be spheroidized for nism, it is believed that the high surface area and reactivity of facial Soap similar to polymer beads included in certain facial particulate bioactive glass provides for a release of sodium cleaners. which increases pH and increase oxygen in the wound or burn 40 Anti-inflammatory properties of bioactive glass are par which otherwise has a lower pH. This has an antimicrobial ticularly useful in both soak and anti-itch Soak products. Such effect when bioactive glass is used and when used in combi novel products reduce redness and skin irritation. nation with an antibiotic permits the antibiotic to function by Generally, bath and shower soap in bar, liquid and gel form activating various growth factors implicated in tissue repair. and bath salt products comprise sodium or ammonium These reactions cause a higher negative Surface charge on the 45 hydroxide, tallow, coconut or palm kernel oil and fragrance. glass Surface and the development of a high specific Surface Common formulations of bath and shower Soap in bar, area (e.g., from 0.5 m2/gby 12 hours) which attracts collagen, liquid, and gel form and bath salt products comprise triclo fibronectin and cells. Moreover, the bioactive glass provides carboin, Soap, Sodium tallowate, sodium pamitate, sodium for the precipitation of calcium and phosphorous naturally cocoate, palm kernelate types, water, PEG-6, methyl ether, present in wound exudate and blood which cause the rapid 50 fragrance, glycerin, Sorbitol, Sodium chloride, tetra sodium formation of a calcium and phosphate layer that may incor etibronate, pentasodium pentetate, BHT and various coloring porate collagen, fibrin and fibronectin to stabilize the wound agents. quickly and effectively. In some cases, wounds, burns, or Bath and shower soap in bar, liquid, and gel form and bath abrasions healed with the composition or method of the may also include one or more of the following: acetamidopro present invention heal without the necessity of scab forma 55 pyl trimonium chloride, alkyl aryl polyether alcohol, allan tion. That is, new epithelial tissue is formed directly. toin, aminomethyl propanol, ammonium laureth Sulfate, When bioactive glass is to be used in combination with an ammonium lauryl Sulfate, behenamidopropyl pg-dimonium antibiotic it is preferable to mix the particulate bioactive glass chloride, benzopheonone 4, BHT, biotin, boric acid, C12-15 and the antibiotic just before application to wound, burn, or alkylbenzoate, calcium pantothenate, carbomer, cetyl alco abrasion. Accordingly, bioactive particulate glass and a topi 60 hol, chromium hydroxide green, cocamide DEA, cocami cal antibiotic may be incorporated into a two part system dopropyl oxide, cocoa butter, cocobetane PEG 18, cocoglyc wherein bioactive glass and topical antibiotic are mixed and eryl ether Sulfonate, coconut fatty acid, corn oil, cottonseed simultaneously applied. For example, a two part mixing oil, decylglucoside, diazolidinyl urea, dimethicone, dimethi Syringe with two separate storage chambers and a mixing cone copolyol, disodium cocoyl, disodium EDTA, disodium chamber can be used. Other two part systems could also be 65 phosphate, EDTA, ethoxydiglycol, ethyl alcohol, etidonic used. For example, particulate bioactive glass can be incor acid, etidronic acid, glyceryl laurate, glycol Stearate, gly porated into a bandage and the topical antibiotic can be colipids, guar hydroxypropyltrimonium chloride, hexylene US 8,551,508 B2 39 40 glycol, hydrolyzed silk protein, hydroxpropyl, hydroxypro Formula, Stiff Stuff, Style, Suave, Superset, Tegrin, The Dry pyl methylcellulose, imidazolidinyl urea, iodopropylbutyl Look, Theorie, Thermasilk. Thicker Fuller Hair, Tigi, Tom's carbamate, isopropyl lanolate, isopropyl myristate, lanolin of Maine, Top Brass, Tres Flores, Tresemme, Ultimate Look, oil, lauramide DEA, lauramide MEA, laureth-10, laureth-23, UltraSwim, University Medical, Vaseline, Venture, Vidal Sas lauric acid, lauryl alcohol, lauryl Sulfate, lecithin, lemon soon, Vital Care, Vitalis, White Rain, Wildroot, Willow Lake, juice, linoleamide DEA, magnesium cocoate, magnesium Youth Hair, Zincon, and products produced by high-end and laurate, magnesium Stearate, methylgluceth-10, methylglu generic manufacturers. ceth-20, methylcellulose, methylchloroisothiazolinone, Generally, shampoo and hair detangling products comprise methylisothiazolinone, methylparaben, mineral oil, oleate? ammonium lauryl Sulfonate, triethanolamine, lauramide cocoate, oleyl alcohol, oleyl lactate, palm acid, palmitic acid, 10 DEA, lecithin, glycol Stearate, methylparaben and methyl paraffin, PEG 55 propylene glycol oleate, PEG 7 glyceryl isothiozoline. cocoate, PEG-12, PEG-120 methyl glucose dioleate, PEG Bioactive glass and sol-gel derived bioactive glass can 20, PEG-3 distearate, PEG-5M, PEG-75, PEG-8, PEG-90M, react with aqueous fluids to form a solution that is rich in petrolatum, phenoxyethanol, polyduaternium-10, inorganic elements, such as calcium, phosphorous, Sodium polycuaternium-22, polysorbate 20, PPG-5-ceteth-20, pro 15 and silicon. Incorporating bioactive glass into Such hair care pylene glycol, propylparaben, retinyl palmitate, silk peptide, products allows these inorganic elements to precipitate on Sodium benzoate, sodium citrate, sodium cocglyceryl ether hair to form a mineralogical layer (i.e., hydroxyapatite). This Sulfonate, sodium cocoylglutamate, Sodium cocoylisethion mineralogical layer is expected to add strength to hair, while ate, sodium dodecylbenzene Sulfonate, Sodium dodecylben also possibly improving the “softness” and “style-ability” of Zenesulfonate, sodium formate, Sodium hydroxide, sodium hair. In addition, bioactive glass provides an anti-microbial isethionate, Sodium laurate, sodium laureth Sulfate, sodium effect which reduces the occurrence of dandruff. laureth Sulfate, Sodium lauroyl lactylate, sodium lauroylsar Common formulations of shampoo and hair detangling cosinate, sodium myreth Sulfate, sodium palm kernelate, products comprise water, ammonium laureth Sulfate, ammo Sodium ricinoleate, sodium Stearate, Sodium styrenefacry nium lauryl Sulfate, glycol distearate, dimethicone, cocamide lates copolymer, Sodium styrenel acrylates/divinylbenzene 25 MEA, cetyl alcohol, fragrance, polymethacrylamidopropyl. copolymer, Sodium sulfate, Stearamidopropyl PG-dimonium trimonium chloride, sodium citrate, DMDM hydantoin, chloride phosphate, Stearic acid, Sunflower seed oil, tallow sodium chloride, PEG-14M, dihydrogenated tallowmidoet acid, tealauryl Sulfate, tea-oleate, TEA-Stearate, titanium hylhydroxyethylmonium, disodium EDTA, phenoxyethanol, dioxide, tocopheryl acetate, triclosan, Sodium c 14-16 olefin citric acid, methyldibromoglutaronitrile, ammonium Xylene sulfonate, triethanolamine, trisodium EDTA, trisodium etidr 30 Sulfonate and various coloring agents. onate, trisodium HEDTA, ultramarine blue, sodium laureth Shampoo and hair detangling products may also include sulfate, water, disodium laureth sulfosuccinate, cocami one or more of the following: 2-oleamido-1,3-octadecanediol dopropyl betaine, sodium laureth-13 carboxylate, fragrance, (ceramide-r), acetamide MEA, acrylates/C10-30 alkyl acry glycerin, panthenol, aloe gel, ammonium chloride, DMDM late crosspolymer, acrylic acid polymer (carbomer 1342), hydantoin, PEG-150 distearate, glycol distearate, citric acid, 35 alcohol, aloe Vera gel, aluminum starch octenylsuccinate, polycuaternium-7, cocamide MEA, tetrasodium EDTA, lau amodimethicone, arginine, benzophenone-3, benzophenone reth-7. Various coloring agents, and various plant, mineral and 4, biotin, butylated hydroxytoluene, butylene glycol, butylpa Vitamin extracts. raben, carbomer, carboxylic acid, cetrimonium chloride, The present invention provides for novel formulations of chloroxylenol, coal tar distillate, cocamide DEA, cocamide bath and shower Soap in bar, liquid, and gel form and bath salt 40 MIPA, cocamidopropyl betaine, cocamidopropyl hydrox products by incorporating bioactive glass into a combination ySultaine, cocamidopropylamine oxide, cocobetaine, cocodi of any of the above-listed ingredients. monium hydroxypropyl hydrolyzed hair keratin, cocotrimo Shampoo Detangling, , Hair Gel and Hair Spray nium chloride, cyclomethicone, cysteine, DEA Products methoxycinnamate, decyl polyglucose, diazolidinyl urea, The present invention includes novel formulations which 45 dimethiconol, dimethyl ether, disodium cocoamphodiac incorporate bioactive glass into various brands of shampoo, etate, disodium laureth SulfoSuccinate, disodium lauroam hair detangling, hairmousse, hair gel and hairspray products phodiacetate, disodium oleamido MEA SulfoSuccinate, diso Such as the products marketed under the brand names Adorn, dium phosphate, disodium ricinoleamido, ergocalciferol, Agree, Alberto VO5, Allercreme, Aloe Vera 80, American ethylparaben, glycerin distearyldimonium chloride, glycerin, Crew, Aqua Net, Aussie, Aussie Land, Baby Magic, Balsam, 50 glycol Stearate, glycosaminoglycans, guar hydroxypropyltri Breck, Brite-Life, Brylcreem, Citre Shine, Clairol, Color monium chloride, hydrochloric acid, hydrolyzed animal pro Soft, Condition 3-in-1, Consort, Cortexx, DeepEarth, Deno tein, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed rex, Dep, DHS, Dippity-Do, Dry Look, Dry Style, Elta, Euro silk, hydrolyzed vegetable protein, hydrolyzed wheat protein, pean Mystique, Final Net, Finesse, Flex, Free and Clear, hydrolyzed wheat starch, hydrolyzed yeast, hydroxypropyl Freeman, Freeze It, Frizz Control, Frizz Ease, Garden Bot 55 guar hydroxypropyltrimonium chloride, hydroxypropyl anika, Gillette, Good Sense, Groom Clean, Hask, Head & methylcellulose, hydroxypropyltrimonium hydrolyzed Shoulders, Henna Gold, Herbold, Infusium 23, Ionil T, Ivory, wheat protein, imidazolidinyl urea, inositol, iodopropyl Jason, Jeris, Jheri Redding, Jhirmack, John Frieda, Johnson & butylcarbamate, iodopropynyl butylcarbamate, isobutane, Johnson, Johnson's, Joico, Kiss Kids, Kiss My Face, La isolaureth-6, isostearamidopropyl morpholine lactate, kera Bella, L.A. Looks, Landers, Looney Tunes, L'Oreal, Loving 60 tin amino acids, ketoconazole, lactamide MEA, lauramide Care, Marci Gelle, Mane in Tail, Mink Difference, Nestle, DEA, lauramphoglycinate, laureth-10, laureth-23, laureth-4, Neutrogena, Nexxus, Nizoral, No Rinse, Ogilvie, Pantene, laureth-6, lauryl alcohol, lecithin, magnesium citrate, mag Paul Mitchell, Perma Soft, Pert Plus, Physique, Pinaud, Pro nesium laureth Sulfate, measulfoSuccinate, menthol, meth tein 29, Pro-V. Prell, Progaine, Psssssst, Queen Helene, Rave, enamine, methoxypropylgluconamide, methylchloroisothia Redken, Revlon, Royal Crown, Russ Kalvin's Generic, Salon 65 Zolinone, methylisothiazolinone, methylparaben, mica, Grafix, Salon Selectives, Salon Style, Scalpicin, Sebastian, octoxynol-40, octyl Dimethyl PABA, octyl hydroxystearate, Sebucare, Sebulex, Sebutane, Selsun Blue, St. Ives Swiss octyl methoxycinamate, olealkonium chloride, palmitic acid, US 8,551,508 B2 41 42 pantethine, panthenol, panthenyl ethyl ether, pantothenic tin, hydrolyzed soy protein, hydrolyzed wheat protein, hydro acid, PEG-12, PEG-120 methyl glucose dioleate, PEG-15 lyzed wheat starch, hydrophilic polyether polyurethane, coco polyamine, PEG-150 distearate, PEG-23M, PEG-27 hydroxyethyl cellulose, hydroxypropyl guar, hydroxypropyl lanolin, PEG-55 propylene glycol oleate, PEG-60 almond methylcellulose, iodopropynylbutylcarbamate, isododecane, glycerides, PEG-600, PEG-7 glyceryl cocoate, PEG-80 sor isopropyl alcohol, isosteareth-10, keratin protein, lactamide bitan laurate, phosphoric acid, phytantriol, phytic acid, MEA, laneth-16, lauramide DEA, lauramide MEA, laureth polyduaternium-16, polyduaternium-10, polyduaternium 11, laureth-23, laureth-4, laureth-7, laureth-9, lecithin, 11, polyduaternium-30, polyduaternium-4, polyduaternium linoleamidopropyl, linoleic acid, lysine, lysine hydroxypro 46, polyduaternium-7, polysorbate 20, polysorbate 80, potas pyl trimonium chloride, methylchloroiosothiazolinone, sium cocoylhydrolyzed collagen, potassium sorbate, PPG-12 10 methylchloroisothiazolinone, methylchloroisothiazolinone, buteth-16, PPG-5 laureth 5, PPG-9, propylene glycol, propy methylisothiazoline, methylisothiazolinone, methylparaben, lparaben, pyrithione Zinc, quaternium-15, quaternium-22, mineral oil, myristoyl hydrolyzed collagen, niacinamide, SD quaternium-75, quaternium-80, retinyl palmitate, ricinolea alcohol 40, nonoxynol-10, octyl hydroxyStearate, octyl sali midopropyl ethyldimonium ethosulfate, SD alcohol 40, cylate, octylacrylamide? acrylates copolymer, octylacryla serum protein, silk amino acids, silk protein, silsesquioxane 15 mide/acrylates/butylaminoethyl meth, octylmethoxycin copolymer, sodium benzoate, sodium C14-17 alkyl SEC sul namate, olealkonium chloride, oleic acid, oleth 20, oleth-16, fonate, Sodium cocoyl sarcosinate, Sodium glutamate, palmitic acid, palmitoyl myristyl serinate, PEG-15 cocamine Sodium hydroxide, Sodium hydroxymethyglycinate, sodium chloride, PEG-40 hydrogenated castor oil, PEG-6 cocamide, laureth sulfate, sodium laureth-13 carboxylate, sodium lau PEG-60 hydrogenated castor oil, PEG-75 lanolin, PEG-8 riminodipropionate, sodium lauroyl sarcosinate, Sodium lau Sorbitol, phenoxyethanol, phenyl trimethicone, phospholip ryl Sulfate, sodium methylparaben, Sodium myreth Sulfate, ids, phytantriol, polyacrylamide, polyduaternium-11, Sodium oleth Sulfate, Sodium phosphate, sodium styrene? polyduaternium-46, polyduaternium-7, polysorbate 20, acrylates/divinylbenzene copolymer, Sodium Sulfate, sodium polysorbate 80, polyZophenone-4, potassium dimethicone trideceth sulfate, solubilized coal tar extract, soluble col copolyol panthenyl phosphate, potassium hydroxide, potas lagen, soyamide DEA, stearyl alcohol, talloweth-60 myristyl 25 sium sorbate, PPG-12-PEG-50 lanolin, PPG-5-ceteth-20, glycol, TEA-dodecylbenzenesulfonate, TEA-dodecylphe PPG-9 diethylmonium chloride, proline, PVP. pyridoxine nylsulfonate, TEA-laurylsulfate, tetrasodium EDTA, tissular HCL, quaternium-15, retinyl palmitate, ribonucleic acid, fluid extract, titanium dioxide, tocopheryl acetate, topical tar serine, silk amino acids, silk protein, Sodium benzoate, solution, trideceth-12, triethanolamine lauryl sulfate, trim sodium C13-15 pareth-8 butyl phosphate, sodium C13-15 ethylsilylamodimethicone, wheat oligosaccharides, wheat 30 pareth-8 phosphate, sodium C14-16 olefin sulfonate, sodium germamidopropyl dimethylamine, Xanthan gum, yeast chloride, Sodium cocoyl isethionate, sodium hydroxymeth extract, hydrolyzed soy protein, sodium PCA, ethoxydigly ylglycinate (amino acid derived), sodium PCA, sorbitol, col, linoleamidopropyl PG-dimonium chloride phosphate, soyamide DEA, stearalkonium chloride, steareth-16, ste hydrogenated polydecene, trimethylolpropane, phenoxy areth-2, Stearic acid, Stearyl alcohol, tea-dodecylbenzene ethanol and various fruit, mineral and vitamin extracts. 35 sulfonate, tetrasodium EDTA, threonine, tocopheryl acetate, The present invention provides for novel formulations of trideceth-12, triethanolamine, trisopropanolamine, urethane/ shampoo and hair detangling products by incorporating bio C1-C20 peg alkyl copolymer, VA/crotonates/vinyl neodecan active glass into a combination of any of the above-listed date copolymer, various fruit, plant, vitamin extracts, wheat ingredients. germamidopropyl ethyldimonium ethosulfate, yeast extract, Generally, hair mousse, hair gel and hair spray products 40 isobutane, AMP-isostearoylhydrolyzed soy protein, butylene comprise mineral oil, lanolin, Stearic acid and Zinc pyrithione. glycol, and SD alcohol 40. Common formulations of hair mousse, hair gel, and hair The present invention provides for novel formulations of spray products comprise water, isobutane, polyduaternium-4. hair mousse, hair gel, and hairspray products by incorporat propane, propylene glycol, C9-11 pareth-8, DMDM hydan ing bioactive glass into a combination of any of the above toin, fragrance, panthenol, disodium EDTA, panthenyl ethyl 45 listed ingredients. ether, pantethine, lauramine oxide, keratin amino acids and The antimicrobial and pH effects of bioactive glass are citric acid. particularly useful in shampoo and other hair care products to Hair mousse, hair gel, and hair spray products may also reduce bacteria and to normalize the pH level of hair. In include one or more of the following: acetamide MEA, acry addition, the ability of bioactive glass to release minerals late copolymer, acrylates/dimethicone/methacrylate copoly 50 which bind to the hair surface is useful for enhancing hair mer, alanine, alcohol denat, allantoin, aminoethylpropanol, strength, body, and Volume. aminomethyl propanol, ammonium benzoate, ammonium Examples 11-13 below provide exemplary embodiments hydroxide, amodimethicone, arachidonic acid, arginine, of shampoo formulations incorporating bioactive glass, ascorbyl palmitate, behenic acid, benzophenone-3, ben including Sol-gel-derived bioactive glass. Zophenone-4, betaine, boric acid, butyl ester of PVM/MA 55 copolymer, C13-14 isoparaffin, calcium pantothenate, car Example 11 bomer, carbopol, catalase, cetearyl octanoate, ceteth-16, cet eth-20, cetrimonium bromide, cetrimonium chloride, cetyl Composition of Hair Shampoo with Bioactive Glass alcohol, chlorhexidine dihydrochloride, cocamide DEA, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, 60 collagen, cyclomethicone, DEA-methoxycinnamate, diazo lidinyl urea, diisobutyl adipate, dimethicone copolyol, dime thiconol, dimethyl ether, dimethyl lauramine isostearate, INGREDIENTS wt % dimethyl Stearamine, dioctyl sebacate, distearly dimonium Standapol ES-2 3O.O chloride, ethosulfate, ethyl ester of PVM/MA copolymer, 65 Crosultaine C-50 1O.O ethyldimonium, gelatin, glutamic acid, glycerin, glycine, Foamid C S.O hyaluronic acid, hydrofluorocarbon 152A, hydrolyzed elas US 8,551,508 B2 44 -continued Hammer, Arrid XX, Ban, Banish, Brut, Certain Dri, Clearly Fresh & Natural, Crystal Clean, Crystal Stick, Degree, Desert INGREDIENTS wt % Essence, Dove, Dry Idea, English Leather, Gillette, Hi & Dri, Deionized Water 47.3 Jason, Jockey Club, Kiss My Face, Lady Crystal, Lady Jaguar C-14S O.S Mitchum, Lady , Lady's Choice, , Phenobact 1.O Mitchum, Nair, Nature's Gate, Nautica, Nullo, Old Spice, Fragrance (Wildberry AFF #24551) O.2 Pinaud, Power Stick, Revlon Hi & Dri, Right Guard, Secret, Citric Acid monohydrate powder 3.0 Soft & Dry, Speed Stick, Suave, Sure, , Tom's of Schott Glass Bioactive (<4Lave. part. size) 3.0 Maine, Tussy, Soft & Dri, Yodora, and products produced by 10 high-end and generic manufacturers. The anti-microbial and hygroscopic properties of bioactive glass in deodorant and anti-perspirant formulation control Example 12 odor causing bacteria, while the anti-inflammatory properties reduce underarm irritation. Bioactive glass may be incorpo Hair with 45s5 Glass 15 rated into Solidamorphous forms, similar to deodorant "crys tals'. A wipe with the polished solid form also has an anti microbial effect. Three Separate Formulas: CPD3-15A, B, C, D Generally, anti-perspirant or deodorant products comprise aluminum chlorohydrate, aluminum chloride, Zirconium chlorides or triclosan. Common formulations of anti-perspirant and deodorant INGREDIENTS wt %. A wt % B wt % C wt % D products in Stick, roll-on, aerosol, creme, pad, and powder Standapol ES-2 3O.O 3O.O 3O.O 3O.O form comprise active ingredients consisting of aluminum Consultaine C-50 1O.O 1O.O 1O.O 1O.O Zirconium tetrachlorohydrex gly or aluminum chlorohydrate. Foamid C S.O S.O S.O S.O 25 Anti-perspirant and deodorant products may also include Deionized Water 48.0 48.0 48.0 48.0 one or more of the following: alcloxa, alcohol, allantoin, aloe Phenobact 1.O 1.O 1.O 1.O Citric Acid monohydrate powder 1.O 1.O veragel, aluminum chloride, PPG-14 butyl ether, cyclomethi Schott Glass 45s5 (<4Lave. S.O S.O cone, baking Soda, behenyl alcohol, benzethonium chloride, part. size) benzoic acid, BHT, C12-15 alkylbenzoate, C18-36 acid trig 30 lyceride, ceteareth-20, cetearyl alcohol, citric acid, corn 1OO.O 94.0 95.0 99.0 starch, cyclomethicone, cyclopentasiloxane, cyclotetrasilox ane, dibenzylidene sorbitol, dicaprylate/dicaprate, diisopro pyl adipate, diisopropyl sebacate, dimethicone, dipropylene Example 13 glycol, L. panthenol, farnesol, fragrance, glycerin, glyceryl 35 oleate, glyceryl Stearate, hectorite, hydrofluorocarbon 152A, Hair Shampoos with Bioactive Glass Formulas hydrogenated castor oil, hydrogenated polyisobutane, hydro CPD3-31 A, B, C, D genated vegetable oil, hydroxyethylcellulose, isobutane, iso propyl alcohol, isopropyl myristate, laureth-4, methylpara ben, mineral oil, myristyl myristate, octoxynol-9, octyl 40 isononanoate, octyl palmitate, octyldodecanol, PEG-100 stearate, PEG-20, PEG-25 propylene glycol stearate, PEG-8 INGREDIENTS wt %. A wt % B wt % C wt % D distearate, pentadecalactone, petrolatum, PG, phenyl trime Steo CS-230 3O.O 3O.O 3O.O 3O.O thicone, polyethylene, polyol, polysaccharides, polysorbate Crosultaine C-50 1O.O 1O.O 1O.O 1O.O 20, polythylene, potassium alum, potassium sorbate, PPG-14 Foamid C S.O S.O S.O S.O 45 butyl ether, PPG-1-PEG-9 lauryl glycol ether, propane, pro Deionized Water 49.O 48.0 47.0 46.0 Phenobact 1.O 1.O 1.O 1.O pylene carbonate, propylene glycol, propylparaben, purified Citric Acid monohydrate powder 1.O 2.0 3.0 clay, quaternium-18, SD alcohol 40, silica, silk powder, Bioglass (<5Lave. part. Size) S.O S.O S.O S.O sodium bicarbonate, sodium laureth 13 carboxylate, sodium Stearate, soyaethyl morpholinium ethosulfate, starch, Stearyl 1OO.O 1OO.O 1OOO 1OOO 50 alcohol, talc, T-butyl alcohol, T-butyl hydroquinone, tetraso dium EDTA, tribehenin, triclosan, triclosan, triethyl citrate, Initial pH Values urea, various coloring agents, various mineral and Vitamin pH 31A 8.9 extracts, vegetable oil, vegetable starches, water, Xanthan pH 31B 8.2 gum, Zinc oxide. pH 31C 5.7 55 The present invention provides for novel formulations of pH 31D 4.8 anti-perspirant and deodorant products by incorporating bio 24 Hour pH Values active glass into a combination of any of the above-listed pH-31A 9.6 ingredients. pH-31B 9.2 The antimicrobial, anti-inflammatory, and hygroscopic pH 31C 8.5 60 effects of bioactive glass are particularly useful in anti-per pH31D 7.2 spirant and deodorant products to reduce bacteria, odor and Anti-Perspirant and Deodorant Products moisture. The present invention includes novel formulations which Aftershave and Shaving Lotion Products incorporate bioactive glass into various brands of anti-perspi The present invention includes novel formulations which rant and deodorant products in powder, creme, roll-on, aero 65 incorporate bioactive glass into various brands of aftershave Sol and stick form Such as the products marketed under the and shaving lotion products such as the products marketed brand names 5 Day, Allercreme, Almay, Aqua Velva, Arm & under the brand names Aceite. Afta, Aqua Velva, Aspen, Brut, US 8,551,508 B2 45 46 Bump Fighter, Burt’s Bees, Earth Science, Edge, Flents, alcohol, lanolin oil, laureth-23, lecithin, menthol, methylpa Gillette, Hoyt Co., Ice Sport, Iodex, Jason, Jovan, Mennen, raben, milk protein, myristyl propionate, nonoxynol 10, oxi Old Spice, Pinaud, Pomada, Requa, Samborns, Saxon, Skin dized polyethylene, paraffin, PEG 14M, PEG 150 pentaeryth Bracer, Super Macho, Williams, and products produced by rity1 tetrastearate, PEG 6 caprylic/capric glycerides, pentane, high-end and generic manufacturers. pentasodium pentetate, petrolatum, phenycarbinol, polyeth Aftershave and shaving lotion formulations which include ylene, polyduaternium 10, polysorbate 20, polysorbate 60, bioactive glass provide excellent anti-inflammatory effects to potassium myristate, PPG-12-PEG-65, propane, propyl gal reduce post-shaving irritation. late, propylene glycol, propylparaben, resorcin, retinyl Generally, aftershave and shaving lotion products com palmitate, SD alcohol 40, Soap, Sodium benzoate, sodium prise propylene glycol, menthol and benzoic acid. 10 borate, sodium chloride, sodium lauryl Sulfate, Sodium meta Common formulations of aftershave and shaving lotion silicate, Sodium myristate, Stearyl alcohol, TEA Stearate, tea products comprise SD alcohol 40, water, glycerin, menthol, maleate, tetrasodium etibronate, titanium dioxide, tocopheryl fragrance, benzophenone-1 and various coloring agents. acetate, triclosan, isobutane, cyclomethicone, and C12-15 Aftershave and shaving lotion products may also include alkylbenzoate. one or more of the following: aloe extract, aluminum starch 15 The present invention provides for novel formulations of octenylsuccinate, benzoic acid, benzyl alcohol, BHT, C12-15 and gel products by incorporating bioactive alkylbenzoate, carbomer 980, cassava flour, cyclomethicone, glass into a combination of any of the above-listed ingredi dimethicone, disodium EDTA, ethylenediamine, isodecyl entS. oleate, isopropyl myristate, methylparaben, myristyl propi The antimicrobial effects of bioactive glass are particularly onate, panthenol, PEG/PPG-17/6 copolymer, PEG-60 hydro useful in shaving products to reduce bacteria and the possi genated castor oil, PG, phenoxyethanol, polysorbate 80, bility of infection from nicks and cuts inflicted during shav PPG-15, propylene glycol, SD alcohol 39-C, stearyl ether, 1ng. tetrahydroxypropyl, tocopheryl acetate, triethanolamine, Depilatory and Hair Bleaching Products various plant, fruit, and vitamin extracts, Xanthan gum, pro The present invention includes novel formulations which pylene glycol, benzoic acid, benzophenone-2, BHT, PG, and 25 incorporate bioactive glass into various brands of depilatory, benzyl alcohol. epilatory and hair bleaching products in cream, wax, and The present invention provides for novel formulations of powder form such as the products marketed under the brand aftershave and shaving lotion products by incorporating bio names Andrea, Ardell, Better-Off, Bikini Bare, Hair Off, active glass into a combination of any of the above-listed Jolen, Nair, Natural, Neet, Nudit, One Touch, Sally Hanson, ingredients. 30 Zip, and products produced by high-end and generic manu The anti-inflammatory effects of bioactive glass are par facturers. ticularly useful in aftershave and shaving lotion products to Generally, depilatory, epilatory, and hair bleaching prod reduce inflammation. ucts comprise the active ingredient calcium thioglycolate or Shaving Products calcium hydroxide. The present invention includes novel formulations which 35 Common formulations of depilatory, epilatory or hair incorporate bioactive glass into various brands of shaving bleaching products comprise water, mineral oil, calcium products in creme, gel, powder and Soap form such as the hydroxide, cetearyl alcohol, calcium thioglycolate, sodium products marketed under the brand names Afta, Alba thioglycolate, ceteareth-20, various floral and herbal, and Botanica, Aveeno, Barbasol, Brut, Bump Stopper, Burma Vitamin extracts, and various coloring agents. Shave, Burt’s Bees, CAM, , Earth Science, Edge, 40 Depilatory, epilatory and hair bleaching products may also Everready, Gillette, Jason, Kiss My Face, Lady Legs, Magic include one or more of the following: ammonium bicarbon Platinum, Magic Shaving Powder, Noxzema, Old Spice, Pal ate, benzalkonium chloride, camphor, cetyl alcohol, chamo molive, Pinaud, Remington, Requa, Rise, Shave in the mile extract, citric acid, dimethicone, fragrance, glyceryl Shower, , Skinmate, Skintimates, Soft Shave, Stearate, hydrogen peroxide, iron oxides, isopropyl myristate, Tom’s of Maine, Williams, and products produced by high 45 isopropyl palmitate, isopropyl Stearate, maltodextrin, octox end and generic manufacturers. ynol-9, pentaerythrityl tetracaprylate/caprate, petrolatum, Generally, shaving products in cream gel, powder, or Soap phosphoric acid, potassium Sorbate, SD alcohol 40, Stearami form comprise a moisturizer Such as aloegel and a protectant dopropyl dimethylamine, Stearyl Stearate, Sweet almond oil, Such as Stearic acid. calcium glyceryl Stearate, octyl palmitate, Stearic acid, pro Common formulations of shaving products cream gel, 50 pylene glycol, triethanolamine, imidazolidinyl urea, PEG powder, or soap powder comprise water, triethanolamine, 100 stearate, soluble collagen, lanolin alcohol, disodium palmitic acid, Stearic acid, isopentane, monoglycerides, Sor EDTA, carbomer, methylparaben, thioglycolate, Stearyl alco bitol, PEG-90M, PVP fragrance, isobutane, various coloring hol, and silica. agents, and various floral, Vitamin, and mineral extracts. The present invention provides for novel formulations of Shaving products in cream gel, powder, or soap form may 55 depilatory, epilatory, and wax products by incorporating bio also include one or more of the following: 1-dodecanol, allan active glass into a combination of any of the above-listed toin, aloe extract, aluminum starch octenylsuccinate, ammo ingredients. nium hydroxide, barium sulfide, behentrimonium methosul The anti-inflammatory and anti-microbial effects of bioac fate, benzaldehyde, benzophenone-1, benzyl alcohol. BHA, tive glass are particularly useful in depilatory, epilatory, and BHT bromelain, butane, C16 to C22, calcium carbonate, 60 wax products to reduce inflammation, bacteria, and odor. calcium hydroxide, calcium thioglycolate, carbomer, cellu Toothpaste Products lose polymer, cetearyl alcohol, cetyl alcohol, chlorhexidine Bioactive glass may also be incorporated into various gluconate, corn starch, diazolidinyl urea, dimethicone, dim brands of toothpaste products such as the products marketed ethyl Sulfate quaternized, dioctyl Succinate, esters with tri under the brand names Act, Aim, Aquafresh, Arm & Hammer, ethanolamine, fatty acid esters, glycerides, glycerin, glyceryl 65 Biore, Biotene, Boiron, Breath Remedy, Brite-Life, Butler, oleate, glyceryl Stearate, guanidine carbonate, hydroxyethy Cepacol, Close-Up, Colgate, Crest, Dentu-Creme. Desert cellulose, isopropyl myristate, isopropyl palmitate, lanolin Essence, Enamelon, Fixodent, Fresh N Brite, Gel-Kam, US 8,551,508 B2 47 48 Gleem, Interplak, Keep, Kids Dental Kare, Listerine, Menta limited to enamel, dentin, pulp, tooth root structure, cemen dent, Natural White, Nature's Gate, Orajel, Oral-B, Pearl tum, root dentin, coronal dentin, any dental manufacture, etc. props, Pepsodent, Plak Smacker, Plus+White, Pollident, For example, the following composition by weight will Q-Dent, Rembrandt, Sensodyne. Thermodent, Tom's of provide a bioactive glass Suitable for toothpaste and mouth Maine, Topol, , Ultra Plus, Vademecum, Viadent, 5 wash formulations: and products produced by high-end and generic manufactur CS. Generally, toothpaste products comprise fluoride, tri closan, pyrophosphates, silica, baking Soda, potassium nitrate Component Percent and natural and/or artificial flavoring. 10 SiO2 40-60 Common formulations of toothpaste products comprise CaO 10-30 sodium fluoride, water, sorbitol, hydrated silica, Zinc citrate Na2O 1O-35 trihydrate, sodium lauryl sulfate, SD alcohol 38-B, flavor, POs 2-8 CaF2 O-2S cellulose gum, Sodium saccharin, and various coloring B2O3 O-10 agents. 15 KO O-8 Toothpaste products may also include one or more of the MgO O-5 following: acesulfame potassium, alumina, ammonium chlo ride, beta-d-glucose, calcium peroxide, calcium Sulfate, car bomer, carboxymethylcellulose, citric acid, coenzyme Q10. Such bioactive glasses provide an efficacious material for dicalcium phosphate dihydrate, glycerin, hydrogen peroxide, interaction with the tooth structure and do not trigger an lactoperoxidase, glucose oxidase, lysozyme, magnesium overwhelmingly adverse immune response. chloride, methylparaben, microdent poloxamer, monoammo Bioactive glasses of specified particle sizes are particularly nium phosphate, papain, PEG 300, PEG 60, hydrogenated useful in toothpaste and mouthwash formulations especially castor oil, PEG-12, PEG-32, PEG-6, PEG-75, phosphoric when small and very small particles are combined. For acid, poloxamer 407, poloxapol 1220, Potassium Nitrate, 25 example, when compositions including Small particles that potassium Sorbate, potassium thiocyanate, propylene glycol, are capable of bonding with tooth structure (e.g., less than propylparaben, pyrophosphate, SD alcohol 38-B, Silica, sim about 90 microns) as well Smaller particles (e.g., less than ethicone, sodium benzoate, Sodium bicarbonate, Sodium car about 10) are used in combination, the larger of these particles bonate, Sodium carrageenan, Sodium chloride, Sodium citrate, adhere to tooth structure and act as ionic reservoirs while the Sorbitol and related polyols, sodium hydroxide, sodium lau 30 Smaller are capable of entering and lodging inside of various royl sarcosinate, Sodium monofluorophosphate, sodium tooth structure Surface irregularities. The larger of these par monofluurophosphate, sodium percarbonate, sodium phos ticles provide a reservoir of additional calcium and phospho phate, sodium tripolyphosphate, tetrapotassium pyrophos rous so that the mineralization, or depositing of the calcium phate, tetrasodium pyrophosphate, titanium dioxide, triso phosphate layer begun by the Small particles can continue. dium phosphate, PEG-8, various natural and artificial 35 Additional calcium and phosphorous can be leached to all flavorings, Xanthan gum, Zinc chloride, Zirconium silicate, tooth structure as well as to particles which have become thymol, methyl salicylate, and benzoic acid. attached to the inside or at the openings of surface irregulari Bioactive glass compositions are useful in, for example, ties of tooth structure such as dentinal tubules. This in turn enamel remiralization, incipient caries remineralization, cari provides for continuation of the entire reaction and continued ous dentin remineralization, caries prevention, arresting 40 decay, reversing decay, anti-caries, pit and fissure sealants, growth of the smaller of these particles which have lodged prophylactic pastes, fluoride treatments, dentinal sealants, inside or over the openings of Such surface irregularities and etc. Bioactive glass may be included in , liners, can result in effectively coating or filling the Surface irregu bases, gels, and restorative material e.g., packing, indirect larity. This excess concentration of ions of calcium and phos pulp capping agent, etc. Such compositions are also useful in 45 phorous is necessary for continued reaction of the Smaller of the treatment of surfaces after periodontal Surgery to decrease these particles to take place because the Smaller particles dentinal sensitivity and enhance tissue attachment. These quickly exhaust their ions as a result of their relatively high compositions are active in treating various defects associated surface area. The larger of these particles will react and with a variety of dental and other conditions and actually release their ions more slowly as a longer term effect. Fur chemically and physically bond to the tooth thereby reminer 50 thermore, the larger of these particles will mechanically alizing tooth structure. abrade the tooth Surface opening various Surface irregularities As referred to herein, remineralization is the formation of allowing Small particles to enter and react with the Surface hydroxyapatite. The formation of hydroxyapatite begins with irregularity. exposure of a bioactive glass composition to aqueous solu This effect is very beneficial in a variety of applications. tions. It is believed that the sodium ions (Na+) in the bioactive 55 For example, in preventing caries or decay, the composition glass exchanges with H+ ions in body fluids causing pH to of the present invention is capable of penetrating into the increase. Calcium and phosphorus then migrate from the depths of the Smallest of surface irregularities and receiving a bioactive glass forming a calcium-phosphorous rich Surface continued supply of ions from larger nearby particles so that layer. An underlying silica rich Zone slowly increases as the it is able to grow after exhausting its stored ion Supply. This is Sodium ion in the bioactive glass continues to exchange with 60 also very useful in sealing pits and fissures and a much more the hydrogen ion of the solution. After time, the calcium effective and long lasting seal is obtained. phosphorous rich layer crystallizes into a hydroxyapatite For some applications extremely small particles are used. material. Collagen can become structurally integrated with For example, particles that are in the range of 2 microns are the apatite agglomerates. An effective remineralizing amount used to fit inside dentin tubules that are approximately 1-2 refers to any amount capable of forming hydroxyapatite. 65 microns in diameter. The occlusion of these tubules leads to a As the term “a tooth structure' is used herein, it is intended significant reduction in the amount of sensitivity after, for to refer to any feature or features of a tooth including but not example, periodontal Surgery. A particularly effective com US 8,551,508 B2 49 50 bination includes a mixture of particles, wherein the mixture The addition of fluoride in bioactive glass compositions comprises particles less than 2 microns and particles more enhances and strengthens the tooth structure. Other examples than 45 microns. include Solgel glasses having, for example, about 40 to about Theses bioactive glass compositions generally do not 86% by weight SiO, substantially no amount of sodium, require time to set and are not easily washed away by about 6-36% by weight Ca and about 2-12% by weight P0s. mechanical abrasion caused by brushing, exposure to mild Bioactive glass compositions comprising extremely small acids in food, salivary flow or other liquids which normally particles may also be used. For example, particles that are in come in contact with the teeth. Such compositions can gen the range of 2 microns are beneficial. Particle size may be erally withstand significant agitation, rinsing with water and determined by Scanning electron microscopy or laser light long term soaking in simulated Saliva for five days. Moreover, 10 scattering techniques (e.g., Coulter LS100). As stated previ many of the Small particles do not require a set time because ously, relatively small bioactive particulate glass does not they begin to chemically react and adhere to tooth structure as generate a significant immune response. Moreover, it is gen Soon as they come into contact with these surfaces and fluids erally not engulfed by macrophages and rendered inactive. naturally present in the mouth. Although such compositions These compositions may be formulated as oral hygiene are effective with a single application, it is likely that multiple 15 compositions such as dentifrices, toothpaste, gels, powders, applications will be more efficacious. mouthwashes, irrigating solutions, and presentations for As previously noted, relatively small particulate bioactive Sucking or chewing Such as gums, pastilles, tablets, and loZ glass does not generate a significant immune response. More enges. Such oral hygiene compositions may comprise over, it is generally not engulfed by macrophages and ren between 0.1 to 50% by weight. Formulations comprising 1 to dered inactive. 25% by weight are preferable, while formulations comprising In addition, these bioactive glass compositions are capable 5 to 10% by weight of the bioactive glass are even more of providing a bioactive layer that will form a new structural preferable. layer which is a lasting remineralization of tooth structure. In addition to the active ingredients, suitable oral hygiene This has been verified by the reformation of a hydroxycar compositions may contain the usual carriers, binders, Surfac bonate apatite layer on dentin surfaces after treatment with 25 tants, humectants, coloring agents, pigments, antiplaque bioactive glass compositions with FourierTransform Infrared agents, anti-bacterial agents, bioadhesive-type agents, abra spectroscopy (FTIR). sives, anticaries agents, flavorings, Sweeteners, bulking Such bioactive glass compositions may comprise particles agents, and the like. having a particle size of about 20 microns with about 30 In the case of a toothpaste formulation, an abrasive typi percent of the particles less than 10 microns. Other formula 30 cally includes amorphous, gelled, precipitated, or fumed tions may comprise bioactive glass particles have an average silica, plastics particles, alumina, calcium carbonate, and Zinc particle size of 10 microns with at least 25% smaller than 2 orthophosphate, insoluble metaphosphates and calcium pyro microns. phosphate. Silica is an especially suitable abrasive. The bio These compositions may be formulated into toothpaste. In active glass particles may replace all, Some, or none of the fact, the particles may replace the silica currently used in 35 abrasive currently used in toothpastes. toothpastes. The addition of fluoride in the glass composition Inorganic thickeners may be included in the dentifrice's will enhance and strengthen the tooth structure. In addition to and further include fumed silicas such as Cabosil available direct application of the bioactive glass to the teeth, these from Cabot Corporation, and thickening silicas including bioactive glass compositions may also be applied in a saline those available from J. M. Huber designated Zeodent 165. or distilled water based medium. These compositions may 40 Organic thickeners such as natural and synthetic gums and also be formulated into mouthwash, gel or they may be colloids may also be incorporated in dentifrice compositions. applied by a dentist as a paste. Examples of Such thickeners include carrageenan (Irish These compositions can be used in methods for whitening, moss), Xanthan gum and sodium carboxymethyl cellulose, lightening or bleaching teeth. These methods are also useful starch, polyvinlpyrrolidone, hydroxyethyl propyl cellulose, for removing stains from teeth. These methods include con 45 hydroxbutyl methyl cellulose, hydroxypropyl methyl cellu tacting teeth with an effective tooth-whitening amount of lose, and hydroxyethyl cellulose (co-dried blends of microc bioactive glass, especially methods using multiple applica rystalline celluloselcellulose gum). The inorganic or organic tions. Each application may include between about 0.02 to 0.3 thickener may be incorporated in Such compositions at a grams of bioactive glass. Suitably, these methods of whiten concentration of about 0.05 to about 2% by weight and pref ing teeth comprise contacting the teeth with an effective 50 erably about 0.1 to about 1.5% by weight. tooth-whitening amount of bioactive glass twice daily for two Fluoride-providing salts having anti-caries efficacy may weeks or more. “Tooth-whitening amount generally refers to also be incorporated in the oral compositions and are charac any amount that will result in a Vita shade guide lightening of terized by their ability to release fluoride ions in water. It is one or more shades in a patient with a pre-treatment shade preferable to employ a water-soluble salt fluoride providing darker than A3.5 after 4 weeks of application twice daily for 55 about 10 to 5,000 ppm of fluoride ion and preferably about two minutes or more per application. 1000 to 1500 ppm of fluoride ion. Among these materials are Methods for whitening teeth may also comprise contacting water-soluble alkali metal salts, for example, sodium fluo teeth with an effective tooth-whitening amount of particulate ride, potassium fluoride, Sodium monofluorophosphate and bioactive and biocompatible glass comprising silicon oxide Sodium fluorosilicate. Sodium monofluorophosphate is a pre or hydroxide and optionally one or more elements such as Na, 60 ferred fluoride-providing salt. K, Ca, Mg, B, Ti, Al, P N or F. Pigments may include non-toxic, waterinsoluble inorganic Such bioactive glass compositions usually comprises at pigments such as titanium dioxide and chromium oxide least Na, Ca and P. although it is possible to use simple greens, ultramarine blues and pinks and ferric oxides as well Sodium silica glasses together with external sources of cal as waterinsoluble dye lakes prepared by extending calcium or cium and phosphate. An external source of calcium and phos 65 aluminum salts of FD&C dyes on alumina such as FD&C phate may be from saliva itself, or may beformulated into the Green #1 lake, FD&C Blue #2 lake, FD&C R&D #30 lake oral hygiene composition. and FD&C Yellow #15 lake. The pigments have a particle size US 8,551,508 B2 51 52 in the range of 5-1000 microns, preferably 250-500 microns, The present invention provides for novel formulations of and are present at a concentration of 0.5 to 3% by weight. mouthwash and mouth rinse products by incorporating bio Dyes are generally sensitive to the presence of the peroxide active glass into a combination of any of the above-listed ingredient and are not included in the dentifrice although ingredients. FD&C Green #3 has been found to be resistant to fading when 5 In addition to direct application of the bioactive glass to the CaO2 is present in the dentifrice. teeth, these bioactive glass compositions can also be applied Any suitable flavoring or Sweetening material may be in a saline or distilled water based medium. employed. Examples of Suitable flavoring ingredients are These oral formulations may be used together with a flavoring oils, e.g., oils of spearmint, peppermint, winter Source of calcium and/or phosphate in the manufacture of a green, Sassafras, clove, sage, eucalyptus, marjoram, cinna 10 mon, lemon, and orange, and methyl salicylate. Suitable composition for whitening teeth. Sweetening agents include Sucrose, lactose, maltose, Sorbitol, The antimicrobial and abrasive effects of bioactive glass Sodium cyclamate, perillartine, and Sodium saccharin. Suit are particularly useful in mouthwash and mouth rinse prod ably, flavor and Sweetening agents may together comprise ucts to reduce bacteria and to remove stains. from 0.01% to 5% or more of the preparations. 15 Eye Drop Products Various other materials may be incorporated into-these The present invention includes novel formulations which oral compositions. For example, preservatives, silicones and incorporate bioactive glass into various brands of eye drop chlorophyll compounds, vitamins such as vitamins B6, B12, products such as the products marketed under the brand C, E and K, antibacterial agents such as chlorhexidine, halo names Medic's Choice, Alcon, All Clear, Baush & Lomb, genated diphenyl ethers such as triclosan, desensitizing Bio, Tears Naturale, Clear Eyes, Murine Plus, Naphcon, agents such as potassium nitrate and potassium citrate and OcuClear, Opcon-A, Prefrin, Vasoclear, Visine, and products mixtures thereof may be included. These adjuvants are incor produced by high-end and generic manufacturers. porated in the dentifrice in amounts which do not Substan Generally, eye drop products comprise polyethylene glycol tially adversely affect the properties and characteristics 300, naphazoline hydrochloride and benzalkonium chloride. desired, and are selected and used in properamounts, depend 25 Eyedrop products may also include one of the following: ing upon the particular type of component involved. boric acid, edetate disodium, water, sodium borate, polyvinyl The making of gels, toothpastes, rinses, mouthwashes, alcohol, povidone, tetrahydrozoline hydrochloride, dextrose, gums, and chewing gums are well known in the art. Bioactive disodium EDTA, potassium chloride, water, sodium bicar glasses can be introduced into these products by a variety of bonate, sodium chloride, Sodium citrate, sodium phosphate, methods including simple mixing. In some circumstances it 30 oxymetazoline HCl, hydroxpropyl methyl cellulose, phe will be necessary to keep the bioactive glass from coming into niramine maleate, liquifilm, phenylephrine HCl, sodium contact with the aqueous or other components of the delivery acetate, sodium thiosulfate and hydrochloric acid. vehicle to prevent the bioactive glass from pre-reacting. This The present invention provides for novel formulations of can be accomplished in a number of ways including, for eye drop products by incorporating bioactive glass into a example, two piece Syringes with a mixing chamber. 35 combination of any of the above-listed ingredients. Mouthwash and Mouth Rinse Products Contact Lens Treatment Products The present invention includes novel formulations which Bioactive glass may also be incorporated into various incorporate bioactive glass into various brands of mouthwash brands of contact lens treatment products, including cleaning and mouth rinse products such as the products marketed Solutions for hard and soft lens, Saline solutions, and rewet under the brand names Act, Doctor Tichenor, Glyoxide Anti 40 ting Solutions, such as the products marketed under the brand septic, Betadine, Biotene, Cepacol, Colgate, Good Sense, names Alcon, Allergan, Barnes Hind, Bausch & Lomb, Bos Lavoris, Listerine, Listermint, Plax, Reach, Rembrandt, Sali ton, Ciba, Clean-N-Soak, Clerz Z. Liquifilm, Opti-Soak, vart, Scope, Signal, Targon, Tom's of Maine, Viadent, Vince, ProFree, Resolve, Soac-Lens, Wet-N-Soak, Alcon, Allergan, Weleda, and products produced by high-end and generic Ciba Vision, Complete, Lens Plus, Miraflow, Opti-Clean, manufacturers. 45 Opti-Free, Opti-Zyme, Pliagel, ReNu, Sensitive Eyes, Ultra Generally, mouthwash and mouth rinse products comprise Zyme, drugstore.com, Softwear, Unisol, Clear Eyes, Clerz Z. fluoride, antibacterial agents, hydrogen peroxide and sodium Opti-One, and products produced by high-end and generic carbonate. manufacturers. Common formulations of mouthwash and mouth rinse Generally, contact lens treatment products comprise boric products comprise thymol, eucaluptol, methyl salicylate 50 acid, sodium chloride, thimersol, and edetate disodium. menthol, water, alcohol, benzoic acid, poloxamer 407, Contact lens treatment products may also include one or Sodium benzoate, and caramel. more of the following: benzalkonium chloride, alkyl ether Mouthwash and mouth rinse products may also include Sulfate, ethoxylated alkyl phenol, tri-quaternary cocoa-based one or more of the following: aloe Vera, calcium chloride, phospholipid, silica gel, titanium dioxide, fragrance, phe calcium lactate, cetylpyridinium chloride, citric acid, domi 55 nylmercuric nitrate, polyvinyl alcohol, anionic detergents, phen bromide, glucono delta lactone, glucose oxidase, glyc sodium phosphates, polysorbate 80, hydroxyethyl cellulose, erin, hydrogenated Starch, hydroxyethylcellulose, lactofer polycuad, papain, cocoamphocarboxyglycinate, Sodium lau rin, lactoperoxidase, lysozyme, magnesium chloride, ryl Sulfate, hexylene glycol, pancreatin, tyloxapol, Sorbic methylparaben, natural and artificial flavorings, nitrogen, acid, Subitilisin A, poloxame 407, amphoteric 10, tween 21 poloxamer 237, polysorbate 20, polysorbate 80, potassium 60 stabilizer, microclens, potassium chloride, proteolytic chloride, potassium phosphate, povidone-iodine, propylene enzyme, sodium carbonate, poloxamine, Sodium borate, iso glycol, Saccharin, Saccharin Sodium, SD alcohol 38-B, tonic saline, antimicrobial buffer system, Sodium perborate, Sodium carboxymethylcellolose, sodium chloride, sodium hydrogen peroxide, phosphonic acid, nitrogen, borate buffer citrate, sodium gluconate, Sodium hydroxide, Sodium lauryl system, water, EDTA, caramide, glycerin, and povidine. Sulfate, Sodium saccharin, Sorbitol, Sodium pyrophosphate, 65 In addition, bioactive glass may be added to or included in various natural and artificial flavorings, Xanthan gum, Xylitol, eardrops and nose drops to provide or enhance anti-bacterial, Zinc chloride and Zinc oxide. anti-inflammatory, and hygroscopic effects. US 8,551,508 B2 53 54 Bioactive glass also may be added to or incorporated into allergic hypersensitivity was present following the use of any nail files, e.g., fingernail and toenail files. The anti-inflamma of the protypte cosmetic compositions comprising bioactive tory properties of bioactive glass make it particularly well glass. suited for use with such nail care devices. Patch testing represents a Sound, relatively safe and rea In addition, bioactive glass may be used with men's or 5 sonable reliable method for identifying allergens. A positive women's shaving devices, including but not limited to dis reaction to a correctly applied patch-test proves that the per posable and electric razors. The antibacterial and anti-inflam son has a contact sensitivity to the Substance tested, but not matory properties of bioactive glass make it well-suited for necessarily that the Substance is the cause of the clinical use in Such products. dermatitis. Bioactive glass may also be added to or included in oral 10 In patch testing, the Suspected topical allergen has to pen care products such as Ambisol. The anti-inflammatory and etrate the stratum corneum to the viable (effector) cells of the antimicrobial properties of bioactive glass can be beneficial in skin to present a local challenge to the immune system. Such products. Methods: The product to be tested is applied on a patch of Example 14 below provides exemplary embodiments of 15 filter paper, placed on an impermeable sheet and fixed to the additional prototype cosmetic formulations incorporating skin with adhesive tape (Leukotest(R), Fa. Hartmann). Test bioactive glass, including sol-gel-derived bioactive glass. site: inner side of the forearm. The test patch is left in place for 24 hours then removed. The examination by the dermatolo Example 14 gist follows. A second and third examination are performed after 48 and 72 hours by the dermatologist. Additional Protype Cosmetic Formulations All assessments were performed under standard lighting conditions by the responsible dermatologist. Several prototype cosmetic products comprising bioactive Panellists were instructed to keep the test sites dry over the glass were developed as follows. application period. 1. A Soft focus cosmetic product was developed and com 25 Results: Under the conditions of this test no evidence of prised a sol-gel-derived bioactive glass powder mixed with a primary irritation or allergic hypersensitivity was present. commercially available facial cream. This product gave the None of the thirty patch-tests resulted in positive reactions appearance of wrinkle reduction and skin-tightening when after 24, 48 and 72 hours. The tested products are considered applied to the face. safe for use. 2. A shampoo product, containing 5 wt % of 4 um bioactive 30 Examples 16 and 17 below provide the results of inhibition glass formulated in a combination of Standapol ES-2, Cro Zone tests and demonstrates the anti-microbial effects of bio Sultaine C-50, Foamid C. deionized H0, Phenobact and citric active glass. The anti-microbial effects of bioactive glass are acid. useful in many of the cosmetic formulations described above. 3. A nail-hardening/protecting gel, containing gelled jojoba oil or glycerin and a PemulenR polymer, or glycerin, water, Example 16 citric acid, Jaguar C-14S and phenobact. 4. Makeup formulas, containing gelled jojoba oil and with Inhibition Zone Test Lubrajel(R) MS with various pigments 5. A skin lotion/makeup, containing Polawax, mineral oil, 40 Liquid Caso agar or Sabouraud agar was mixed with the glycerin, Jaguar C14-S, citric acid, Phenobact, colorant and corresponding test organism (target: 10 CFU/plate) and fragrance poured into petri dishes. After the agar had cooled, a disk 6. A Sunscreen product, containing gelled jojoba oil, octyl (approx. 1 cm in diameter) was punched out of the agar and methoxycinnamate and benzophenone-3 was filled with approximately 0.5g 45S (BioaglassTM) bio 7. A deodorant stick containing 8% bioactive glass and com 45 active glass powder. The agar was stored for 2 hours at 5°C. position MV00/036/02/01 and Subsequently incubated. After completion of the incuba 8. A deodorant stick containing 8% bioactive glass and com tion period (1-5 days), the samples were checked for inhibi position MV00/036/01/01 tion Zone formation and growth. 9. A deodorant stick containing 5% bioactive glass and com The test organisms used were: position MV00/030/02/01 50 Bacillus subtilis ATCC 6633 10. A deodorant cream containing 50% bioactive glass and Staphylococcus aureus ATCC 6538 composition MV00/036/03/01 Pseudomonas aeruginosa ATCC 9027 11. A nail hardening creme containing 15% bioactive glass Candida albicans ATCC 10231 and composition MV00/036/04/01A. Aspergillus niger ATCC 16404 12. A nail hardening creme containing 30% bioactive glass 55 Results: and composition MV00/036/04/01B Size of Inhibition Zone in mm Per Sample Batch Example 15 below demonstrates that the cosmetic formu lations comprising bioactive glass, including sol-gel-derived bioactive glass, do not irritate the skin or result in any per ceivable allergic hypersensitivity. 60 Test organism Batch No. Example 15 Bacilius subtiis 1 2 3 1 day 5 5 3 2 days 2 2 1 Skin Sensitivity Tests 3 days 2 1 1 65 5 days 2 O O Several prototype products (Bioglass (30% utl.) in an O/W- Formulation) were tested to determine if skin irritation or US 8,551,508 B2 56 Pseudomonas aeruginosa ATCC 9027 Candida albicans ATCC 10231 Test organism Batch No. Aspergillus niger ATCC 16404 Staphylococcusatiretts 1 2 3 Results: Organism count using different amounts of glass 5 powder 1 day 4 4 4 2 days 3 3 2 3 days 3 3 2 5 days 3 2 2 Test organism Content of glass in Ing 10 Bacilius subtilis 10 100 2OO 500 1OOO 1 day >1O >1O >10 O O 2 days >10 >105 >104 O O Test organism Batch No. 3 days >10 >105 >104 O O 5 days >1O >10 -- Pseudomonas aeruginosa 1 2 3 15 1 day 4 4 3 2 days 2 2 1 3 days 2 2 O 5 days 2 O O Test organism Staphylococcits Content of glass in Ing

(iiietis 10 100 2OO 500 1OOO 1 day >1O >1O >10 O O Test organism Batch No. 2 days >10 >105 >104 O O 25 3 days >10 >105 >104 O O Candida albicans 1 2 3 5 days >1O >10 -- 1 day 3 3 3 2 days O 1 1 3 days O O O 5 days O O O 30 Test organism Pseudomonas Content of glass in ng aeruginosa 10 100 200 500 1OOO Test organism Batch No. 1 day >1O >10 >10' O O 35 2 days >10 >105 >104 O O Aspergilius niger 1 2 3 3 days >10 >105 >104 O O 5 days >10 >105 -- 1 day 5 5 5 2 days 5 5 4 3 days 3 3 2 5 days 2 2 O 40 pH controls on nutrient media without seeding with microor Test organism Content of glass in Ing ganisms, but in the presence of the sample resulted in the Candida albicans 10 100 2OO 500 1OOO following: 45 1 day >10 >105 O O O 2 days >10 >10 >300 O O 3 days >10 >10 >300 O O 5 days >10 >105 ------on glass powder: pH >= 10 on agar near glass powder pH 9.5 on agar (periphery): pH 8.5 50 (control plate without glass powder: pH 7.5)

Test organism Content of glass in Ing Example 17 Aspergilius niger 10 100 2OO 500 1OOO 55 1 day n.d. n.d. n.d. n.d. n.d. Concentration Dependent Inhibition Test 2 days >10 s.300 >30 O O 3 days >10 >300 >30 O O Liquid Caso agar or Sabouraud agar was mixed with the 5 days >10 ------corresponding test organism (target: 10 CFU/plate) as well as variable amounts (see chart below) of 45S bioactive glass 60 + = growth detectable after subcultivation powder and poured into petri dishes. The agar was stored for - = no growth detectable after subcultivation 2 hours at 5°C. and subsequently incubated. After completion n.d. = not performed of the incubation period (1-5 days) the samples were checked The antimicrobial effect of bioactive glass could be for inhibition Zone formation and growth. detected both in the inhibition Zone test as shown in Example The test organisms used were: 65 16 and as a function of concentration as shown in Example 17. Bacillus subtilis ATCC 6633 The reduction in microbial growth correlates with a pH Staphylococcus aureus ATCC 6538 increase in the medium. US 8,551,508 B2 57 58 Examples 18 and 19 below demonstrate the effect of bio Stability test S990046 (for V99/020/02/02e) active glass on a variety of microorganisms. Stability test S990030 (for V99/020/03/01h) Stability test S990047 (for V99/020/03/02e) Results: Example 18 Aqueous Supernatent Except for Aspergillus niger, all load tests show a logical Microbiological Test Series course of the test series. From a concentration of between 3% and 5% of bioactive Microbiological test series with individual microorgan glass, no growth is detectable even after 6 load cycles. Bio isms of an aqueous solution of bioactive glass (clear Super active glass is most effective against Staphylococcus aureus. natant), O/W emulsion, W/O emulsion each with different 10 Aspergillus niger, starting from the 4th load cycle, no concentrations of bioactive glass. longer shows any growth inhibition. Bioactive glass is effec Conditions: tive against Aspergillus niger at higher concentrations up to Individual microorganism Suspension the 4th load cycle. (Note: this result is not surprising since With common salt (in the aqueous Solution) Aspergillus niger, compared to other species, frequently pre pH value unchanged 15 sents a problem with other preservation systems as well.) Non-sterilized aqueous Solution O/W Emulsion/W/O Emulsion Arrangement: Even at lower concentrations of bioactive glass (2%), a Overview tables of load test of individual microorganisms clear preservative effect is observed. But here, too, Aspergil Test formulas V.99/020/01/11-19 (aqueous supernatant) lus niger exhibits the behavior described above. Test formulas V99/020/02/01a-h (O/W emulsion) Stability (a-h-different concentrations BioGlas/none to 0.2% S990O29=OFW emulsion base V99/020/02/01 h=0.2% VSM12650) VSM12650 Test formulas V99/020/02/02a-f (O/W emulsion) Normal test: -7°C./40° C.; stable (a-f-different concentrations BioGlas/none to 20% Extreme test: =14°C./60° C.; separation in 3rd cycle VSM12650) S990O46=O/W emulsion base V99/020/02/O2e=20% Test formulas V99/020/03/01a-h (W/O emulsion) 25 VSM12650 (a-h-different concentration BioGlas/none to 0.2% Normal test: stable VSM12650) Extreme test: stable Test formulas V99/020/03/02a-f (W/O emulsion) S990030=W/O emulsion base (a-f-different concentration BioGlas/none to 20% VSM12650 VSM12650) 30 Normal test: separation after 3rd cycle Load test MB990669-713 (aqueous supernatant) Extreme test: n/a Load test MB990714-743 (O/W emulsion) S990047=W/O emulsion base V99/020/03/02e=20% Load test MB990744-773 (W/O emulsion) VSM12650 Stability test S990029 (for V99/020/02/01h) Separation of emulsion even before the start of the test series.

LOAD TEST with BIOGLAS ASPERGILLUSNIGER Test Series 3A V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99,020 O2/O2 OWEmulsion V99,02003/02 WO Emulsion

Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 Aqueous Solution (Supernatant without Sediment) (V99/020/01/11-19)

O.S90 ------+++ Explanation: O.8% ------+++ Cycle 0: Smear without 196 ------+++ inoculation 296 ------+++ Cycles 1-6: inoculated 3% ------+++ with above species 59 ------+++ Concentration in Sample 10% ------+++ container; ca. 10 15% ------20% ------O/W Emulsion (V99/020/02/02)

296 ------+++ Explanation: 59 -- + Cycle 0: Smear without 10% inoculation 15% ------++ Cycles 1-6: inoculated 20% ------++ with above species Blank test ------+++ Concentration in Sample container; ca. 10 Blank test: without BioGlas W/O Emulsion (V99/020/03/02)

296 ------+++ Explanation: 59 ------+ Cycle 0: Smear without 10% ------inoculation 15% Cycles 1-6: inoculated US 8,551,508 B2 59 60 -continued

LOAD TEST with BIOGLAS ASPERGILLUSNIGER Test Series 3A V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99,020 O2/O2 OWEmulsion V99.020,0302WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 20% with above species Blank test ------+++ Concentration in Sample container; ca. 10 Blank test: without BioGlas

RESULTS OF LOAD TEST with BIOGLAS CANDIDA ALBICANS Test Series 3B V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99,020 O2/O2 OWEmulsion V99.020,0302WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 Aqueous Solution (Supernatant without Sediment) (V99/020/01/11-19)

O.S9/o ------+++ Explanation: O.8% ------+++ Cycle 0: Smear without 190 ------+++ inoculation 2% ---- +++ Cycles 1-6: inoculated 3% with above species 59% Concentration in Sample 10% container; ca. 10 15% 20%

2% Explanation: 59% Cycle 0: Smear without 10% inoculation 15% Cycles 1-6: inoculated 20% with above species Blank test ------+++ Concentration in Sample container; ca. 10 Blank test: without BioGlas W/O Emulsion (V99/020/03/02) 2% ------+++ Explanation: 59% -- Cycle 0: Smear without 10% inoculation 15% Cycles 1-6: inoculated 20% with above species Blank test ------+++ Concentration in Sample container; ca. 10 Blank test: without BioGlas

LOAD TEST with BIOGLAS ESCHERICHLA COLI Test Series 3C V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99.020,0202 OWEmulsion V99,02003/02 WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 Aqueous Solution (Supernatant without Sediment) (V99/020/01/11-19)

O.S9/o ------+++ Explanation: O.8% -- Cycle 0: Smear without US 8,551,508 B2 61 62 -continued

LOAD TEST with BIOGLAS ESCHERICHLA COLI Test Series 3C V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99.020,0202 OWEmulsion V99,02003/02 WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

190 ------+++ inoculation 2% +++ Cycles 1-6: 3% inoculated with above 59% species 10% Concentration in 15% sample container: ca. 20% - 106

2% Explanation: 59% Cycle 0: Smear without 10% (+) inoculation 15% Cycles 1-6: 20% inoculated with above Blank test species Concentration in sample container: ca. 106 Blank test: without BioGlas W/O Emulsion (V99/020/03/02) 2% -- (+) (++) (++) Explanation: 59% Cycle 0: Smear without 10% inoculation 15% Cycles 1-6: 20% inoculated with above Blank test ++ species Concentration in sample container: ca. 106 Blank test: without BioGlas

(+), (++): contamination with foreign microorganisms

LOAD TEST with BIOGLAS PSEUDOMONAS AERUGINOSA Test Series 3D V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99,020 O2/O2 OWEmulsion V99.020,0302WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 Aqueous Solution (Supernatant without Sediment) (V99/020/01/11-19) O.S9/o ------+++ Explanation: O.8% ------+++ Cycle 0: Smear without 190 ------+++ inoculation 2% ------+++ Cycles 1-6: inoculated 3% ------+++ with above species 59% -- Concentration in Sample 10% container; ca. 10 15% 20%

2% Explanation: 59% Cycle 0: Smear without 10% inoculation 15% Cycles 1-6: inoculated 20% with above species Blank test Concentration in Sample container; ca. 10 Blank test: without BioGlas US 8,551,508 B2 63 -continued

LOAD TEST with BIOGLAS PSEUDOMONAS AERUGINOSA Test Series 3D V99/020/01/11-V99/020/01/19 Aqueous Solution/Supernatant V99,020 O2/O2 OWEmulsion V99.020,0302WO Emulsion Concentration Cycle O Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 W/O Emulsion (V99/020/03/02)

2% ------+++ Explanation: 59% Cycle 0: Smear without 10% inoculation 15% Cycles 1-6: inoculated 20% with above species Blank test ------+++ Concentration in Sample container; ca. 10 Blank test: without BioGlas

2O Example 19 -continued Microbiological Test Series A. niger 10 CFU/ml 25 pH Value Microbiological Test Series with individual microorgan Cons. No. before isms of selected O/W emulsion (V99/020/04/03 (G4)=new MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 start of test laboratory sample V99/020/06/01) 1000 a)2 ------10.9 Conditions: 1001 b) 5 11.6 individual microorganism Suspension 30 1002 c) 10 11.8 1003 d) 15 12.1 pH value changed to values typical in cosmetics (citric 1004 e) 20 12.2 acid) 1005 f) none ------7.1 non-sterilized Arrangement: C. albicans 10 CFU/ml 35 overview table of load test of individual microorganisms pH Value overview table of pH adjustment and change over time Cons. No. before test formulas V99/020/06/Ola-f MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 start of test load test MB991 000-1034 1006 a)2 10.9 Results/Conclusions: 40 1007 b).5 11.6 1008 c) 10 (+++P) - 11.8 Although, microorganism sterility with O/W emulsions is 1009 d) 15 12.1 difficult to achieve the first smear (blank) shows sterility 1010 e) 20 12.2 except for E. coli. In addition, despite selecting a suitable 1011 f) none ------7.1 O/W emulsion base this base has its own preservative effect against E. coli and Staphylococcus aureus. 45 The results from Example 19 indicate: 1. The pH value of the O/W base increases again in the course of the test series to the values before adjustment Load Test with Bioglas with citric acid. The pH value of the sample without Test Series 7B 50 Escherichia coli. Pseudomonas aeruginosa bioactive glass remains unchanged. V99/020/06/01 OW Emulsion (Dragil) 2. Microorganism growth is clearly inhibited. non-sterilepH non-adjusted

3 With high concentrations even a difficult to control Product organism Such as Aspergillus niger is effectively inhib NEOW Cream Test Number Prod. date Test start ited. 55 (Dragil) W99,020.06.01 Oct. 11, 1999 Oct. 15, 1999 4. High pH value correlates with microorganism inhibition. E. coli 107 CFU/ml pH Value Load Test with Bioglas Cons. No. before Test Series 7A 60 MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 start of test Aspergilius nigeri Candida albicans V99/020/06/01 OW Emulsion (Dragil) 1012 a)2 10.9 non-sterilepH non-adjusted 1013 b) 5 11.6 1014 c) 10 11.8 Product 1015 d) 15 12.1 NEOW Cream Test Number Prod. date Test start 1016 e) 20 12.2 (Dragil) W99,020.06.01 Oct. 11, 1999 Oct. 15, 1999 65 1017 f) none ------7.1 US 8,551,508 B2 65 66 -continued ing but not limited to, rugs woven from wool, various syn thetic fibers, and articles of clothing. Ps. aeruginosa 107 CFU/ml A traditional cleaning agent may be, for example, a com pH Value pound containing one or more Surfactants useful for dissolv Cons. No. before ing dirt in a solvent, especially in an aqueous solvent. Surfac MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 start of test tants are generally effective in cleaning grease or oily dirt. 1018 a) 2 10.9 However, other dirt, such as proteins or dirt containing pro 1019 b) 5 11.6 teins, e.g., blood, other staining Substances such as coffee or 102O c) 10 11.8 tea, as well as invisible dirt, including dirt from microorgan 1021 d) 15 12.1 10 isms, cannot be cleaned in this way alone. For this reason a 1022 e) 20 12.2 bleaching agent and/or disinfecting agent are usually added to 1023 f) none ------7.1 the cleaning formulations, so that the remaining dirt is at least removed to the point that it is no longer visible. Stains are usually removed oxidatively after the grease and pigment dirt 15 is dissolved. Load Test with Bioglas Oxidative removal is generally accomplished, for example, Test Series 7C with chlorine-containing chemicals. Chlorine-containing Staphylococcus aureus. Escherichia coli (pH adjusted) chemicals generally remove only the coloring part of the V99/020/06/01 OW Emulsion (Dragil) stain, whereas the other indissoluble substances remain with non-sterilepH non-adjusted the basic Substance. Because of its high reactivity, the disad Product Vantage of chlorine is that it aggressively attacks colored NEOW Cream Test Number Prod. date Test start Surfaces or Substances such as fabrics changing the color tone (Dragil) W99,020.06.01 Oct. 11, 1999 Oct. 15, 1999 or causing the colors to bleed. In addition, chlorine aggres St. aureus 107 CFU/ml sively attacks the Substance to be cleaned, especially fabrics, 25 so that their basic structure is destroyed after multiple wash pH Value ings. Cons. No. before Previous attempts to alleviate the oxidizing effect of chlo MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 start of test rine involved the use per-acetic acid. Although per-acetic acid 1024 a)2 10.9 has an adequate disinfecting effect, its ability to penetrate 1025 b) 5 11.6 30 porous material is insufficient, which in turn leads to an 1026 c) 10 11.8 unsatisfactory sterilization effect. In addition, per-acetic acid 1027 d) 15 12.1 1028 e) 20 12.2 has an oxidizing effect, although to a smaller degree. 1029 Ole 7.1 Although the oxidizing effect of per acetic acid may not create a color-destroying bleaching effect, in most cases its E. coli 107 CFU/ml (control measurement with adjusted pH value) 35 disinfecting effect is not sufficient. For this reason is not pH Value possible, for example, to remove aerobic spore producers. Cons. No. Now. Furthermore, the use of per-acids results in significant dam MB99 Bioglas % Blank Cycle 1 Cycle 2 Cycle 3 O9, 1999 age to Some materials, such as woolens. Accordingly, a goal of one embodiment of present inven 1030 a)2 ------8.5 40 1031 b) 5 10 tion is to produce cleaning agents which are non-toxic, yet 1032 c) 10 ---- 10 provide an antimicrobial effect, while also providing good 1033 d) 15 10 cleaning qualities. 1034 e) 20 10 Since bioactive glass releases Ca" ions, it was expected that the presence of bioactive glass in an aqueous solution Cleaning Agents 45 would significantly increase the hardness of the solution. It General was therefore expected that calcification would increase resulting in a reduction of cleaning action, so that these The present invention provides novel cleaning agent com glasses would not be suitable for use as washing and cleaning positions comprising bioactive glass. The present invention agents. Moreover, it was expected that the abrasive effect of also provides methods of making and using these novel non 50 glass particles would result in a mechanical damage of mate toxic cleaning agents. rials, especially in textiles, which would lead to a corrosion of Particulate bioactive glass and/or aqueous extracts of par the fabric. Nevertheless, applicants unexpectedly found that a ticulate bioactive glass can be added to standard household variety of effective cleaning agents could beformulated com cleaning agents as well as industrial cleaning agents. The prising bioactive glass. Surprisingly, the effectiveness of the resulting formulations provide cleaning agents with 55 washing agent is not hindered by the release of alkaline ions enhanced cleaning and anti-microbial properties. In addition and there is no increase in the hardness of the water or calci to the direct anti-microbial effects of bioactive glass, the fication. Also, these novel cleaning agents do not corrode or increased pH resulting from the presence of bioactive glass damage the materials being cleaned, especially textile fab also enhances cleaning. In addition, bioactive glass has a high rics, as feared through the addition of the glass particles. affinity for proteinaceous matter, such as blood and food as 60 Bioactive glass is well-suited as a glass cleaner since it is well as oil and grease. Cleaning agents containing bioactive “softer than standard household cleaners and is suitable as a glass may be used to effectively clean and disinfect Surfaces mild abrasive. In addition, the soluble minerals released by including, but not limited to painted walls, wood furniture, bioactive glass strengthens glass. For example, silicon vinyl floors (waxable and nonwax), vitreus china, porcelain released by bioactive glass is especially helpful in strength enamel, stainless steel, plastic laminate (FormicaR), plastic, 65 ening and protecting glass products by preventing crack acrylic, fiberglass, and chrome. These new cleaning agents propagation. Bioactive glass coats cracks in glass and builds may also be used to effectively clean textile materials, includ up a protective silicon layer. US 8,551,508 B2 67 68 The present invention also provides a cleaning agent con aqueous extract of bioactive glass to effectively prevent or taining bioactive glass which not only acts as a biocide control microbial contamination. An effective antimicrobial against viruses and bacteria, but is also gentle on skin and amount of bioactive glass may also refer to a combination of materials, causes no allergic reactions and cleans hard to particulate bioactive glass and aqueous extract of bioactive remove dirt Such as set-in proteins. The present invention also glass to effectively prevent or control microbial contamina provides non-toxic cleaning agents having biocidal and dirt tion. removing properties to be used in conjunction with a solvent Bioactive glass may be added to or included in cleaning having at least one surface active agent. agent formulations using, for example, techniques or combi In one embodiment the cleaning agent is non-toxic and has nations of techniques such as general mixing with slow biocide and dirt-removing features for joint usage with a 10 dissolving agent containing at least a Surface active agent and medium, moderate, or even vigorous agitation. Sufficientagi contains bioactive glass particles that release more than 250 tation should be provided to achieve relative homogeneity. ug of alkaline ions per gram of glass particles. In another Preferably, mixing and agitation will avoid excessive aeration embodiment the cleaning agent comprises bioactive glass and will have a low sheer rate. Other methods or combina particles which release at least 300 ug of alkaline ions per 15 tions of methods of blending, dispersing, mixing, combining, gram of glass particles. and/or emulsifying may be utilized. Agitation may be The glass particles preferably have an average particle size achieved, for example, with devices such as standard mixers. of smaller than 400 um. In another embodiment the glass General mixing and blending may be achieved, for example, particles have an average particle size of smaller than 100 um. with an impeller. In one embodiment the cleaning agent comprises tenside as Bioactive glass may be added to or included in virtually any a surface active agent. In another embodiment the cleaning known cleaning agent formulation. Applicants anticipate as agent contains bioactive glass which has components within well that bioactive glass will be suitable for inclusion in any as the following ranges on a % weight basis: 40-60% SiO, yet to be developed cleaning agent formulation. In one 10-30% CaO; 0-35% NaO; 2-8% P.O; 0-25% CaF: 0-10% embodiment the bioactive glass may be particulate. In B.O.; 0-8% KO; and 0-5% MgO. 25 another embodiment the bioactive glass may be an aqueous In one embodiment the cleaning agent comprises approxi solution derived from particulate bioactive glass. In still mately 1-7% of the weight of glass particles in terms of the another embodiment the bioactive glass may be a combina total weight of cleaning agent. In one embodiment the inven tion of particulate bioactive glass and an aqueous Solution tion provides a method of making a cleaning agent in which derived from bioactive glass. glass particles are added to at least one surface active agent, 30 In one embodiment the method of making these novel which release at least 250g of alkaline ions per gram of glass cleaning agents comprises combining a cleaning agent with particles. In another embodiment the invention provides a one or more surfactants and with bioactive glass. The method method of using a cleaning agent in clean objects such as a may also include adding a solvent. In one embodiment the variety of surfaces and textile materials. In one embodiment method comprises adding particulate bioactive glass and/or the cleaning agent is a dish-washing agent. In another 35 an aqueous extract of bioactive glass. The aqueous solutions embodiment the invention provides a method of using a of bioactive glass may be dried, for example, by spray drying cleaning agent for cleaning in hospitals, clinics, and in the or by drying in vacuo to provide an antimicrobial composi gastronomy industry. tion. The compositions can be incorporated into other anti In one embodiment the cleaning agent containing bioactive microbial Solutions or cleaning agents to provide an addi glass releases more than 250 ug of alkaline ions per gram of 40 tional antimicrobial component to the solutions or cleaning glass particles. The glass particles contained in the cleaning agents. agent according to another embodiment of the present inven The present invention will be more clearly understood with tion preferably release more than 300 ug, and especially more reference to the following non-limiting examples. than 500 ug of alkaline ions per gram of glass particles. Glass Categories of Cleaners particles that release more than 1 mg of alkaline ions per gram 45 The present invention will produce novel formulations of glass are even more especially preferred. which incorporate bioactive glass into various brands of Such cleaning agents are not only useful for cleaning and cleaning products including: laundry detergents, stain remov sterilizing Surfaces and textile materials but also may be used ers, and fabric softening products, dish washing products, air to clean and sterilize Surgical instruments. In addition, clean fresheners, deodorizing products, bathroom tissues, facial ing agents containing bioactive glass are useful as dish wash 50 tissues, paper towels, napkin products, cotton Swabs, handi ing agents, especially for use in dish washers. These novel wipes, scouring and sponge products, oven cleaning prod cleaning agents may also be used in for disinfecting and ucts, toilet cleaning products, tub and shower cleaning prod cleaning Surfaces and materials in the sanitation, hospital, and ucts, carpet cleaning products, all purpose cleaning products, gastronomy industries. and jewelry and metal cleaning products. Methods of Making 55 Laundry Detergent, Stain Remover and Fabric Softening The present invention also provides a method of making Products cleaning agent compositions comprising bioactive glass. An The present invention includes novel formulations which effective antimicrobial amount of the bioactive glass is added incorporate bioactive glass into various brands of varieties of to or included in a cleaning agent formulation. An "effective, laundry detergent, stain remover, and fabric softening prod antimicrobial amount of bioactive glass' refers to a sufficient 60 ucts, such as the products marketed under the brand names amount of bioactive glass having an appropriate particle size , All, Arm & Hammer, Biz, Bold, Bounce, Carbona, to effectively prevent or control microbial contamination. Cheer, Cling Free, Clorox, Dow, Downy, Dreft, Dryel, Era, The amount and particle size of bioactive glass to include in Fab, Febreze, , Gain, Ivory, K2R, Oxydol, Purex, a cleaning agent formulation will vary depending on the Rit, Shout, , Spray & Wash, Stain Devil, Sun Cuddle, desired length and degree of purity as well as the anticipated 65 , Thoro, Tide, Ultra, Windfresh, , , ZOut, microbial challenge. An “effective antimicrobial amount of and products produced by high-end and generic manufactur bioactive glass' also may refer to a sufficient amount of an CS. US 8,551,508 B2 69 70 Generally, laundry detergent, stain remover, and fabric Air freshener and room deodorizing products also may softening products comprise cleaning agents (anionic and include one or more of the following: alkyl methylbenzyl nonionic Surfactants), enzymes, water softener, dispensing ammonium saccharinate and ethanol. aid (propylene glycol), buffering agents, water, stabilizing The present invention provides for novel formulations of agents, soil Suspending agents, color-protecting agents, col airfreshenerand room deodorizing products by incorporating oring agents and fragrance. bioactive glass into a combination of any of the above-listed Common formulations of laundry detergent, stain remover, ingredients. and fabric Softening products comprise cleaning agents (an The antimicrobial and pH effects of bioactive glass are ionic an nonionic Surfactants), buffering agent, stabilizer, particularly useful in air freshener and room deodorizing perfume, brightening agents and coloring agents. 10 products to reduce bacteria and odor. Bathroom and Kitchen Paper Products Laundry detergent, stain remover, and fabric softening The present invention includes novel formulations which products may also include one or more of the following: incorporate bioactive glass into various brands of bathroom Sodium hypochlorite, hydrogen peroxide, water softeners tissue, facial tissue, paper towel and napkin products such as (aluminosilicates, Sodium carbonate), various processing 15 the products marketed under the brand names Angel Soft, aids (sodium sulfate), various washer protection agents, vari Bounty, Brawny, Brite-Life, Charmin, Cottonelle, Good & ous Soil Suspending agents, cationic Surfactants and various Plenty, Green Forest, Hi Dri, Kleenex, Marcal, Mardi Gras, preservatives. Md Bath Tissue, Northern, Puffs, Purely Cotton, Scott, Scot The present invention provides for novel formulations of ties, So-Dri, Soft N Gentle, Sparkle, Vanity Fair, Viva, Wash laundry detergent, stain remover, and fabric Softening prod N Dri, Zee, and products produced by high-end and generic ucts by incorporating bioactive glass into a combination of manufacturers. any of the above-listed ingredients. Common formulations of bathroom tissue, facial tissue, The antimicrobial and pH effects of bioactive glass are paper towel, and napkin products comprise purified wood particularly useful in laundry detergent products to reduce pulp, skin conditioners, coloring agents and fragrance. bacteria and odor and to increase pH. 25 The present invention provides for novel formulations of Dish-Washing Products bathroom tissue, facial tissue, paper towel and napkin prod The present invention includes novel formulations which ucts by incorporating bioactive glass into a combination of incorporate bioactive glass into various brands of dish-wash any of the above-listed ingredients. ing products such as the products marketed under the brand Cleaning Accessory Products names Ajax, All, Cascade, Crystal White, Dawn, Dove, Earth 30 The present invention includes novel formulations which Friendly, Easy Off, Electrosol, Extra Plus, Glass Magic, incorporate bioactive glass into various brands of cotton Ivory, Jet Dry, Joy, Palmolive, Sun Light, Surf, and products Swab, handiwipe, scouring and sponge products such as the produced by high-end and generic manufacturers. products marketed under the brand names Arden, Ecko, Generally, dish-washing products comprise a detergent, an Guardsman, Handi Wipes, Johnson & Johnson, , Mr. alkaline compound to increase pH, a surfactant and a fra 35 Clean, O-Cel-O, Pledge, Q-tips, S.O.S., Scotch Brite, and grance. products produced by high-end and generic manufacturers. Common formulations of dish-washing products comprise The present invention provides for novel formulations of triclosan, water, ammonium laureth Sulfate, lauryl polyglu cotton Swab, handiwipe, Scouring and sponge products by cose, sodium dodecylbenzenesulfonate, SD alcohol 3-A, incorporating bioactive glass into a combination of any of the Sodium Xylene Sulfonate, quaternium-15, lauramide myrista 40 above-listed ingredients. mide MEA, fragrance and various coloring agents. The antimicrobial and pH effects of bioactive glass are Dish-washing products also may include one or more of the particularly useful in cotton Swab, handiwipe, Scouring and following: chlorine bleach, silicate salts, lauryl polyglucose, sponge products to reduce bacteria and odor. Additionally, the DMDM hydantoin, methylchloroisothiazolinone, calcium abrasive effects of bioactive glass aid in the removal of dirt carbonate, methylisothiazolinone, anionic Surfactants, 45 and stains. sodium carbonate, trisodium HEDTA, sodium metabisulfite, Oven Cleaning Products and various quality control agents. The present invention includes novel formulations which The present invention provides for novel formulations of incorporate bioactive glass into various brands of oven clean dish-washing products by incorporating bioactive glass into a ing products such as the products marketed under the brand combination of any of the above-listed ingredients. 50 names Dow, Easy Off, Kleen King, and products produced by The antimicrobial and pH effects of bioactive glass are high-end and generic manufacturers. particularly useful in dish-washing products to reduce bacte Generally, oven cleaning products comprise the active ria and to increase cleaning power. ingredient sodium hydroxide. Air-Freshener and Room Deodorizing Products Common formulations of oven cleaning products comprise The present invention includes novel formulations which 55 water, Surfactants, grease cutting agents, Sodium hydroxide, incorporate bioactive glass into various brands of air fresh water conditioning agents, fragrance, and various coloring ener and room deodorizing products such as the products agents. marketed under the brand names Airwick, Arm & Hammer, The present invention provides for novel formulations of Clorex, Country Air, Country Rose, Dale, Enoz, Glade, oven cleaning products by incorporating bioactive glass into Lemon Fresh, Little Tree, Lysol, Moonlight Bay, One Drop, 60 a combination of any of the above-listed ingredients. Pine Closet, , Solid Sachet, Wizard, and products The antimicrobial effects of bioactive glass are particularly produced by and high-end and generic manufacturers. useful in oven cleaning products to reduce bacteria and odor. Common formulations of air freshener and room deodor Toilet Cleaning Products izing products comprise N-alkyl, dimethyl benzyl ammo The present invention includes novel formulations which nium chloride, octyl decyl dimethyl ammonium chloride, 65 incorporate bioactive glass into various brands of toilet clean dioctyl dimethyl ammonium chloride, and didecyl dimethyl ing products such as the products marketed under the brand ammonium chloride. names Blu Boy, Bowl Fresh, Clorox, Dale, Dow, Lime Away, US 8,551,508 B2 71 72 Lysol, Septonic, Sno Bol, Tiolet Duck, Ty-D-Bol, , cleaning products such as the products marketed under the Willert Bowl, and X-14, and products produced by high-end brand names Amazing White, Biz, Borateem, Cloralen, Clo and generic manufacturers. roX, Ajax, Armstrong, Barkeepers Friend, Behold, Bon Ami, Generally, toilet cleaning products comprise the active , Brite, Cameo, Cinch, Clear Calcium Lime Rust ingredient oxacil acid. 5 Remover, Clorox, Comet, Dow, Easy-Off, Endust, Fantastik, Common formulations of toilet cleaning products com Formula 409, Glass Magic, , International Brass & prise bromine, chlorine, 1-bromo-3-chloro-5,5-dimethylhy Metal Polish, Johnson, Lysol, Mop & Glo, Mr. Clean, Mur dantoin, 1,3-dichloro-5,5-dimethylhydantoin, and 1,3- phy’s, Old English, Pine O Pine, Pine Sol, Pledge, Proctor & dichloro-5-ethyl-5-methylhydantoin. Gamble, Orange Clean, Orange Glo, Scotts, Simple Green, Toilet cleaning products also may include one or more of 10 the following: hydrogen chloride, alkyl, dimethyl benzyl SoftScrub, Sparkle, Spic & Span, Tilex, Twinkle, Xtra, Wein ammonium chloride, octyl decyl dimethyl ammonium chlo mans, Windex, Wright, Wrights, and products produced by ride, didecyl dimethyl ammonium chloride, and dioctyl dim high-end and generic manufacturers. ethyl ammonium chloride. Generally, all purpose cleaning products comprise Sodium The present invention provides for novel formulations of 15 hypochlorite and/or calcium hypochlorite, a detergent, toilet cleaning products by incorporating bioactive glass into ammonia and alcohol. a combination of any of the above-listed ingredients. Common formulations of all purpose cleaning products The antimicrobial and pH effects of bioactive glass are comprise Sodium dichloro-S-triazinetrione dihydrate, clean particularly useful in toilet cleaning products to reduce bac ing agents (calcium carbonate, Sodium carbonate, anionic teria and odor. Surfactants), perfume, various quality control agents and vari Tub and Shower Cleaning Products ous coloring agents. The present invention includes novel formulations which All purpose cleaning products also may include one or incorporate bioactive glass into various brands of tub and more of the following: dipropylene glycol butyl ether, citric shower cleaning products such as the products marketed acid, bleach, N-alkyl dimethylbenzyl ammonium chlorides, under the brand names Clean Shower, Comet, Dow, Edfred, 25 N-alkyl dimethyl ethylbenzyl ammonium chloride, ammo Lime-Away, Lysol, Parsons, Pine Sol, Scrub Free, Shower nia-D, octyl decyl dimethyl ammonium chloride, dioctyl Power, Soft Scrub, Tilex, X-14, and products produced by dimethyl ammonium chloride, isopropanol and Surfactants. high-end and generic manufacturers. The present invention provides for novel formulations of Generally, tub and shower cleaning products comprise all purpose cleaning products by incorporating bioactive Sodium hypochlorite and/or calcium hypochlorite, a deter 30 glass into a combination of any of the above-listed ingredi gent and bleach. entS. Common formulations of tub and shower cleaning prod The antimicrobial and pH effects of bioactive glass are ucts comprise alkyl, dimethyl benzyl ammonium chlorides particularly useful in general purpose cleaning products to and detergents. reduce bacteria and odor. Additionally, the abrasive quality of Tub and shower cleaning products also may include one or 35 bioactive glass aids in the removal of dirt and stains. more of the following: dipropylene glycol butyl ether, citric Jewelry and Metal Cleaning Products acid, perfume, water, calcium carbonate, sodium hypochlo The present invention includes novel formulations which rite, dimethyl ethylbenzyl ammonium chlorides, glycol ether, incorporate bioactive glass into various brands of jewelry and Surfactants, soil Suspending agents, cleaning agents, Various metal cleaning products such as the products marketed under processing agents, various coloring agents, and Various qual 40 the brand names Brasso, International Brass & Metal Polish, ity control agents. Twinkle, and Wrights. The present invention provides for novel formulations of The present invention provides for novel formulations of tub and shower cleaning products by incorporating bioactive jewelry and metal cleaning products by incorporating bioac glass into a combination of any of the above-listed ingredi tive glass into any of the above-listed ingredients. entS. 45 The abrasive and pH effects of bioactive glass are particu The antimicrobial and pH effects of bioactive glass are larly useful in jewelry and metal cleaning products to reduce particularly useful in tub and shower cleaning products to bacteria and to remove stains. reduce bacteria and odor. Food Preservatives, Nutritional Supplements and Functional Carpet Cleaning Products Food Formulations The present invention includes novel formulations which 50 Food Preservatives incorporate bioactive glass into various brands of carpet Numerous foods are potentially infected with bacteria, cleaning products such as the products marketed under the such as E. coli. Ground beef and chicken are particularly brand names Arm & Hammer, Carpet Fresh, Folex, Formula Susceptible to bacterial infection. Aqueous solutions includ 409, Glade, Simply Spot-Less, Spot Shot, Resolve, Shout, ing an aqueous extract from bioactive glass have anti-bacte Woolite, and products produced by high-end and generic 55 rial properties. The anti-bacterial effect is due, in part, to the manufacturers. basic nature of the solution (pH greater than about 7, prefer Generally, carpet cleaning products comprise the active ably greater than about 9, more preferably greater than about ingredient sodium bicarbanate and fragrance. 10.5). However, sodium hydroxide solutions of relatively The present invention provides for novel formulations of high pH are not as effective at killing bacteria. Accordingly, carpet cleaning products by incorporating bioactive glass into 60 the Solutions have additional antibacterial elements present a combination of any of the above-listed ingredients. than merely a relatively high pH. The antimicrobial and pH effects of bioactive glass are The bioactive glass compositions may be sprayed on con particularly useful in carpet cleaning products to reduce bac taminated Surfaces, or incorporated into food products Such teria and odor. as ground beef. Since bioactive glass has been approved for All Purpose Cleaning Products 65 various uses by the FDA, the extract of bioactive glass should The present invention includes novel formulations which be harmless to humans. In addition, bioactive glass has no incorporate bioactive glass into various brands of all purpose effect on taste or texture. US 8,551,508 B2 73 74 It should be noted that in addition to bioactive glass, anti Common formulations of antacid products comprise aspi biotics may also be added to food preservatives, nutritional rin, Sodium bicarbonate, citric acid, Sodium citrate, sodium Supplements and functional food formulations. The addition acetylsalicylate, aspartame, flavor and phenylalanine. of antibiotics to food preservatives, nutritional Supplements Antacid products also may include one or more of the and functional food formulations which include bioactive following: calcium carbonate, magnesium Stearate, mineral glass is particularly effective informulations which are orally oil, Sodium hexametaphosphate, starch, Stearic acid, Sucrose, ingested. talc, aluminum hydroxide, magnesium carbonate, alginic Functional Foods/Nutritional Supplements acid, calcium Stearate, aspartame, croscarmellose Sodium, It has been shown in several animal models that soluble silica, various artificial and natural flavorings, and various silica is essential for proper absorption/metabolization of cal 10 coloring agents. cium. Thus, without adequate levels of soluble silica, the The present invention provides for novel formulations of effects of supplemented calcium may be defeated. Accord antacid products by incorporating bioactive glass into a com ingly, the addition of bioactive glass to calcium Supplemented bination of any of the above-listed ingredients. foods may improve calcium absorption. The anti-inflammatory and antimicrobial effects of bioac In addition, antacids are increasingly being sold as calcium 15 tive glass are particularly useful in antacid products to reduce Supplements. Accordingly the addition of bioactive glass to inflammation and bacteria. antacid formulation may increase calcium absorption, and Calcium Supplement Products due to its effects on pH also reduces acid. The present invention includes novel formulations which Likewise, other calcium Supplements and calcium added to incorporate bioactive glass into various brands of calcium foods such as orange juice, cereals, and nutritional shakes can Supplement and calcium Supplemented products including: benefit from the increased calcium absorption provided by dietary Supplements in pill and chewable form, antacids, pain bioactive glass. In addition, the anti-inflammatory properties relievers, toothpaste, cereals, Snack foods, beverages, and of bioactive glass make it suitable as a treatment for internal various food seasonings and spreads such as the products inflammations such as stomach and intestinal inflammations. marketed under the brand names Alka-Mints, Amitone, Basic Methods of Making 25 Nutrition, Bayer, Biotene, Black Radiance, Brite-Life, Cal For enteral administration, the bioactive glass particulates cet, Cal-Max, Caltrate, Centrum Kids, Citracel, Dical-D, Di can be incorporated into an inert carrier in discrete units such Gel, drugstore.com, Enamelon, Ensure, Equalactin, Estro as capsules, cachets, tablets or lozenges, each containing a ven, FiberCon, Flintstones, Florical, FosFree, Futurebiotics, predetermined amount of the particles; as a powder or gran Gas-X, GNC, Good Sense, Healthy Woman, Konsyl, Maalox, ules; or a suspension or solution in an aqueous liquid or 30 Mylanta, Natrol, Naturalife, Natural Wealth, Naturally Sci non-aqueous liquid, e.g., a syrup, an elixir, an emulsion or a entific, Nature Made, Nature's Bounty, Nature's Reward, draught. Suitable carriers may be starches or sugars and Nature's Way, Neo-Calglucon, Nephro-Calci, NutritionNow, include lubricants, flavorings, binders, and other materials of One-A-Day, Olry. Os-cal, Pharm Assure, PhenSafe, Phillips, the same nature. Posture, Prelief, Provate, R&C, R&D, Rainbow Light, Rev A tablet may be made by compression or molding, option 35 lon, Roberts, Rolaids, Schiff, Similac, Solgar, Stuart Prenatal, ally with one or more accessory ingredients. Compressed Sundown, Surfak, Thompson, Titralac, Tums, Twinlab, tablets may be prepared by compressingina Suitable machine Viactiv, VitaFresh, and products produced by high-end and the active compound in a free-flowing form, e.g., a powder or generic manufacturers. granules, optionally mixed with accessory ingredients, e.g., Common formulations of calcium Supplement and calcium binders, lubricants, inert diluents, Surface active or dispersing 40 Supplemented products comprise calcium carbonate, dicytl agents. Molded tablets may be made by molding in a Suitable Sodium SulfoSuccinate, hydrogenated cereal Solids, magne machine, a mixture of the powdered active compound with sium Stearate, polyethylene glycol, Sorbitol, Sugar, various any Suitable carrier. artificial and natural flavorings and various coloring agents. A syrup Suspension may be made by adding the active Calcium Supplement and calcium Supplemented products compound to a concentrated, aqueous solution of a Sugar, e.g., 45 also may include one or more of the following: adipic acid, Sucrose, to which may also be added any accessory ingredi silicon dioxide, sodium polyphosphate, starch, talc, aspar ents. Such accessory ingredients may include flavoring, an tame, mannitol, maltodextrin, cellulose, mineral oil, agent to retard crystallization of the Sugar or an agent to crospovidone, hydroxypropyl methylcellulose, vegetable increase the solubility of any other ingredient, e.g., as a poly glycerides, acacia gum, titanium oxide, polysorbate 80, hydric alcohol, for example, glycerol or Sorbitol. 50 Sodium lauryl Sulfate and Stearic acid. Categories of Functional Foods/Nutritional Supplements The present invention provides for novel formulations of One embodiment of the present invention will produce calcium Supplement and calcium Supplemented products by novel formulations which incorporate bioactive glass into incorporating bioactive glass into a combination of any of the various brands of a variety of functional food and nutritional above-listed ingredients. Supplements including: antacid products, calcium Supple 55 Silica Supplemented Products ment products, and silica Supplement products. The present invention includes novel formulations which Antacid Products incorporate bioactive glass into various brands of silica The present invention includes novel formulations which Supplement and silica Supplemented products including the incorporate bioactive glass into various brands of antacid following: dietary Supplements in pill and chewable form, products such as the products marketed under the brand 60 toothpaste, shampoo, body wash, and various food season names Alka-Mints, Alka-Seltzer, Amitone, Axid, Brite-Life, ings and spreads, Such as the products marketed under the Bromo Seltzer, Di-Gel, Gas-X, Gaviscon, Gelusil, Good brand names Body Essential, Crest, Futurebiotics, GNC, Sense, Imodium, Kaopectate, Lactaid, Maalox, Mag-OX, Natrol, Nature's Herbs, Nature's Way, Peter Thomas Roth, Mylanta, Pepcid AC, Pepto-Bismol, Phazyme, Phillips, Pre and high-end and generic manufacturers. lief, Riopan, Rolaids, Sal De Picot, Tagamet, Tempo, Titralac, 65 Common formulations of silica Supplement and silica Tums, Zantac, an products produced by high-end and generic Supplemented products comprise Stearic acid, dicalcium manufacturers. phosphate, cellulose, and magnesium Stearate. US 8,551,508 B2 75 76 Silica Supplement and silica Supplemented products may Bioactive glass may also be added to or included in the also include one or more of the following: rice powder, silica, following products: fungicide/pesticide for agriculture, gelatin and water. marine antifoulant, coating for glass and cleaners for indus The present invention provides for novel formulations of trial food and beverage containers, concrete, ceramics, and silica Supplement and silica Supplemented products by incor 5 tile, to name a few, to make these products highly resistant to porating bioactive glass into a combination of any of the microbial contamination and to increase the pH. above-listed ingredients. The numbered embodiments provided below further exem Alternatively, bioactive glass itself may be considered the plify the invention and aspects thereof. silica Supplement or may replace the silica found in existing 1. A cosmetic composition comprising bioactive glass and a formulations of silica Supplements. 10 Substantially anhydrous cosmetic formulation. Applicants have found that bioactive glasses provide Supe 2. The composition of embodiment 1, wherein the bioactive rior and unexpected results in comparison to standard dietary glass is melt-derived. silica Supplements. Applicants have found that bioactive 3. The composition of embodiment 1, wherein the bioactive glasses release soluble silica into physiological environments glass is sol-gel-derived. in beneficial ways that have notheretofore been appreciated. 15 4. The composition of embodiment 1, wherein the bioactive Bioactive glasses also provide for an unusually large physical glass is an aqueous extract. Surface area that presents silanol groups which have activity 5. The composition of embodiment 1, wherein the substan that in many ways is similar to soluble silica. Note that this is tially anhydrous cosmetic formulation is selected from the particularly true for sol-gel-derived glasses. group consisting of lipstick, lipbalm, , eye foun Applicants have found that both the released soluble silica dation, make-up foundation, and face powder. and the available silanol groups provide for an efficient 6. The composition of embodiment 1 in the formulation of mechanism for sequestering and removing metal ions from Example 4B. the body. The glass particles, which may be micron-sized, 7. The composition of embodiment 1 in the formulation of sequester orbind metalions and are flushed through organs of Example 4C. the body (e.g. the kidneys and intestines) and excreted from 25 8. The composition of embodiment 1 in the formulation of the body. In this way, bioactive glasses can be used to reduce Example 5. or minimize the toxic effects of many metal ions. 9. The composition of embodiment 1 in the formulation of Bioactive glasses are particularly helpful in reducing or Example 6. minimizing the toxic effects of aluminum. In addition to the 10. The composition of embodiment 1 in the formulation of sequestering or binding discussed above, bioactive glasses 30 Example 7. release additional calcium and phosphate, which aluminum 11. The composition of embodiment 1 in the formulation of tends to bind. The aluminum so bound is thus made less Example 8. available for toxic effects or damaging physiological pro 12. The composition of embodiment 27 in the formulation of CCSSCS. Example 9. Accordingly, dietary Supplements incorporating bioactive 35 13. The composition of embodiment 27 in the formulation of glass may be beneficial for treating or preventing many harm Example 10B. ful disease processes and conditions associated with, for 14. A method of making a cosmetic composition comprising example, aluminum including, but not limited to, osteoporo combining bioactive glass with a Substantially anhydrous sis, osteodystrophy, and other conditions in which stimula cosmetic formulation. tion of osteoblastic activity is desired. 40 15. The method of embodiment 14, wherein the bioactive In addition, these dietary Supplements by binding alumi glass is melt-derived. num, may be beneficial in preventing, slowing, or reversing 16. The method of embodiment 14, wherein the bioactive the effects of Alzheimer's disease, various forms ofencepha glass is sol-gel-derived. lopathy, and various forms of myocardial dysfunction. 17. The method of embodiment 14, wherein the bioactive In addition to aluminum, bioactive glass can be used to 45 glass is an aqueous extract. bind other metalions, including, for example, lead, cadmium, 18. The method of embodiment 14, wherein the substantially Zinc, and iron. Accordingly, harmful or toxic effects of these anhydrous cosmetic formulation is selected from the group and other metal ions may be prevented, slowed, or reversed. consisting of lipstick, lipbalm, eye shadow, eye foundation, Miscellaneous Products make-up foundation, and face powder. In addition to the products listed above, bioactive glass 50 19. The method of embodiment 14 to make the formulation of may be added to or included in the following household Example 4B. products: dust filters, wall paint/wallpaper, toilet seat covers, 20. The method of embodiment 14 to make the formulation of mold remover, ceramic/bathroom tile laminates, water filters, Example 4C. mattress fillers, cleaning agents for Solariums and Sun beds, 21. The method of embodiment 14 to make the formulation of toilet brushes, pet litter (such as the products marketed under 55 Example 5. the brand names Litter Clean, Tidy Cat, Arm & Hammer, 22. The method of embodiment 14 to make the formulation of Classy Cat, Everfresh, Fresh Step, Jonny, Sani-Scoop and Example 6. Scoop Away) and cutting boards to make these products 23. The method of embodiment 14 to make the formulation of highly resistant to microbial contamination and to increase Example 7. the pH. 60 24. The method of embodiment 14 to make the formulation of The present invention also provides novel products useful Example 8. in the animal care and Veterinary fields. Bioactive glass may 25. The method of embodiment 34 to make the formulation of also be added to or included, for example, in the following Example 9. animal/veterinary products to make these products highly 26. The method of embodiment 34 to make the formulation of resistant to microbial contamination and to increase the pH: 65 Example 10B. sand for birdcages, kitty litter, flea powder, and dry shampoos 27. A cosmetic composition comprising bioactive glass, a for animals. cosmetic formulation and a buffer. US 8,551,508 B2 77 78 28. The composition of embodiment 27, wherein the bioac 54. A method of blocking UV light from exposed skin com tive glass is melt-derived. prising applying the cosmetic composition of embodiment 50 29. The composition of embodiment 27, wherein the bioac to the exposed skin. tive glass is sol-gel-derived. 55. A method of blocking UV light from exposed skin com 30. The composition of embodiment 27, wherein the bioac- 5 prising applying the cosmetic composition of embodiment 51 tive glass is an aqueous extract. to the exposed skin. 31. The composition of embodiment 27, wherein the buffer is 56. A moisture-absorbing cosmetic composition comprising citric acid. bioactive glass and a cosmetic formulation. 32. The composition of embodiment 27, wherein the cos 57. The cosmetic composition of embodiment 56, wherein metic formulation is selected from the group consisting of 10 the bioactive glass is sol-gel derived. lipstick, lipbalm, eye shadow, eye foundation, make-up foun 58. A method of absorbing moisture comprising applying the dation, and face powder. cosmetic composition of embodiment 56 to a source of mois 33. The composition of embodiment 27 in the formulation of ture. Example 9. 59. A personal care composition comprising bioactive glass 34. A method of making a cosmetic composition comprising 15 and a personal care product. combining bioactive glass, a cosmetic formulation, and a 60. The composition of embodiment 59, wherein the bioac buffer. tive glass is melt-derived. 35. The method of embodiment 34, wherein the bioactive 61. The composition of embodiment 59, wherein the bioac glass is melt-derived. tive glass is sol-gel-derived. 36. The method of embodiment 34, wherein the bioactive 62. The composition of embodiment 59, wherein the bioac glass is sol-gel-derived. tive glass is an aqueous extract. 37. The method of embodiment 34, wherein the bioactive 63. The composition of embodiment 59, wherein the personal glass is an aqueous extract. care product is selected from the group consisting of diaper 38. The method of embodiment 34, wherein the buffer is citric 25 products, adult incontinence products, feminine hygiene acid. products, shampoo products, hair care products, deodorant 39. The method of embodiment 34, wherein the cosmetic products, foot care products, baby care products, Sunscreen formulation is selected from the group consisting of lipstick, products, body products, skin care products, and lipbalm, eye shadow, eye foundation, make-up foundation, nutritional Supplement products. and face powder. 30 64. A method of making a personal care composition com 40. The method of embodiment 34 to make the formulation of bining bioactive glass, and a personal care product. 65. The method of embodiment 64, wherein the bioactive Example 9. glass is melt-derived. 41. A non-irritating, stable cosmetic composition comprising 66. The method of embodiment 64, wherein the bioactive bioactive glass and a cosmetic formulation, wherein the pH of glass is sol-gel-derived. the composition is between about 8 and about 12. 67. The method of embodiment 64, wherein the bioactive 42. A method of making a non-irritating, stable cosmetic glass is melt-derived. composition comprising combining bioactive glass and a cos 68. The method of embodiment 64, wherein the personal care metic formulation, wherein the pH of the composition is product is selected from the group consisting of diaper prod between about 8 and about 12. 40 ucts, adult incontinence products, feminine hygiene products, 43. A non-irritating cosmetic composition comprising bioac shampoo products, hair care products, deodorant products, tive glass and a cosmetic formulation, wherein said cosmetic foot care products, baby care products, Sunscreen products, formulation comprises at least on Substance that is skin-irri body cleanser products, skin care products, and nutritional tating when not in the composition. Supplement products. 44. A method of reducing and/or preventing skin irritation 45 69. A non-irritating, stable personal care composition com comprising applying the cosmetic composition of embodi prising bioactive glass and a personal care product, wherein ment 43 to the skin. the pH of the composition is between about 8 and about 12. 45. An odor reducing cosmetic composition comprising bio 70. A method of making a non-irritating, stable personal care active glass and a cosmetic formulation. composition comprising combining bioactive glass and a per 46. A method of reducing odor comprising applying the cos 50 Sonal care product, wherein the pH of the composition is metic composition of embodiment 45 to a source of odor. between about 8 and about 12. 47. A UV-filtering cosmetic composition comprising bioac 71. An odor-reducing personal care composition comprising tive glass and a cosmetic formulation. bioactive glass and a personal care product. 48. The cosmetic composition of embodiment 47, wherein 72. A method of reducing odor comprising applying the per the bioactive glass is sol-gel-derived. 55 Sonal care composition of embodiment 71 to a source of odor. 49. The cosmetic composition of embodiment 47 in the for 73. A UV-filtering personal care composition comprising bio mulation of Example 1. active glass and a personal care product. 50. The cosmetic composition of embodiment 47 in the for 74. The UV-filtering personal care composition of embodi mulation of Example 2. ment 73, wherein the bioactive glass is sol-gel-derived. 51. The cosmetic composition of embodiment 47 in the for- 60 75. The personal care composition of embodiment 73, mulation of Example 3. wherein the personal care product comprises Sunscreen. 52. A method of blocking UV light from exposed skin com 76. The personal care composition of embodiment 73 in the prising applying the cosmetic composition of embodiment 47 formulation of Example 1. to the exposed skin. 77. The personal care composition of embodiment 73 in the 53. A method of blocking UV light from exposed skin com- 65 formulation of Example 2. prising applying the cosmetic composition of embodiment 49 78. The personal care composition of embodiment 73 in the to the exposed skin. formulation of Example 3. US 8,551,508 B2 79 80 79. A method of blocking UV light from exposed skin com microcrystalline wax, jojoba oil, vitamin E, methyl paraben, prising applying the personal care composition of embodi propyl paraben, and 45s bioactive glass. ment 73 to the exposed skin. 100. The method of embodiment 14 to make a composition 80. A method of blocking UV light from exposed skin com comprising Red 7 Ca Lake, Red 6 Ba Lake, Red 33 Al Lake, prising applying the personal care composition of embodi castor oil, carnauba wax, candellila wax, oZokerite wax, ment 76 to the exposed skin. microcrystalline wax, jojoba oil, vitamin E, methyl paraben, 81. A method of blocking UV light from exposed skin com propyl paraben, 45s bioactive glass, and 58s bioactive glass. prising applying the personal care composition of embodi 101. The method of embodiment 14 to make a composition ment 77 to the exposed skin. comprising jojoba glaze and bioactive glass, wherein the 82. A method of blocking UV light from exposed skin com 10 bioactive glass has an average particle size less than about 5 prising applying the personal care composition of embodi microns. ment 78 to the exposed skin. 102. The method of embodiment 14 to make a composition 83. A moisture-absorbing personal care composition com comprising glycerin, Pemulen R TR-2, and bioactive glass, prising bioactive glass and a personal care product. wherein the bioactive glass has an average particle size less 84. The moisture-absorbing personal care composition of 15 than about 5 microns. embodiment 83, wherein the bioactive glass is sol-gel 103. The method of embodiment 14 to make a composition derived. comprising jojoba glaze, brown iron oxide, titanium dioxide, 85. A method of absorbing moisture comprising applying the talc, and sol-gel-derived bioactive glass. personal care composition of embodiment 83 to a source of 104. The method of embodiment 34 to make a composition moisture. comprising mineral oil, Polawax R, glycerin, deionized 86. A hair care composition comprising bioactive glass and a water, jugular C-14S, phenobact, fragrance, citric acid mono hair care product, wherein the hair care composition provides hydrate powder, and sol-gel-derived bioactive glass. a mineral coating to the hair. 105. The method of embodiment 34 to make the formulation 87. The hair care composition of embodiment 86 in the for of Example 10C. mulation of Example 11. 25 106. The method of embodiment 34 to make a composition 88. The hair care composition of embodiment 86 in the for comprising crodafos CES, Volpo 10, Volpo 3, jojoba oil, mulation of Example 12A. cyclomethicone D5, deionized water, NaOH, TiO2, red iron 89. The hair care composition of embodiment 86 in the for oxide, 50/50 Black/brown iron oxide blend, propylene glycol, mulation of Example 13 A. jaguar 13S, germaben II, and 45s bioactive glass. 90. The composition of embodiment 1 comprising Red 7 Ca 30 107. The method of embodiment 34 to make a composition Lake, Red 6 Ba Lake, Red 33 Al Lake, castor oil, carnauba comprising crodafos CES, Volpo 10, Volpo 3, jojoba oil, wax, candellila wax, ozokerite wax, microcrystalline wax, cyclomethicone D5, deionized water, NaOH, TiO2, red iron jojoba oil, vitamin E, methyl paraben, propyl paraben, and oxide, 50/50 Black/brown iron oxide blend, propylene glycol, 45s bioactive glass. jaguar 13S, germaben II, and 58s bioactive glass. 91. The composition of embodiment 1 comprising Red 7 Ca 35 108. The composition of embodiment 47 comprising jojoba Lake, Red 6 Ba Lake, Red 33 Al Lake, castor oil, carnauba glaze, octyl methoxycinnamate, benzophenone-3 and bioac wax, candellila wax, oZokerite wax, microcrystalline wax, tive glass. jojoba oil, vitamin E, methyl paraben, propyl paraben, 45s 109. The composition of embodiment 47 comprising jojoba bioactive glass, and 58s bioactive glass. glaze, octyl methoxycinnamate, benzophenone-3 and Sol 92. The composition of embodiment 1 comprising jojoba 40 gel-derived bioactive glass. glaze and bioactive glass, wherein the bioactive glass has an 110. The composition of embodiment 73 comprising jojoba average particle size less than about 5 microns. glaze, octyl methoxycinnamate, benzophenone-3 and bioac 93. The composition of embodiment 1 comprising glycerin, tive glass. PemulenR TR-2, and bioactive glass, wherein the bioactive 111. The composition of embodiment 73 comprising jojoba glass has an average particle size less than about 5 microns. 45 glaze, octyl methoxycinnamate, benzophenone-3 and Sol 94. The composition of embodiment 1 comprising jojoba gel-derived bioactive glass. glaze, brown iron oxide, titanium dioxide, talc, and sol-gel 113. The composition of embodiment 86 comprising stan derived bioactive glass. dopol ES, crosultaine C-50, foamid C. deionized water, jag 95. The composition of embodiment 27 comprising mineral uar C-14S, phenobact, fragrance, citric acid monhydrate oil, Polawax R, glycerin, deionized water, juguar C-14S, phe 50 powder, and bioactive glass. nobact, fragrance, citric acid monohydrate powder, and sol 114. The hair care composition of embodiment 86 in the gel-derived bioactive glass. formulation of Example 12D. 96. The composition of embodiment 27 in the formulation of 115. The composition of embodiment 86 comprising stan Example 10C. dopol ES, crosultaine C-50, foamid C. deionized water, phe 97. The composition of embodiment 27, comprising crodafos 55 nobact, citric acid monhydrate powder, and bioactive glass. CES, Volpo 10, Volpo 3, jojoba oil, cyclomethicone D5, 116. The hair care composition of embodiment 86 in the deionized water, NaOH, TiO2, red iron oxide, 50/50 Black/ formulation of Example 13B. brown iron oxide blend, propylene glycol, jaguar 13S, germa 117. The hair care composition of embodiment 86 in the ben II, and 45s bioactive glass. formulation of Example 13C. 98. The composition of embodiment 27, comprising crodafos 60 117. The hair care composition of embodiment 86 in the CES, Volpo 10, Volpo 3, jojoba oil, cyclomethicone D5, formulation of Example 13D. deionized water, NaOH, TiO2, red iron oxide, 50/50 Black/ 118. The composition of embodiment 86 comprising steol brown iron oxide blend, propylene glycol, jaguar 13S, germa CS-230, crosultaine C-50, foamid C. deionized water, phe ben II, and 58s bioactive glass. nobact, citric acid monhydrate powder, and bioactive glass. 99. The method of embodiment 14 to make a formulation 65 119. The composition of embodiment 86 comprising steol comprising Red 7 Ca Lake, Red 6 Ba Lake, Red 33 Al Lake, CS-230, crosultaine C-50, foamid C. deionized water, phe castor oil, carnauba wax, candellila wax, oZokerite wax, nobact, and bioactive glass. US 8,551,508 B2 81 82 120. The composition of embodiment 1 comprising jojoba 138. The composition of embodiment 134 wherein the nutri oil, Lubrajel R. MS, pigment, and bioactive glass. tional supplement is selected from the group consisting of: 121. The composition of embodiment 1 comprising Polawax, antacids, calcium supplements, and silica supplements. mineral oil, glycerin, Jaguar C14-S, citric acid, Phenobact, 139. The composition of embodiment 134, further compris ing iodine. colorant, fragrance, and bioactive glass. 140. A method of making a nutritional supplement composi 122. The composition of embodiment 59 comprising a tion comprising combining bioactive glass and a nutritional deodorant stick and bioactive glass, wherein the bioactive Supplement. glass is between about 4% and about 10% by weight of the 141. The method of embodiment 140, wherein the bioactive composition. glass is melt-derived. 123. The composition of embodiment 59 comprising a 10 142. The method of embodiment 140, wherein the bioactive deodorant cream and bioactive glass, wherein the bioactive glass is sol-gel-derived. glass is between about 30% and about 60% by weight of the 143. The method of embodiment 140, wherein the bioactive composition. glass is an aqueous extract. 124. A cleaning agent composition comprising bioactive 144. The method of embodiment 140, wherein the nutritional glass and a cleaning agent. 15 Supplement is selected from the group consisting of antacids, 125. The composition of embodiment 124, wherein the bio calcium supplements, and silica supplements. active glass is melt-derived. What is claimed is: 126. The composition of embodiment 124, wherein the bio 1. A non-irritating, stable personal care composition com active glass is sol-gel-derived. prising bioactive glass, and a personal skin care product 127. The composition of embodiment 124, wherein the bio wherein the pH of the composition is between about 8 and active glass is an aqueous extract. about 12, wherein the composition exhibits moisture-absorb 128. The composition of embodiment 124, wherein the clean ing properties and wherein the composition is substantially ing agent is selected from the group consisting of: laundry anhydrous. detergents, stain removers, fabric softening products, dish 2. The composition of claim 1 further comprising at least washing products, air fresheners, deodorizing products, bath 25 one substance that is skin-irritating when not in the compo room tissue, facial tissue, paper towel products, napkin prod sition. ucts, cotton Swabs, handiwipes, scouring products, sponge 3. The composition of claim 1, wherein the bioactive glass products, oven cleaning products, toilet cleaning products, is an aqueous extract. tub and shower cleaning products, carpet cleaning products, 4. The composition of claim 1, wherein the particle size of all purpose cleaning products, jewelry products, and metal 30 the bioactive glass has an average particle size of less than 10 cleaning products. microns. 5. The composition of claim 1, wherein the particle size of 129. A method of making a cleaning agent composition com the bioactive glass has an average particle size of less than 5 prising combining bioactive glass and a cleaning agent. microns. 130. The method of embodiment 129, wherein the bioactive 35 glass is melt-derived. 6. The composition of claim 1, wherein the personal care 131. The method of embodiment 129, wherein the bioactive composition is a cream, lotion, lipstick, make-up compound, glass is sol-gel-derived. or tinctures. 7. The composition of claim 1, wherein the bioactive glass 132. The method of embodiment 129, wherein the bioactive is present in an amount of up to 95% of the total weight of the glass is an aqueous extract. 40 133. The method of embodiment 129, wherein the cleaning formulation. agent is selected from the group consisting of: laundry deter 8. The composition of claim 1, wherein the bioactive glass gents, stain removers, fabric softening products, dish washing is present in an amount of up to 70% of the total weight of the products, air fresheners, deodorizing products, bathroom tis formulation. Sue, facial tissue, paper towel products, napkin products, cot 9. The composition of claim 1, wherein the bioactive glass ton Swabs, handiwipes, scouring products, sponge products, 45 is present in an amount of up to 50% of the total weight of the oven cleaning products, toilet cleaning products, tub and formulation. shower cleaning products, carpet cleaning products, all pur 10. The composition of claim 1, wherein the bioactive glass pose cleaning products, jewelry products, and metal cleaning is present in an amount of up to 40% of the total weight of the products. formulation. 134. A nutritional supplement composition comprising bio 50 11. A non-irritating, stable personal care composition com active glass and a nutritional supplement. prising bioactive glass, a personal skin care product, and citric 135. The composition of embodiment 134, wherein the bio acid, wherein the pH of the composition is between about 5 active glass is melt-derived. and about 8. 136. The composition of embodiment 134, wherein the bio 12. The composition of claim 1, wherein the particle size of active glass is sol-gel-derived. 55 the bioactive glass has an average particle size of less than 2 137. The composition of embodiment 134, wherein the bio microns. active glass is an aqueous extract.