Dental adhesive

Abstract

The present invention relates to an aqueous dental composition having a pH of at most 7. Furthermore, the present invention relates to the use of a specific composition for the preparation of an aqueous dental composition.

1 . An aqueous dental composition having a pH of at most 7, comprising:
 (a) 1 to 70 percent by weight based on the total weight of the composition of a polymerizable compound of the following formula (I):
   A-L-B  (I)
 
 wherein 
 A is a group of the following formula (II) 
   
       
         
           
           
               
               
           
         
         
           
             X 1  is CO, CS, CH 2 , or a group [X′Z] k , wherein X′ is an oxygen atom, a sulfur atom or NH, Z is a straight chain or branched C 1-4  alkylene group, and k is an integer of from 1 to 10; 
             R 1  is a hydrogen atom,
 —COOM, 
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 
             R 2  is a hydrogen atom,
 —COOM 
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  and —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, or 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  and —SO 3 M, 
 
           
           L is a divalent C 2-12  alkenylene linker group, which may contain 1 to 3 carbonyl groups or heteroatoms selected from oxygen, nitrogen and sulfur, and which may be substituted by a hydroxyl group, a C 6-14  aryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, wherein M is a hydrogen atom or a metal atom; 
           B is selected from
 (i) a group according to the definition of A, 
 (ii) a group of the following formula (III) 
 
         
       
       
         
           
           
               
               
           
         
         
           
             
               X 2  independently has the same meaning as defined for X′ in formula (II), 
               R 1′  and R 2′  are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), 
               R is a hydrogen atom, 
                a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
                a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
                a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
             
             (iii) a group of the following formula (IV) 
           
         
       
       
         
           
           
               
               
           
         
         
           
             
               wherein 
               X 3  is CO, —CH 2 CO—, CS, or —CH 2 CS—, 
               R 1′  and R 2″  which are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), or 
             
             (iv) a group [Z′X″] m E, wherein
 Z′ is a straight chain or branched C 1-4  alkylene group, 
 X″ is an oxygen atom, a sulfur atom or NH, 
 E is a hydrogen atom, 
  PO 3 M 2 , 
  a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
  a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
  a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, and 
 m is an integer of from 1 to 10; and 
 
             wherein M of any one R 1 , R 2 , L, R and E, which M are independent from each other, each represent a hydrogen atom or a metal atom; 
           
         
         (b) 2 to 20 percent by weight based on the total weight of the composition of a polymerizable compound of the following formula (V):
   A′-L′-A′   (V)
 
 wherein the 
 A′ which are independent from each other, each represent a group of the following formula (VI) 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X 2 * independently has the same meaning as defined for X 1  in formula (II), 
             R 1 * and R 2 * are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), 
             R* is a hydrogen atom,
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 
           
           L′ is a divalent C 2-12  alkylene linker group, which may contain 1 to 3 carbonyl groups or heteroatoms selected from oxygen, nitrogen and sulfur, and which may be substituted by a hydroxyl group, a C 6-14  aryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, wherein M is a hydrogen atom or a metal atom;
 wherein M of any one R 1′ , R 2 *, L′ and R*, which M are independent from each other, each represent a hydrogen atom or a metal atom; 
 
         
         (c) 1 to 20 percent by weight based on the total weight of the composition of one or more polymerizable monomers having one or more acidic groups; 
         (d) 0.001 to 5 percent by weight based on the total weight of the composition of an initiator system; 
         (e) 0.001 to 1 percent by weight based on the total weight of the composition of a stabilizer; and 
         (f) 25 to 50 percent by weight based on the total weight of the composition of a solvent mixture comprising water and an organic solvent. 
       
     
     
         2 . The aqueous dental composition according to  claim 1 , wherein B is a group according to the definition of A. 
     
     
         3 . The aqueous dental composition according to  claim 1  or  2 , wherein X 1  in formula (II) is CO. 
     
     
         4 . The aqueous dental composition according to any one of the preceding claims, wherein X 2  in formula (VI) is CO. 
     
     
         5 . The aqueous dental composition according to any one of the preceding claims wherein L is —CH 2 CH═CHCH 2 —. 
     
     
         6 . The aqueous dental composition according to any one of the preceding claims, comprising a polymerizable phosphoric acid ester as a polymerizable monomer having one or more acidic groups. 
     
     
         7 . The aqueous dental composition according to any one of the preceding claims, which further comprises a polymerizable monomer having at least three polymerizable double bonds. 
     
     
         8 . The aqueous dental composition according to any one of the preceding claims, wherein the stabilizer is a compound of the following formula (VII) and/or (VIII): 
       
         
           
           
               
               
           
         
         wherein 
         the R 3 , which may be the same or different, independently represent a branched C 3-8  alkyl or alkenyl group or a C 3-8  cycloalkyl or cycloalkenyl group, 
         R 4  represents a hydrogen atom, a C 1-6  alkyl or C 2-6  alkenyl group, or a C 1-6  fluoroalkyl or C 2-6  fluoroalkenyl group, 
         X represents a group selected from a C 18  alkyl group or a C 3-8  cycloalkyl group, and 
         n is 0, 1 or 2. 
       
     
     
         9 . The aqueous dental composition according to any one of the preceding claims, wherein the organic solvent of the solvent mixture is selected from the group consisting of ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, acetone and methyl ethyl ketone, preferably the organic solvent of the solvent mixture is n-propanol or iso-propanol, more preferably iso-propanol. 
     
     
         10 . The aqueous dental composition according to any one of the preceding claims, wherein the solvent mixture comprises at least 1 percent by weight based on the total weight of the composition, of water. 
     
     
         11 . The aqueous dental composition according to any one of the preceding claims, which further comprises a particulate filler. 
     
     
         12 . The aqueous dental composition according to any one of the preceding claims, which is selected from a dental adhesive composition, a dental bonding agent, a dental primer, a dental infiltrant, a pit and fissure sealant, a dental desensitizing composition, a pulp capping composition, a dental composite, dental glass ionomer cement, a dental cement, a seal and protecting composition for naked tooth necks, and a dental root canal sealer composition. 
     
     
         13 . Use of a composition comprising
 (a) a polymerizable compound of the following formula (I):
   A-L-B  (I)
 
 wherein 
 A is a group of the following formula (II) 
   
       
         
           
           
               
               
           
         
         
           
             X 1  is CO, CS, CH 2 , or a group [X′Z] k , wherein X′ is an oxygen atom, a sulfur atom or NH, Z is a straight chain or branched C 1-4  alkylene group, and k is an integer of from 1 to 10; 
             R 1  is a hydrogen atom,
 —COOM, 
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 
             R 2  is a hydrogen atom,
 —COOM 
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  and —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, or 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  and —SO 3 M, 
 
           
           L is a divalent C 2-12  alkenylene linker group, which may contain 1 to 3 carbonyl groups or heteroatoms selected from oxygen, nitrogen and sulfur, and which may be substituted by a hydroxyl group, a C 6-14  aryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, wherein M is a hydrogen atom or a metal atom; 
           B is selected from
 (i) a group according to the definition of A, 
 (ii) a group of the following formula (III) 
 
         
       
       
         
           
           
               
               
           
         
         
           
             
               X 2  independently has the same meaning as defined for X 1  in formula (II), 
               R 1′  and R 2′  are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), 
               R is a hydrogen atom, 
                a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
                a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
                a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
             
             (iii) a group of the following formula 
           
         
       
       
         
           
           
               
               
           
         
         
           
             
               wherein 
               X 3  is CO, —CH 2 CO—, CS, or —CH 2 CS—, 
               R 1″  and R 2″  which are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), or 
             
             (iv) a group [Z′X″] m E,
 wherein 
  Z′ is a straight chain or branched C 1-4  alkylene group, 
  X″ is an oxygen atom, a sulfur atom or NH, 
  E is a hydrogen atom, 
  PO 3 M 2 , 
  a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
  a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
  a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, and 
  m is an integer of from 1 to 10; and 
 
             wherein M of any one R 1 , R 2 , L, R and E, which M are independent from each other, each represent a hydrogen atom or a metal atom; and 
           
         
         (b) 2 to 20 percent by weight based on the total weight of the composition of a polymerizable compound of the following formula (V):
   A′-L′-A′   (V)
 
 wherein the 
 A′ which are independent from each other, each represent a group of the following formula (VI) 
 
       
       
         
           
           
               
               
           
         
         
           
             wherein 
             X 2 * independently has the same meaning as defined for X 1  in formula (II), 
             R 1 * and R 2 * are independent from each other and independently have the same meaning as defined for R 1  and R 2  in formula (II), 
             R* is a hydrogen atom,
 a straight chain or branched C 1-16  alkyl group which may be substituted by a C 3-6  cycloalkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 3-6  cycloalkyl group which may be substituted by a C 1-16  alkyl group, a C 6-14  aryl or C 3-14  heteroaryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 a C 6-14  aryl or C 3-14  heteroaryl group which may be substituted by —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, 
 
           
           L′ is a divalent C 2-12  alkylene linker group, which may contain 1 to 3 carbonyl groups or heteroatoms selected from oxygen, nitrogen and sulfur, and which may be substituted by a hydroxyl group, a C 6-14  aryl group, —COOM, —PO 3 M, —O—PO 3 M 2  or —SO 3 M, wherein M is a hydrogen atom or a metal atom;
 wherein M of any one R 1 *, R 2 *, L′ and R*, which M are independent from each other, each represent a hydrogen atom or a metal atom; 
 
         
         for the preparation of an aqueous dental composition.