(45)  Date of Patent:  Aug. 26, 2014  (IO)  Patent No.:  US 8,815,974 B2  c12)  United States Patent  Matsushige et al.  (54)  DENTAL ADHESIVE COMPOSITION  (75)  Inventors:  Koji Matsushige,  Tokyo (JP);  Qian Cui,  Tokyo (JP);  Ayumi Dodomi,  Tokyo (JP)  (73)  Assignee:  Tokuyama Dental Corporation,  Tokyo  (JP)  ( * )  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 38 days.  (21)  Appl. No.:  13/511,952  (22)  PCT Filed:  Dec. 2, 2010  (86)  PCT No.:  PCT  I  JP2010/071597  § 371 (c)(l),  (2), ( 4) Date:  May 24, 2012  (87)  PCT Pub. No.:  WO2011/068164  (51)  Int. Cl.  A61K6/083  A61K6/00  (2006.01)  (2006.01)  (52)  U.S. Cl.  CPC ....................................  A61K 6/0023  (2013.01)  USPC ...........  523/116;  523/115; 523/113; 523/118;  523/28  (58)  Field of Classification Search  None  See application file for complete search history.  13 Claims, No Drawings  (57)  ABSTRACT  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  (65)  Prior Publication Data  (30)  Foreign Application Priority Data  (56)  References Cited  U.S. PATENT DOCUMENTS  4,259,075 A  3/1981 Yamauchi et al.  4,259,117 A  3/1981 Yamauchi et al.  4,368,043 A  1/1983 Yamauchi et al.  4,539,382 A  9/1985 Omura et al.  4,612,384 A  9/1986 Omura et al.  4,650,847 A  3/1987 Omura et al.  5,295,690  A  *  3/1994 Johnson ........................ 473/212  5,556,897  A  9/1996 Honda et al.  6,528,555 Bl  3/2003 Nikutowski et al.  6,583,197 Bl  6/2003 Wada et al.  6,960,079 B2  11/2005 Brennan et al.  8,357,731 B2 *  1/2013 Matsushige et al. ............ 522/79  2004/0254261 Al  12/2004 Kojima et al.  2009/0076189 Al  3/2009 Matsushige et al.  2010/0216907 Al*  8/2010 Matsushige et al. .......... 522/154  2010/0261144 Al  10/2010 Fujinami et al.  2010/0317762 Al*  12/2010 Matsushige et al. .......... 523/118  EP  0363903  4/1990  EP  363903 A2 *  4/1990  A61K6/00  EP  0712622  5/1996  EP  712622 Al *  5/1996  A61K6/00  EP  2022463  2/2009  EP  2123246 Al *  11/2009  A61K6/00  EP  2305205  4/2011  JP  52-113089  9/1977  JP  58-21687  2/1983  JP  2-157207  6/1990  JP  5-85912  4/1993  JP  6-9327  1/1994  JP  6-24928  2/1994  JP  7-82115  3/1995  JP  8-319209  12/1996  JP  9-263604  10/1997  JP  10-236912  9/1998  JP  2000-159621  6/2000  JP  2001-72523  3/2001  JP  2001-122718  5/2001  JP  2004-510796  4/2004  JP  2004-352698  12/2004  JP  2005-529637  10/2005  WO  2007 /139207  12/2007  WO  2008/102489  8/2008  WO  2009/051045  4/2009  WO  2009/063967  5/2009  WO  2010/010901  1/2010  US 2012/0238658 Al  Sep. 20, 2012  Dec. 4, 2009  (JP) ................................. 2009-276046  PCT Pub. Date:  Jun. 9, 2011  wherein VF is a valence number of the fluoride ions (E)  contained in the composition, and TV Pis a total valence  number of the polyvalent metal ions (B) contained in the  composition,  satisfies a range of0.2 to 2.0.  [Means for Solution] A dental adhesive composition which is  acidic and contains an acidic group-containing polymerizable  monomer (A), polyvalent metal ions (B), water (C), a water› soluble organic solvent (D) and fluoride ions (E), wherein at  least 35% by mole of the acidic group-containing polymer› izable monomer (A) is a phosphoric acid-type compound  having a hydrogenphosphoric di ester group, and the contents  of the fluoride ions (E) and the polyvalent metal ions (B) are  so set that a valence number ratio  (RF)  defined by the follow› ing formula (1):  [Problems] To provide a liquid dental adhesive composition  which contains a phosphoric acid-type compound having a  hydrogenphosphoric diester group as an acidic group-con› taining polymerizable monomer and, further, contains poly› valent metal ions, effectively preventing not only the gelation  but also the formation of precipitates (cloudiness) during the  storage.  Primary Examiner  - James J Seidleck  Assistant Examiner  - Peter A Salamon  (74)  Attorney, Agent, or Firm  - Rankin, Hill & Clark LLP  * cited by examiner  International Search Report dated Jan. 18, 2011.  Extended European Search Report dated Dec. 12, 2013 filed in cor› responding European patent application No. 10834614.9.  US008815974B2  Rp~Vp’TVp  (1) 