Self etch all purpose dental compositions, method of manufacture, and method of use thereof

Abstract

A self-etching and self-adhesive dental composition is provided, comprising a polymerizable (meth)acrylate carboxylic acid/anhydride; a copolymerizable multi-functional (meth)acrylate resin; a copolymerizable diluent monomer; and a curing system. The composition has the advantage of not requiring a separate etching and bonding step.

1 . A self-etching and bonding dental resin composition comprising in combination 
 about 20 to about 60 weight percent of a polymerizable (meth)acrylate carboxylic acid/anhydride, based on the total weight of the polymerizable components in the composition;    a copolymerizable multi-functional (meth)acrylate resin;    a copolymerizable diluent monomer; and    a curing system.    
   
   
       2 . The composition of  claim 1 , wherein the polymerizable (meth)acrylate carboxylic acid/anhydride is a compound according to structure (I):  
     
       
         
         
             
             
         
       
     
     wherein 
 n is 0, 1, 2, 3, or 4;  
 q is 1, 2, 3, or 4;  
 A is an anhydride group;  
 a is 0 or 1, with the proviso that a and n are not both 0;  
 R 1 , R 2 , R 3 , and R 4  are each independently hydrogen, hydroxy, C 1 -C 12  alkyl, C 1 -C 12  perhaloalkyl, C 1 -C 12  alkoxy, C 1 -C 12  perhaloalkoxy, C 2 -C 12  alkenyl, C 2 -C 12  alkynyl, (C 1 -C 6  alkyl)-O—(C 1 -C 6  alkylene), or hydroxy(C 1 -C 6  alkylene);  
 x and y are each independently an integer from 1 to 10;  
 R 5  is a hydrogen or methyl group;  
 M is  
                     
 wherein G and J are each independently oxygen or NR 6 , wherein R 6  is hydrogen or C 1 -C 6  alkyl;  
 m is 0, 1, or 2; and  
 W is an aromatic or aliphatic hydrocarbyl linking group having a valency corresponding to z+1; and  
 z is 1, 2, 3, 4, or 5.  
 
   
   
       3 . The composition of  claim 1 , wherein the polymerizable (meth)acrylate carboxylic acid/anhydride is a compound according to structure (II):  
     
       
         
         
             
             
         
       
     
     wherein 
 n is 0, 1, 2, 3, or 4;  
 A is an anhydride group;  
 a is 0 or 1, with the proviso that a and n are not both 0;  
 p is 1, 2, 3, or 4;  
 R 5  is a hydrogen or methyl group;  
 R 7  and R 8  are each independently hydrogen, hydroxy, C 1 -C 12  alkyl, C 1 -C 12  perhaloalkyl, C 1 -C 12  alkoxy, C 1 -C 12  perhaloalkoxy, C 2 -C 12  alkenyl, C 2 -C 12  alkynyl, (C 1 -C 6  allyl)-O—(C 1 -C 6  allylene), or hydroxy(C 1 -C 6  allylene); and  
 d is 1 to 10.  
 
   
   
       4 . The composition of  claim 1 , wherein the polymerizable (meth)acrylate carboxylic acid/anhydride is 1,4-dimethacryloyloxyethylpyromellitic acid; 1,4-diacryloyloxyethylpyromellitic acid; 4-(meth)acryloyloxymethyltrimellitic acid; 4-(meth)acryloyloxymethyltrimellitic acid anhydride; 4-acryloyloxymethyltrimellitic acid; 4-acryloyloxymethyltrimellitic acid anhydride; 4-methacryloyloxyethyltrimellitic acid; 4-methacryloyloxyethyltrimellitic acid anhydride; 4-acryloyloxyethyltrimellitic acid; 4-acryloyloxyethyltrimellitic acid anhydride; 4-(2-hydroxy-3-(meth)acryloyloxy)butyltrimellitic acid; 4-(2-hydroxy-3-(meth)acryloyloxy)butyltrimellitic acid anhydride; 4-(2-hydroxy-3-acryloyloxy)butyltrimellitic acid; 4-(2-hydroxy-3-acryloyloxy)butyltrimellitic acid anhydride; an adduct of 2-hydroxyethyl methacrylate with pyromellitic dianhydride; an adduct of 2-hydroxyethyl acrylate with pyromellitic dianhydride; the reaction product of 2-hydroxyethylmethacrylate with ethylene glycol bistrimellitate dianhydride; the reaction product of 2-hydroxyethylacrylate with ethylene glycol bistrimellitate dianhydride; the adduct of pyromellitic dianhydride with glycerol dimethacrylate; the adduct of pyromellitic dianhydride with glycerol diacrylate; or a combination comprising at least one of the foregoing.  
   
   
       5 . The composition of  claim 1 , wherein the copolymerizable multi-functional (meth)acrylate resin is a urethane (meth)acrylate, a urethane di(meth)acrylate; a polyurethane (meth)acrylate; a diurethane dimethacrylate; a polycarbonate di(meth)acrylate; an ethoxylated bisphenol A di(meth)acrylate; an ethoxylated trimethylolpropane tri(meth)acrylate; a diglycidyl (meth)acrylate adduct of Bisphenol A; or a combination comprising at least one of the foregoing.  
   
   
       6 . The composition of  claim 1 , wherein the copolymerizable multi-functional (meth)acrylate resin is a 2,2′-bis[4-(3-methacryloxy-2-hydroxy propoxy)-phenyl]-propane or a urethane di(meth)acrylate.  
   
   
       7 . The composition of  claim 1 , wherein the copolymerizable multi-functional (meth)acrylate resin is a present in an amount of about 10 to about 40 weight percent based on the total weight of the polymerizable components.  
   
   
       8 . The composition of  claim 1 , wherein the diluent is a hydroxyalkyl(meth)acrylate; an ethylene glycol mono- or di(meth)acrylate having one, two, three, or four repeat glycol units; a 1,2- or 1,3-propylene glycol mono- or di(meth)acrylate having one, two, three, or four glycol repeat units; a C 4 -C 12  diol di(meth)acrylate; a glycerol mono- or di(meth)acrylate; a trimethylolpropane mono-, di, or tri(meth)acrylate; a pentaerythritol mono-, di, or tri(meth)acrylate; a phenyl glycidyl ether (meth)acrylate; or a combination comprising at least one of the foregoing.  
   
   
       9 . The composition of  claim 1 , wherein the diluent is 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxypropyl acrylate; 2-hydroxypropyl methacrylate; 4-hydroxybutyl acrylate; 4-hydroxybutyl methacrylate; ethylene glycol acrylate; ethylene glycol methacrylate; diethylene glycol acrylate; diethylene glycol methacrylate; tri(ethylene glycol) diacrylate; tri(ethylene glycol) dimethacrylate; tetra(ethylene glycol) diacrylate; tetra(ethylene glycol) dimethacrylate; 1,2- or 1,3-propylene glycol acrylate; 1,2- or 1,3-propylene glycol methacrylate; dipropylene glycol acrylate; dipropylene glycol methacrylate; tri(propylene glycol) diacrylate; tri(propylene glycol) dimethacrylate; tetra(propylene glycol) diacrylate; tetra(propylene glycol) dimethacrylate; 1,4-butanediol diacrylate; 1,4-butanediol dimethacrylate; 1,6-hexanediol diacrylate; 1,6-hexanediol dimethacrylate; or a combination comprising at least one of the foregoing.  
   
   
       10 . The composition of  claim 1 , wherein the diluent is present in an amount of about 15 to about 55 weight percent, based on the total weight of the polymerizable components.  
   
   
       11 . The composition of  claim 1 , wherein the cure system is a light-initiated cure system.  
   
   
       12 . The composition of  claim 1 , further comprising, based on the total weight of the composition, about 10 to about 90 weight percent a particulate filler composition.  
   
   
       13 . The composition of  claim 12 , wherein the filler is silica, fumed silica, quartz, strontium silicate, strontium borosilicate, lithium silicate, lithium alumina silicate, amorphous silica, ammoniated or deammoniated calcium phosphate, tricalcium phosphate alumina, zirconia, tin oxide, titania, barium borosilicate glass filler, glass ionomer filler, silica glass filler, calcium silicate, bismuth oxide, bismuth oxychloride, zirconium oxide, barium sulfate, bismuth subcarbonate, or a combination comprising at least one of the foregoing fillers.  
   
   
       14 . A dental restoration comprising the cured composition of  claim 1 .  
   
   
       15 . A method of restoring a tooth, comprising: 
 mixing the first paste and the second paste of  claim 1  to form a self-etching and bonding dental resin cement composition;    applying the self-etching and bonding dental resin composition to a tooth surface or a surface of a dental restoration being bonded;    applying the dental restorative material; and    curing the composition.    
   
   
       16 . The method of  claim 15 , wherein the curing is by exposure to actinic radiation.