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 at least one compound selected from the group consisting of (1) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, and (2) the addition reaction product of N-phenylglycine and glycidyl methacrylate; 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 at least one compound selected from the group consisting of (1) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, and (2) the addition reaction product of N-phenylglycine and glycidyl methacrylate; 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 18

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 the adduct of N(p-tolyl)glycine and glycidyl methacrylate; (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 19

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 the adduct of N(p-tolyl)glycine and glycidyl methacrylate; (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 36

A method for preparing an industrial substrate containing or capable of binding metallic ions for adhesion of resins, surface coatings, monomers, prepolymers, or plastics that harden by free radical reactions, which method comprises: (a) contacting with the surface of the substrate a solution comprising at least one salt of a polyvalent cation which is capable of changing valence by unit steps and which can bind to substrate surface sites, and an anion which contains at least one carboxyl group; (b) contacting with the surface of the substrate a material comprising at least one surface-active comonomer of the formula: ##STR11## where: m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 2; r=0 or 1; m+p+q=2 to 20; R is selected from the following groups: (a) --O) f (CH 2 ) t H; straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (b) --O) f (CH 2 ) t COOH with t=0 to 12, and with f=0 or 1; and (c) --O) f (CH 2 ) d O--H, with d=1 to 12; and with f=0 or 1; (d) F, Cl, Br, 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; and (c) contacting with the surface of the substrate a material comprising at least one coupling agent of the formula: ##STR12## where: g=0 to 7; E is a polymerizable moiety: --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)=CH.sub.2 ; wherein r=0 or 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 37

A method for preparing an industrial substrate containing or capable of binding metallic ions for adhesion of resins, surface coatings, monomers, prepolymers, or plastics that harden by free radical reactions, which method comprises: (a) contacting with the surface of the substrate a solution comprising at least one salt of a polyvalent cation which is capable of changing valence by unit steps and which can bind to substrate surface sites, and an anion which contains at least one carboxyl group; (b) contacting with the surface of the substrate a material comprising at least one surface-active comonomer of the formula: ##STR11## where: m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 2; r=0 or 1; m+p+q=2 to 20; R is selected from the following groups: (a) --O) f (CH 2 ) t H; straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (b) --O) f (CH 2 ) t COOH with t=0 to 12, and with f=0 or 1; and (c) --O) f (CH 2 ) d O--H, with d=1 to 12; and with f=0 or 1; (d) F, Cl, Br, 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; and (c) contacting with the surface of the substrate a material comprising at least one coupling agent of the formula: ##STR12## where: g=0 to 7; E is a polymerizable moiety: --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)=CH.sub.2 ; wherein r=0 or 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 44

A method for bonding composite materials or resins to dentin or enamel which comprises contacting with the surface of the dentin or enamel an aqueous solution of ferric oxalate of concentration between 0.1% and a saturated solution, and then applying a composite material or resin and utilizing at least one means of initiating the polymerization of that composite material or resin.

Claim 45

A method for bonding composite materials or resins to dentin or enamel which comprises contacting with the surface of the dentin or enamel an aqueous solution of ferric oxalate of concentration between 0.1% and a saturated solution, and then applying a composite material or resin and utilizing at least one means of initiating the polymerization of that composite material or resin.

Claim 46

A method for bonding composite materials or resins to dentin or enamel which comprises contacting with the surface of the dentin or enamel (a) an aqueous solution of ferric oxalate; and (b) a solution of a polymerization initiator and 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; and then applying a composite material or resin and utilizing at least one means for initiating the polymerization of that composite material or resin.

Claim 47

A method for bonding composite materials or resins to dentin or enamel which comprises contacting with the surface of the dentin or enamel (a) an aqueous solution of ferric oxalate; and (b) a solution of a polymerization initiator and 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; and then applying a composite material or resin and utilizing at least one means for initiating the polymerization of that composite material or resin.