(C) Peter Meiers - http://www.fluoride-history.de


Fillings and sealants containing and releasing fluorides


see also:

Fluoride and corrosion of amalgam:






In his often-cited book on the history of dentistry, Walter Hoffmann-Axthelm claims that the first mention of the use of fluoride for "caries prevention" (if inserted into a tooth) was in a book by the French dentist Antoine Malagou Désirabode. However, the original text by Désirabode clearly describes the use of fluoride (then still called "fluate", as in "fluate de chaux" for calcium fluoride (fluorspar)) for the preparation of a dental filling material (page 409, Chapter "De l´obliteration ou plombage des dents", in his book "Nouveaux éléments complets de la science et de l´art du dentiste", Paris 1845), a technical use that was later filed in so many patents, without any reference to a "preventive" effect:



Reinhold BONSELS, Kiel, Germany: "Verfahren zur Herstellung von Zahnkitt", German Patent DE 82797, filed Dec. 11, 1894, pat. Sept. 12, 1895 (addition of fluorspar to a filling based upon silk dissolved in concentrated phosphoric acid)


Dr. F. SCHOENBECK & Co., Leipzig, Germany: "Verfahren zur Herstellung von Zahnkitt von glasiger oder porzellanähnlicher, schmelzartiger Struktur", German Patent DE 306,837, filed Sept. 6, 1907, patented July 12, 1918 (addition of cryolite)


George S. MILLER, Chicago, Ill., assignor to Dental Cement Company ltd., of Chicago, Ill.: "Process for making dental cements", US Patent 1,172,723, filed Dec. 17, 1914, patented Feb. 22, 1916 (addition of cryolite)


Heinrich HERZOG, of Basel, Switzerland: "Process for the preparation of a material for protecting and repairing teeth and making artificial teeth", British Patent GB 435,536; filed Dec. 21, 1933, [specification not accepted] (addition of calcium fluoride)

Eugen BRILL, of Berlin, Germany: "Improvements in or relating to dental filling materials", British Patent GB 430,624; filed Sept. 28, 1933 (Germany), Sept. 27, 1934 (Great Britain), patented June 21, 1935 (addition of fluorspar)


Joseph H. SCHLESINGER, assignor to Eagle Chemical Company, New York: "Neutralization of acids exuding from silicious cements", US Patent 2,154,413; filed Nov. 11, 1935; patented April 11, 1939 ("Kaolin, which is the base of most silicious cement preparations on the market, often contains fluorides of aluminum which, in contact with phosphoric acid, will yield hydrofluoric acid; likewise traces of arsenic may be found in kaolin which may give origin to arsenious acid. All these acids, even in minute quantities, when they exude from the cement and come into contact with the tissues or the structure of the tooth will cause pain and eventually devitalize the pulp of the tooth") 


Herbert RAUTER, assignor to Vita Zahnfabrik H. Rauter O.H.G. of Sackingen, Germany: "Improvement in dental cement", British Patent GB 695,278, filed March 21, 1949, patented Aug. 5, 1953 (contains uranium and fluoride)


Adolf KNAPPWOSTassignor, by mesne assignments,  to Vivadent Corporation, Boston, MA.: "Method of caulking fissures", US Patent 2,802,268, filed March 4, 1952, patented Aug. 13, 1957 (caulking fissures which arise after hardening in usual fillings (amalgams, cements, artificial materials) by magnesium silico-fluoride)

Werner SCHMITT, Robert PURRMANN, both of Starnberg, Germany: "Improvements in methods of producing elastic impression compositions", British Patent GB 778,052, filed July 3, 1952, patented July 3, 1957 (addition of sodium silicofluoride or potassium-titanium fluoride)


CIBA Limited, Basle, Switzerland: "Process for making fillings, crowns and prostheses for dental purposes", British Patent GB 827,699; filed April 9, 1958; patented Feb. 10, 1960 (Epoxy-resins; "As Friedl-Crafts catalysts capable of forming complexes there are especially suitable compounds such as stannic chloride, antimony pentachloride, zinc chloride and boron trifluoride")


Kristin BRIGHAM, Ronald C. VICKERY, assignors to Ceramco Inc., Long Island City, N.Y.: "Dental prosthesis model base composition containing calcium fluoride", US Patent 3,647,488, filed Nov. 4, 1969, patented March 7, 1972


Joseph C. MUHLER, assignor to Indiana University Foundation: "Process for producing a dental cement and product produced thereby", US Patent 3,746,555, filed June 7, 1971, patented July 17, 1973 (additions of either stannous fluoride, stannous fluorozirconate, Indium fluorozirconate, Zirconium hexafluorogermanate, Indium hexafluorogermanate ort Zirconyl hexafluorogermanate)


ESPE Fabrik Pharmazeutischer Präparate GmbH, Seefeld, Germany: "Dental filling materials", British Patent GB 1,382,881; filed Jan. 14, 1972; patented Feb. 5, 1975


Werner SCHMITT, Robert PURRMANN, of Starnberg, Peter JOCHUM, of Pilsensee, Heinz Joachim HÜBNER, of Seefeld, all of Germany, assignors to Espe Fabrik pharmazeutischer Präparate GmbH: "Light curable acrylic dental composition with calcium fluoride pigment", US Patent 4,372,836, filed Jan. 2, 1979, patented Feb. 8, 1983


Jack R. GRIFFITH, Heidelberg, Victoria, Australia: "Bonding Dental Porcelain", US Patent 4,378,248, filed June 30, 1981, patented March 29, 1983


Rainer-Reginald MIETHKE, Heinrich NEWESELY, both of Berlin, Germany: "Mit Fluorid angereicherte zahnärztliche Kunststoffe zur Kariesprophylaxe", German Patent DE 3,404,827, filed Feb. 9, 1984, patented Oct. 10, 1984


Henry R. RAWLS, of New Orleans, Barbara F. ZIMMERMAN, of Matairie, both of La., assignors to Research Corporation New York: "Fluoride interpolymeric resin", US Patent 4,572,920, filed March 20, 1985, patented Feb. 25, 1986


Stephen C. KWAN, of Arlington TX, John J. O´Connell, of Tustin CA, assignors to Kerr Manufacturing Company, Romulus, MI: "Fluorine-containing dental materials", US Patent 4,772,325, filed April 30, 1987, patented Sept. 20, 1988 (boron trifluoride which gives off fluoride upon contact with water; "Studies by Forsten and Paunio ... comparing fluoride release by silicate cements and composite resins have shown that the overall release of fluoride from the two materials was comparable...")


Wolfgang WIEDEMANN, of Höchberg, Hans Georg KLINGER, of Rossbrunn, Germany: "Process for preparing a ceramic material for use in dental fillings and dental crowns", US Patent 5,776,233, filed May 13, 1994, patented July 7, 1998 (contains fluoroapatite)

Oswald GASSER, of Seefeld, Rainer GUGGENBERGER, of Herrsching, both of Germany, assignors to Thera Patent GmbH & Co KG, Gesellschaft für industrielle Schutzrechte: "Formable composition and its use as filling material for dental root canals", US Patent 5,520,922, filed Oct. 18, 1994, patented May 28, 1996


British Technology Group ltd., of London, GB: "Introducing fluoride into glass", British Patent GB 2,322,855, filed March 3, 1997, patented Sept. 9, 1998 ("Aluminosilicate glass particles are fluoridated by stirring them into a solution of NH4-HF2, can be used in glass ionomer cement compositions with poly(acrylic acid) without tartaric acid or other chelating agent")

Teja REETZ, of Berlin, Stefan ZIMMER, of Berlin, Wolfgang KRAHL, of Weinböhla: "Mit Fluorid angereichertes zahnärztliches Mittel zur Kariesprophylaxe", German Patent DE 19,735,929, filed Aug. 8, 1997, patented Feb. 11, 1999 (contains up to 50% CaF2 or MgF2, or mixtures thereof to be build in as a fluoride depot for caries prevention)

Jeffrey W. STANSBURY, Joseph M. ANTONUCCI, Kyung M. CHOI, assignor to the United States of America as represented by the Secretary of the Commerce: "High strength polymeric networks derived from (meth)acrylate resins with organofluorine content and process for preparing same", US Patent 6,184,339; filed Nov. 12, 1997; pat. Feb. 6, 2001


Shoji AKAHANE, Hisashi SATO, Hideki YARIMIZU, Kazuo HIROTA, all of Tokyo, JP, assignors to GC coproration: "Dental filling resin composition", US Patent 5,962,550, filed March 5, 1998, patented Oct. 5, 1999


Paul PANZERA, of Mt. Holly, Jona N. PRUDEN, of Bellemead, Dimitri BRODKIN, of West Orange, Lisa M. KAISER, of Parsippany, Richard A. BRIGHTLY, of Monmouth Junction, Carlino PANZERA, of Bellemead, all of NJ (US): "Dental Porcelain Compositions", US Patent 6,206,958, filed July 15, 1999, patented March 27, 2001


Fred RUEGGEBERG, Gary WHITFORD, Don METTENBURG, assignors to Medical College of Georgia: "Fluoride-releasing amalgam dental restorative material", US Patent Application Publication 2002028856; filed Aug. 13, 2001; publ. March 7, 2002

"The present invention relates to a composition of a novel fluoride-releasing dental amalgam restorative material, which provides the capability to reduce the possibility of secondary decay approximate to a restoration as a result of fluoride release."