Dental materials having low polymerization shrinkage

Abstract

The present invention relates to dental materials composed of calix[n]arenes and also to the use thereof for cements, composites, adhesives and coating materials in the dental field. The materials include (a) 0.5 to 90% by weight of at least one polymerizable calix[n]arene according to formula (I), (b) 0.01 to 5% by weight of initiator, (c) 0 to 90% by weight of at least one additional monomer which can polymerize under cationic and/or radical conditions and/or which can polymerize by ring opening, (d) 0 to 85% by weight of filler, (e) 0.01 to 5% by weight of additive and (f) 0 to 70% by weight of solvent.

1 . Dental materials comprising 
 (a) 0.5 to 90% by weight of at least one polymerizable calix[n]arene according to general formula (I),                          (b) 0.01 to 5% by weight of initiator,    (c) 0 to 90% by weight of at least one additional monomer which can polymerize under cationic and/or radical conditions and/or which can polymerize by ring opening,    (d) 0 to 85% by weight of filler,    (e) 0.01 to 5% by weight of additive and    (f) 0 to 70% by weight of solvent.    
     
     
         2 . Dental materials according to  claim 1 , comprising 
 (a) 0.5 to 40% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 2% by weight of initiator,    (c) 1 to 70% by weight of an additional monomer which can polymerize under cationic and/or radical conditions and/or which can polymerize by ring opening,    (d) 3 to 80% by weight of filler and    (e) 0.01 to 3% by weight of additive, the percentages each time adding up to 100%.    
     
     
         3 . Dental materials according to  claim 1 , comprising calix[n]arenes of the general formula (I):  
       
         
           
           
               
               
           
         
       
       in which 
 n=1 to 5,  
 R 1 -R 4 =independently of one another, H, a C 1 - to C 15 -alkyl radical which can be interrupted by O, a phenyl radical or a benzyl radical,  
 X 1  represents a group with the structure: 
 Y 1 —R a   1  (Y a   1 —R b   1 —PG 1 ) m , in which  
 
 Y 1 =not present or O, ester, amide or urethane,  
 R a   1 =an m-valent organic radical which can comprise from 1 to 30 carbon atoms and, if appropriate, also from 0 to 6 heteroatoms, such as O, S or N,  
 m=1 to 3,  
 Y a   1 =not present or O, ester, amide or urethane,  
 R b   1 =not present or a C 1 -C 16 -alkylene radical which can be interrupted by oxygen atoms,  
 PG 1 =a polymerizable group, e.g. a group which can polymerize under radical conditions, such as (meth)acrylate, (meth)acrylamide, vinyl, allyl or styryl; a cyclic group which can polymerize under radical conditions by ring opening, such as, e.g., the groups  
                     
 or a group which can polymerize under cationic conditions, such as, e.g., a vinyl ether or glycidyl group, a cycloaliphatic epoxide or oxetane group or a polymerizable nitrone group, with  
 Y b   1 =not present or O, ester, amide or urethane,  
 R c   1 , R d   1 =independently of one another, C 1 - to C 15 -alkyl radical which can be interrupted by O, a phenyl radical or a benzyl radical; 
 and with furthermore  
 
 X 2 -X 4 =independently of one another, not present, OH or C 1 - to C 10 -alkyl radical and which can have, independently of one another, the same meaning of X 1  and, in addition, can represent a group with the structure: (Y a   2 —R b   2 -AG) p , in which  
 Y a   2 =not present or O, ester, amide or urethane,  
 R b   2 =a p-valent organic radical which can comprise from 1 to 20 carbon atoms and, if appropriate, also from 0 to 4 heteroatoms, such as O or N,  
 p=1 to 3 and  
 AG=an anchoring group, such as —P═O(OH) 2 , —O—P═O(OH) 2 , —COOH or —O—SO 2 OH.  
 
     
     
         4 . Dental materials according to  claim 2 , comprising calix[n]arenes of the formula (I):  
       
         
           
           
               
               
           
         
       
       in which 
 n=1 to 3,  
 R 1 -R 4 =independently of one another, H, a C 1 - to C 10 -alkyl radical which can be interrupted by O, or a benzyl radical,  
 X 1  represents a group with the structure: 
 Y 1 —R a   1 (Y a   1 —R b   1 —PG 1 ) m , in which  
 
 Y 1 =not present or O or ester,  
 R a   1 =an m-valent organic radical which can comprise from 1 to 15 carbon atoms and, if appropriate, also from 0 to 3 oxygen atoms,  
 m=1 to 2,  
 Y a   1 =not present or O or ester,  
 R b   1 =not present or a C 1 -C 16 -alkylene radical which can be interrupted by oxygen atoms,  
 PG 1 =a polymerizable group, a group, which can polymerize under radical conditions, such as (meth)acrylate or (meth)acrylamide, a cyclic group which can polymerize under radical conditions by ring opening, such as, e.g., the groups  
                     
 or a group which can polymerize under cationic conditions, such as, e.g., a cycloaliphatic epoxide or oxetane group or a polyreactive nitrone group, with  
 Y b   1 =not present or O, ester or urethane,  
 R c   1 , R d   1 =independently of one another, C 1 - to C 5 -alkyl radical, a phenyl radical or a benzyl radical; 
 and with furthermore  
 
 X 2 -X 4 =independently of one another, not present or C 1 - to C 10 -alkyl radical and which can have, independently of one another, the same meaning of X 1  and, in addition, can represent a group with the structure: (Y a   2 —R b   2 -AG) p , in which  
 Y a   2 =not present or O or ester,  
 R b   2 =a p-valent organic radical which can comprise from 1 to 10 carbon atoms and, if appropriate, also from 0 to 2 oxygen atoms,  
 p=1 to 2 and  
 AG=an anchoring group, such as, e.g., —P═O(OH) 2 , —O—P═O(OH) 2 , —COOH or —O—SO 2 OH.  
 
     
     
         5 . Dental materials according to  claim 1 , comprising from 0.5 to 90% by weight of a calix[n]arene of the formula (I).  
     
     
         6 . Dental materials according to  claim 1 , additionally comprising initiators, additional monomers which can polymerize under cationic conditions, monomers which can polymerize under radical conditions, fillers and additives or one or more of these substances,  
     
     
         7 . Dental materials according to  claim 6 , comprising, as monomers which can polymerize under radical conditions, monomers which can polymerize by ring opening, in particular mono- or polyfunctional vinylcyclopropanes or bicyclic cyclopropaneacrylates or cyclic allyl sulphides, and polyfunctional (meth)acrylates or mixtures of these monomers.  
     
     
         8 . Dental materials according to  claim 1 , the materials being cements comprising 
 (a) 0.5 to 30% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 2% by weight of initiator,    (c) 1 to 30% by weight of at least one additional monomer which can polymerize under cationic and/or radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 5 to 70% by weight of filler and    (e) 0.01 to 5% by weight of additive,    the percentages each time adding up to 100%.    
     
     
         9 . Dental materials according to  claim 8 , comprising 
 (a) 0.5 to 20% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 1.5% by weight of initiator,    (c) 5 to 20% by weight of at least one additional monomer which can polymerize under radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 10 to 60% by weight of filler and    (e) 0.01 to 3% by weight of additive,    the percentages each time adding up to 100%.    
     
     
         10 . Dental materials according to  claim 1 , the materials being filling composites comprising 
 (a) 0.5 to 30% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 5% by weight of initiator,    (c) 1 to 30% by weight of at least one additional monomer which can polymerize under ionic or radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 5 to 85% by weight of filler and    (e) 0.01 to 5% by weight of additive,    the percentages each time adding up to 100%.    
     
     
         11 . Dental materials according to  claim 10 , comprising 
 (a) 0.5 to 20% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 2% by weight of initiator,    (c) 5 to 20% by weight of at least one additional monomer which can polymerize under radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 10 to 80% by weight of filler and    (e) 0.01 to 3% by weight of additive,    the percentages each time adding up to 100%.    
     
     
         12 . Dental materials according to  claim 1 , the materials being coating materials comprising 
 (a) 0.5 to 70% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 5% by weight of initiator,    (c) 5 to 60% by weight of at least one additional monomer which can polymerize under ionic or radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 1 to 30% by weight of a filler,    (e) 0.01 to 5% by weight of additive and    (f) 0 to 70% by weight of solvent,    the percentages each time adding up to 100%.    
     
     
         13 . Dental materials according to  claim 12 , comprising 
 (a) 1 to 50% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 1.5% by weight of initiator,    (c) 5 to 60% by weight of at least one additional monomer which can polymerize under radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 3 to 20% by weight of a filler,    (e) 0.01 to 3% by weight of additive and    (f) 0 to 30% by weight of solvent,    the percentages each time adding up to 100%.    
     
     
         14 . Dental materials according to  claim 1 , the materials being dental adhesives comprising 
 (a) 0.5 to 50% by weight of at least one calix[n]arene according to formula (I),    (b) 0.01 to 5% by weight of at least one initiator,    (c) 5 to 70% by weight of at least one additional monomer which can polymerize under radical conditions and/or at least one additional monomer which can polymerize by ring opening,    (d) 0 to 30% by weight of filler,    (e) 0.01 to 5% by weight of additives and    (f) 0 to 50% by weight of solvent,    the percentages each time adding up to 100%.    
     
     
         15 . Dental materials according to  claim 14 , comprising 
 (a) 1 to 30% by weight of a calix[n]arene according to formula (I),    (b) 0.01 to 2% by weight of at least one initiator,    (c) 5 to 60% by weight of at least one additional monomer which can polymerize under cationic and/or radical conditions and/or by ring opening,    (d) 3 to 20% by weight of filler,    (e) 0.01 to 3% by weight of additives and    (f) 0 to 20% by weight of solvent,    the percentages adding up to 100%.