Self-etching dental materials based on (meth)acrylamide phosphates

Abstract

Polymerizable dental material, characterized in that it contains at least one (meth)acrylamide phosphate of the following general formula (I): in which R 1 is H or CH 3 ; R 2 is H or a C 1 -C 4 alkyl radical or forms together with the nitrogen atom to which it is bonded and one or more atoms which belong to R 3 or R 3′ a heterocyclic ring; R 3 , R 3′ independently of each other are a linear or branched aliphatic C 1 -C 50 radical with a valency of m+n or p+n, an aromatic C 6 -C 18 radical with a valency of m+n or p+n, or a cycloaliphatic, araliphatic or heterocyclic C 3 -C 18 radical with a valency of m+n or p+n, wherein the carbon chains of the radical or radicals can be interrupted by O, S, CONR 4 , OCONH, or form together with one or more atoms which belong to R 2 and the nitrogen atom, to which the R 2 is bonded a heterocyclic ring, R 3′ being H if p=0, and R 4 being H, C 1 -C 10 alkyl, C 6 -C 12 aryl, C 6 -C 10 aralkyl or a bicyclic C 4 -C 12 radical; n is 1, 2, 3 or 4 if p=0, and is 1 or 2 if p≠0; m is 1, 2, 3 or 4; p is 0, 1, 2, 3 or 4; x is 0 or S.

1 . Polymerizable dental material, which comprises at least one (meth)acrylamide phosphate of the following general formula (I): 
     
       
         
         
             
             
         
       
       in which 
       R 1  is H or CH 3 ; 
       R 2  is H or a C 1 -C 4  alkyl radical; 
       R 3 , R 3′  independently of each other are a linear or branched aliphatic C 1 -C 50  radical with a valency of m+n or p+n, an aromatic C 6 -C 18  radical with a valency of m+n or p+n, or a cycloaliphatic, araliphatic or heterocyclic C 3 -C 18  radical with a valency of m+n or p+n, wherein the carbon chains of the radical or radicals can be interrupted by O, S, CONR 4 , OCONH, R 3′  being H if p=0, and wherein 
       R 4  is H, C 1 -C 10  alkyl, C 6 -C 12  aryl, C 6 -C 10  aralkyl or a bicyclic C 4 -C 12  radical; 
       n is 1, 2, 3 or 4 if p=00, and
 is 1 or 2 if p≠0; 
 
       m is 1, 2, 3 or 4; 
       p is 0, 1, 2, 3 or 4; 
       x is 0 or S. 
     
   
   
       2 . Dental material according to  claim 1 , in which R 2  is a C 1 -C 4  alkyl radical. 
   
   
       3 . Dental material according to  claim 1 , comprising at least one (meth)acrylamide phosphate of formula (I′): 
     
       
         
         
             
             
         
       
       wherein 
       R 1 =H or CH 3 ; 
       R 2 =H or a C 1 -C 4  alkyl radical; 
       R 3 =a linear or branched aliphatic C 1 -C 12  radical, a cycloaliphatic or a heterocyclic C 3 -C 18 , wherein the carbon chain of the radical can be interrupted by O, S, CONH, or OCONH; 
       m=1, 2, 3 or 4; 
       X=O or S. 
     
   
   
       4 . Dental material according to  claim 1 , wherein at least one of the variables has one of the following meanings:
 R 1 =H or CH 3 ;   R 2 =H or a C 1 -C 3  alkyl radical;   R 3 =a linear or branched aliphatic C 1 -C 3  radical with a valency of m+n;   R 3′ =H;   R 4 =H, C 1 -C 3  alkyl;   n=1;   m=1 or 2;   p=0;   x=O.   
   
   
       5 . Dental material according to  claim 1 , which additionally contains a solvent. 
   
   
       6 . Dental material according to  claim 5 , which contains as solvent water or a mixture of water and a solvent miscible with water. 
   
   
       7 . Dental material according to  claim 1 , which additionally contains at least one non-acid, radically polymerizable monomer. 
   
   
       8 . Dental material according to  claim 7 , which contains as non-acid monomer one or more monomers from the following group: mono(meth)acryl compounds, mesityl(meth)acrylate, 2-(alkoxymethyl)acrylic acids, 2-(ethoxymethyl)acrylic acid, 2-(hydroxymethyl)acrylic acid, N-mono and N-disubstituted acrylamides, N-ethylacrylamide, N,N-dimethylacrylamide, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl)acrylamide, N-monosubstituted methacrylamide, N-ethylmethacrylamide, N-(2-hydroxyethyl)methacrylamide, N-vinylpyrrolidone and allyl ethers. 
   
   
       9 . Dental material according to  claim 7 , which contains as non-acid monomer one or more monomers from the following group: urethanes from 2-(hydroxymethyl)acrylic acid and diisocyanates, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, cross-linking pyrrolidones, 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, bisacrylamides, methylene and ethylene bisacrylamide, bis(meth)acrylamides, N,N′-diethyl-1,3-bis(acrylamido)propane, 1,3-bis(methacrylamido)-propane, 1,4-bis(acrylamido)-butane and 1,4-bis(acryloyl)-piperazine. 
   
   
       10 . Dental material according to  claim 1 , which additionally contains at least one initiator for the radical polymerization. 
   
   
       11 . Dental material according to  claim 1 , which additionally contains at least one filler. 
   
   
       12 . Dental material according to  claim 1 , which contains the following components:
 a) 0.5 to 95 wt.-% (meth)acrylamide phosphate according to Formula (I),   b) 0.01 to 15 wt.-% initiator,   c) 0 to 80 wt.-% non-acid radically polymerizable monomer,   d) 0 to 95 wt.-% solvent,   e) 0 to 20 wt.-% filler.   
   
   
       13 . Dental material according to  claim 12 , which additionally contains
 f) 0.01 to 10 wt.-% of one or more further additives.   
   
   
       14 . Dental material comprising
 a) 0.5 to 95 wt.-% of at least one (meth)acrylamide phosphate of the following general formula (I):   
     
       
         
         
             
             
         
       
       
         in which 
         R 1  is H or CH 3 ; 
         R 2  is H or a C 1 -C 3  alkyl radical; 
         R 3 , R 3′  independently of each other are a linear or branched aliphatic C 1 -C 50  radical with a valency of m+n or p+n, an aromatic C 6 -C 18  radical with a valency of m+n or p+n, or a cycloaliphatic, araliphatic or heterocyclic C 3 -C 18  radical with a valency of m+n or p+n, wherein the carbon chains of the radical or radicals can be interrupted by O, S, CONH, OCONH, R 3′  being H if p=0, and wherein 
         n is 1, 2, 3 or 4 if p=0, and
 is 1 or 2 if p≠0; 
 
         m is 1, 2, 3 or 4; 
         p is 0, 1, 2, 3 or 4; 
         X is O or S 
       
       b) 0.01 to 8 wt.-% initiator, 
       c) 0 to 80 wt.-% non-acid radically polymerizable monomer, 
       d) 0 to 80 wt.-% solvent, 
       e) 0 to 20 wt.-% filler. 
     
   
   
       15 . Dental material comprising
 a) 0.5 to 95 wt.-% of at least one (meth)acrylamide phosphate of the following general formula (I′):   
     
       
         
         
             
             
         
       
       
         wherein 
         R 1 =H or CH 3 ; 
         R 2 =H or a C 1 -C 4  alkyl radical; 
         R 3 =a linear or branched aliphatic C 1 -C 50  radical, a cycloaliphatic or a heterocyclic C 3 -C 18 , wherein the carbon chain of the radical can be interrupted by O, S, CONH, or OCONH; 
         m=1, 2, 3 or 4; 
         X=O or S 
       
       b) 0.01 to 8 wt.-% initiator, 
       c) 0 to 80 wt.-% non-acid radically polymerizable monomer, 
       d) 0 to 80 wt.-% solvent, 
       e) 0 to 20 wt.-% filler. 
     
   
   
       16 . Dental material according to  claim 14 , wherein the non-acid radically polymerizable monomer is a (meth)acrylamide monomer. 
   
   
       17 . Dental material according to  claim 15 , wherein the non-acid radically polymerizable monomer is a (meth)acrylamide monomer.