Dental adhesive system

Abstract

Dental cements and abrasives are provided which are polymerizable with visible light. Such adhesives. may be applied in thinner films than heretofore possible and demonstrate superior physical properties. Processes employing such materials are disclosed wherein the polymerizatioa of the adhesive is accomplished by transmmitting visible light through tooth or other structures to effect the sdhesion.

I claim: 
     
       1. A method of bonding an article to a tooth with a visible light-activated adhesive said adhesive comprising binder resin, diluent monomer, initiator for initiating polymerization of said adhesive by exposure to visible light and at least one filler material,   the filler material comprises from 20% to 70% by weight of the adhesive, the layer of adhesive, at least in part, is less than 25 microns (μm) thick and initiation of cure of the adhesive is effected by visible light,   said method comprising curing said adhesive by irradiation with visible light, such visible light being applied through .[.at least one of.]. said article and said tooth.   
     
     
       2. The method of claim 1 wherein said article is an artificial tooth. 
     
     
       3. The method of claim 1 wherein said article is selected from the group consisting of crowns, veneers, caps, bridges, endodontic articles, and dental prostheses. 
     
     
       4. The method of claim 1 wherein at least a portion of said visible light is transmitted through said tooth. 
     
     
       5. The method of claim 1 wherein said article comprises porcelain. 
     
     
       6. The method of claim 1 wherein said article is polymeric material capable of transmitting visible light. 
     
     
       7. The method of claim I wherein said visible light comprises electromagnetic radiation with wavelengths of from about 400 nm. to 500 nm. 
     
     
       8. The method of claim 1 wherein the adhesive composition comprises by weight at least about 20% of an inorganic filler and said initiator comprises an alphadiketone and an amine reducing agent. 
     
     
       9. The method of claim 8 wherein said binder resin comprises bis GMA reacted with aliphatic diisocyanate, said alpha-diketone is selected from the group consisting of camphoroquinone, benzil, biacetyl, 9,10-phenanthrene-quinone, and naphthoquinone, said amine is selected from the group consisting of N-alkyldiaikanolamine and trialkanolamine, and said filler is selected from the group consisting of inorganic glasses and silica. 
     
     
       10. The method of claim 8 wherein the adhesive composition comprises from about 40% to about 70% of said inorganic filler. 
     
     
       11. The method of claim 1 wherein said adhesive is present in a thickness of less than about 25 microns and the average tensile strength of the cured adhesive bond is greater than about 20 Mn/m 2 . .Iadd. 
     
     
       12.  The method of claim 1 wherein said adhesive for adhering an article to a tooth which comprises a binder resin, a diluent monomer, an initiator for initiating polymerization of the adhesive on exposure to visible light and at least one filler material, wherein the binder resin is selected from acrylated polyesters, acrylated polyesters reacted with isocyanates and hydroxyalkyl acrylic species reacted with isocyanates, the initiator comprises an alpha-diketone and an amine reducing agent and the filler comprises from 20% to 70% by weight of the adhesive and the adhesive is usable in a layer less than 25 microns thick. .Iaddend. .Iadd. 
     
     
       13.  A method of adhering an article to a tooth comprising: coating a layer of an adhesive composition onto a surface of at least one of said article or said tooth,   contacting the coated surface with a surface of the remaining one of said article and said tooth such that said surfaces of the respective article and tooth are separated by and in contact with said layer of adhesive, said adhesive comprising a binder resin, a diluent monomer, an initiator for initiating polymerization of said adhesive by exposure to light, and at least one filler material, and exposing to light through at least a portion of the assembly of said article and said tooth and onto said adhesive composition and thereby adhere said surfaces of said article and said tooth to one another through the resulting polymerized adhesive layer, characterized in that the article is glass or porcelain, the binder is selected from acrylated polyesters, acrylated polyester reacted with isocyanates and hydroxyalkyl acrylic species reacted with isocyanates, the initiator comprises an alpha diketone and an amine reducing agent, the filler material comprises from 20% to 70% by weight of the adhesive, the layer of adhesive, at least in part, is less than 25 microns (μm) thick and initiation of cure of the adhesive is effected by visible light which comprises electromagnetic radiation with wavelengths from about 400 nm to about 500 nm. .Iaddend. .Iadd.   
     
     
       14.  A method as claimed in claim 13, characterized in that the binder resin includes a reaction product of bis-GMA (2,2-bis(4-(2-hydroxy-3-methacryloxy-propoxy)phenyl-propane) and an isocyanate. .Iaddend. .Iadd.15. A method as claimed in claim 12, characterized in that the binder resin includes reaction products of bis-GMA and hexamethylene diisocyanate or phenylene diisocyanate. 
     
     
        .Iaddend. .Iadd.16.  A method as claimed in claim 14 characterized in that the alpha diketone is selected from camphoroquinone, benzil, biacetyl, 9,10-phenanthrene quinone and naphthoquinone and, the amine is selected from N-alkyl-dialkanolamine and trialkanolamine and, the fillers are selected from inorganic glasses and silica. .Iaddend. .Iadd.17. A method as claimed in claim 16 characterized in that the alpha-diketone is camphoroquinone and comprises between 0.01% and 0.25% by weight of the adhesive and the amine reducing agent is N-methyl-diethanolamine and comprises between 0.10% and 0.05% by weight of the adhesive. .Iaddend. .Iadd.18. A method as claimed in claim 13 wherein the article is subject to a silanation treatment prior to application of the adhesive. .Iaddend. 
     
     
        .Iadd.19.  The method of claim 13 wherein said layer of adhesive is less 
     
     
        than about 15 microns thick. .Iaddend. .Iadd.20.  A method of adhering an article to a tooth comprising: coating a layer of an adhesive composition onto a surface of at least one of said article or said tooth,   contacting the coated surface with a surface of the remaining one of said article and said tooth such that said surfaces of the respective article and tooth are separated by and in contact with said layer of adhesive, said adhesive comprising a binder resin, a diluent monomer, an initiator for initiating polymerization of said adhesive by exposure to light, and at least one filler material, and exposing to light at least a portion of the assembly of said article and said tooth separated by said adhesive layer to permit light to be transmitted through at least one of said article and said tooth and onto said adhesive composition and thereby adhere said surfaces of said article and said tooth to one another through the resulting polymerized adhesive layer, characterized in that the article is glass or porcelain, the binder is selected from acrylated polyesters, acrylated polyester reacted with isocyanates and, hydroxyalkyl acrylic species reacted with isocyanates, the initiator comprises an alpha diketone and an amine reducing agent, the filler material is selected from inorganic glasses and silica and comprises from 20 to 70% by weight of the adhesive, the layer of adhesive, at least in part, is less than 25 microns (μm) thick and initiation of cure of the adhesive is effected by visible light which comprises electromagnetic radiation with wavelengths   
     
     
        from about 400 nm to about 500 nm. .Iaddend. .Iadd.21.  A method as claimed in claim 20, characterized in that the binder resin includes a reaction product of bis-GMA (2,2-bis[4-(2-hydroxy-3-methacryloxy-propoxy)phenyl]propane) and an 
     
     
        isocyanate. .Iaddend. .Iadd.22.  A method as claimed in claim 21 characterized in that the binder resin includes reaction products of bis-GMA and hexamethene diisocyanate or phenylene diisocyanate. .Iaddend. .Iadd.23. A method as claimed in claim 21 characterized in that the alpha diketone is selected from camphoroquinone, benzil, biacetyl, 9,10-phenanthrene quinone and naphthoquinone and, the amine is selected from N-alkyl-dialkanolamine and trialkanolamine. .Iaddend. .Iadd.24. A method as claimed in claim 23 characterized in that the alpha-diketone is camphoroquinone and comprises between 0.01% and 0.25% by weight of the adhesive and the amine reducing agent is N-methyl-diethanolamine and comprises between 0.01% and 0.05% by weight of the adhesive. .Iaddend. .Iadd.25. A method as claimed in claim 20 wherein the article is subject to a silanation treatment prior to application of the adhesive. .Iaddend. 
     
     
        .Iadd.26.  The method of claim 20 wherein said layer of adhesive is less 
     
     
        than about 15 microns thick. .Iaddend. .Iadd.27.  An adhesive adhering an article to a tooth formed from a composition comprising a binder resin, a diluent monomer, an initiator for initiating polymerization of the adhesive on exposure to visible light and at least one filler material, wherein the binder resin is selected from acrylated polyesters, acrylated polyesters reacted with isocyanates and hydroxyalkyl acrylic species reacted with isocyanates, the initiator comprises an alpha-diketone and an amine reducing agent and the filler comprises from 20% to 70% by weight of the adhesive and the adhesive is in a layer less than 25 microns thick. .Iaddend.