Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates

Claim 1

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin or enamel an aqueous solution comprising at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin or enamel surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with calcium and which contains at least one carboxyl group; (b) contacting with the surface of the dentin or enamel a solution comprising N-phenylglycine in a solvent; and (c) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, and (3) 4-methacryloxyethyltrimellitic anhydride.

Claim 2

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin or enamel an aqueous solution comprising at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin or enamel surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with calcium and which contains at least one carboxyl group; (b) contacting with the surface of the dentin or enamel a solution comprising N-phenylglycine in a solvent; and (c) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, and (3) 4-methacryloxyethyltrimellitic anhydride.

Claim 13

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting the surface of the dentin or enamel with an aqueous solution comprising ferric oxalate; (b) washing and then drying the surface of the dentin or enamel; (c) contacting the surface of the dentin or enamel with a first acetone solution comprising N-phenylglycine in acetone; (d) removing any excess of the first acetone solution and rinsing the surface of the dentin or enamel with acetone, removing any excess acetone and drying the surface; (e) contacting the surface of the dentin or enamel with a second acetone solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate and (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate.

Claim 14

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting the surface of the dentin or enamel with an aqueous solution comprising ferric oxalate; (b) washing and then drying the surface of the dentin or enamel; (c) contacting the surface of the dentin or enamel with a first acetone solution comprising N-phenylglycine in acetone; (d) removing any excess of the first acetone solution and rinsing the surface of the dentin or enamel with acetone, removing any excess acetone and drying the surface; (e) contacting the surface of the dentin or enamel with a second acetone solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate and (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate.

Claim 31

A method for preparing the surface of dentin, enamel or industrial substrates for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin, enamel or industrial substrate an aqueous solution comprising at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin, enamel, or industrial substrate surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with cations of the substrate surface and which contains at least one carboxyl group; (b) contacting with the surface of the dentin, enamel or industrial substrate a solution comprising a solvent and a surface-active compound of the formula: ##STR12## where: d=0 or 1; m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 12, r=0 to 10; m+p+q=0 to 20; R is selected from the following groups: (2) --O) f (CH 2 ) t H straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (2) --O) f (CH 2 ) t COOH, with t=0 to 12, and with f=0 or 1; (3) --O) f (CH 2 ) d O--H, with d=1 to 12, and with f=0 or 1; and (4) F, Cl, Br and I; and the number of R groups per molecule is 0 to 5, and these R groups may be in the para meta, or ortho positions relative to the nitrogen; (d) contacting with the surface of the dentin, enamel, or industrial substrate a solution comprising at least one coupling agent of the formula: ##STR13## where: g=0 to 7; E is a polymerizable moiety: CH.sub.2 =--COO(CH(CH.sub.2).sub.j H).sub.q (CHOH).sub.m (CH.sub.2).sub.p OCO--C--CH.sub.2).sub.r H) wherein r=0 to 1; p=0 to 12; m=0 to 6; q=0 to 2; j=0 or 1; p+m+q=2 to 20; the number of E groups per molecule is 1 to 8; A is an anhydride group --OCOCO-- (attached to vicinal ring carbon atoms); the number of A groups per molecule is 0 to 1; X is a halide group; and the number of X groups per molecule is 0 to 8, and y is 0 to 1.

Claim 32

A method for preparing the surface of dentin, enamel or industrial substrates for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin, enamel or industrial substrate an aqueous solution comprising at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin, enamel, or industrial substrate surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with cations of the substrate surface and which contains at least one carboxyl group; (b) contacting with the surface of the dentin, enamel or industrial substrate a solution comprising a solvent and a surface-active compound of the formula: ##STR12## where: d=0 or 1; m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 12, r=0 to 10; m+p+q=0 to 20; R is selected from the following groups: (2) --O) f (CH 2 ) t H straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (2) --O) f (CH 2 ) t COOH, with t=0 to 12, and with f=0 or 1; (3) --O) f (CH 2 ) d O--H, with d=1 to 12, and with f=0 or 1; and (4) F, Cl, Br and I; and the number of R groups per molecule is 0 to 5, and these R groups may be in the para meta, or ortho positions relative to the nitrogen; (d) contacting with the surface of the dentin, enamel, or industrial substrate a solution comprising at least one coupling agent of the formula: ##STR13## where: g=0 to 7; E is a polymerizable moiety: CH.sub.2 =--COO(CH(CH.sub.2).sub.j H).sub.q (CHOH).sub.m (CH.sub.2).sub.p OCO--C--CH.sub.2).sub.r H) wherein r=0 to 1; p=0 to 12; m=0 to 6; q=0 to 2; j=0 or 1; p+m+q=2 to 20; the number of E groups per molecule is 1 to 8; A is an anhydride group --OCOCO-- (attached to vicinal ring carbon atoms); the number of A groups per molecule is 0 to 1; X is a halide group; and the number of X groups per molecule is 0 to 8, and y is 0 to 1.