Multifunctional acrylates used as cross-linkers in dental and biomedical self-etching bonding adhesives

Abstract

This invention describes an adhesive used for bonding dental and medical biomaterials to hard tissues via a molecular bridge formed from calcium-reactive amines and acrylic or methacrylic ester monomers to hard tissues such as enamel, dentin, and bone. This formulation consists of an acid-stable polymerizable compound with multi-functional acrylate cross-linkers. This formula provides good self-adherence without prior preparation of the hard tissue substrates. The formulation can contain chemical- and/or light-activated free-radical initiators.

1 . An adhesive composition comprising a mixture of:
 a. one or more polymerizable acrylic or methacrylate compounds;   b. one or more hydrophilic acrylate or methacrylate compounds;   c. one or more calcium reactive amines;   d. one or more acrylic or methacrylic esters, wherein said esters form a multifunctional acrylic cross-link between said polymerizable acrylic or methacrylic compounds;   e. one or more polymerization initiators; and   f. filler materials, wherein said filler materials contain glass powder and fluoride-containing compounds.   
     
     
         2 . The adhesive composition of  claim 1 , wherein said polymerizable acrylic compounds are: ethyl acrylate, propyl acrylate, isopropyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, glycerol mono- and di-acrylate, ethyleneglycol diacrylate, polyethyleneglycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, mono-, di-, tri-acrylate, mono-, di-, tri-, and tetra-acrylates of pentacrythritol and dipentaerythritol, 1,3-butanediol diacrylate, 1,4-butanedioldiacrylate, 1,6-hexane diol diacrylate, 2,2′-bis[3(4-phenoxy)-2-hydroxypropane-1-acrylate]propane, 2,2′ bis(4-acryloxyphenyl)propane, 2,2′-bis[3(4-phenoxy)-2-hydroxypropane-1-acrylate]propane, dipentaerthritol pentaacrylate esters (SR 399) and dipentaerthritol pentaacrylate esters (SR 399 LV). 
     
     
         3 . The adhesive composition of  claim 1 , wherein said polymerizable methacrylate compounds include: methacrylates, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, the diglycidyl methacrylate of bis-phenol A (2,2-Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane) (BisGMA), glycerol mono- and di-methacrylate, ethyleneglycol dimethacrylate, polyethyleneglycol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), neopentylglycol dimethacrylate, trimethylol propane trimethacrylate, mono-, di-, tri-, and tetra-methacrylates of pentacrythritol and dipentaerythritol, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, Bis[2-(methacryloyloxy)ethyl]phosphate (BisMEP),1,6-hexanediol dimethacrylate, 2-2′-bis(4-methacryloxyphenyl)propane, 2,2′-bis[4(2-hydroxy-3-methacryloxy-phenyl)]propane, 2,2′ bis[4(2-hydroxy-3acryloxyphyenyl)propane, 2,2′-bis(4-methacryloxyethoxyphenyl)propane, 2,2′-bis(4-acryloxyethoxyphenyl)propane, 2,2′-bis(4-methacryloxypropoxyphenyl)propane, 2,2′-bis(4-acryloxypropoxyphenyl)propane, 2,2′-bis(4-methacryloxydiethoxyphenyl)propane, 2,2′-bis(4-acryloxydiethoxyphenyl)propane, 2,2′-bis[3(4-phenoxy)-2-dydroxypropane-1-methacrylate]propane. 
     
     
         4 . The adhesive composition of  claim 1 , wherein said hydrophilic acrylate compounds are 2-hydroxyethyl acrylate, and hydroxypropyl acrylate. 
     
     
         5 . The adhesive composition of  claim 1 , wherein said methacrylate compound is hydroxyethylmethacrylate (HEMA). 
     
     
         6 . The adhesive composition of  claim 1 , wherein said calcium reactive amines are ethyl-4-Dimethylaminobenzoate (EDMAB) and 4-(dimethylamino) benzoic acid (DMABA). 
     
     
         7 . The adhesive composition of  claim 1 , wherein said acrylic ester is SR 399 LV. 
     
     
         8 . The adhesive composition of  claim 1 , wherein said methacrylic ester is bis[2-(methacryloyloxy)ethyl]phosphate (BisMEP). 
     
     
         9 . The adhesive composition of  claim 1 , wherein said polymerization initiator is chemical initiator, photo-initiator, or combination thereof. 
     
     
         10 . The adhesive composition of  claim 9 , wherein said chemical initiator is BPO. 
     
     
         11 . The adhesive composition of  claim 9 , wherein said photo-initiator are selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide and camphorquinone (CQ). 
     
     
         12 . The adhesive composition of  claim 1 , wherein said glass powder is a mixture of glass particles 0.02 to 40 microns in size. 
     
     
         13 . The adhesive composition of  claim 1 , wherein said adhesive is a bonding agent between a substrate and a hard tissue. 
     
     
         14 . The composition of  claim 13 , wherein said hard tissue is selected from the group consisting of enamel, bone, and dentin. 
     
     
         15 . The adhesive composition of  claim 13 , wherein said substrate is selected from the group consisting of acrylates, composite resins, ceramics, and metals. 
     
     
         16 . The adhesive composition of  claim 1 , wherein said adhesive is a bonding agent that can be used for the stabilization of avulsed, inverted, or luxated teeth to adjacent unaffected teeth. 
     
     
         17 . The adhesive composition of  claim 1 , wherein
 a. said polymerizable methacrylate compound is TEGDMA;   b. said hydrophilic methacrylate compound is HEMA;   c. said calcium reactive amine is EDMAB;   d. said acrylic or methacrylic ester are BisMEP and SR399LV;   e. said polymerization initiator are CQ and BPO;   f. said glass powder is Ba Glass.   g. said filler materials are GI SP2034, Ba Glass, Aerosil 200; and   h. and fluoride-containing compound is GI SP 2034.   
     
     
         18 . A method of dental restoration using the adhesive composition of  claim 1 , comprising
 a. blending said mixture thoroughly at a powder to liquid ratio of 3:1 by weight;   b. applying said mixture to a dental substrate;   c. allowing said mixture to harden;   d. repeating steps a-c until said mixtures resembles the physiological shape of the missing teeth.   
     
     
         19 . The adhesive composition of  claim 1 , wherein said filler materials comprise Barium, Aerosil 200, Pigments, Calcium Fluoroaluminosilicate glass, Silica, Alumina, Aluminum Fluoride, Calcium Fluoride, Sodium Fluoride, Aluminum Phosphate, Calcium, Strontium, Zinc, Sodium, Potassium, Lanthanum, and Alumino-silicates or any combination thereof.