US4659751A
Expired / Lapsed
US
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Simplified method for obtained strong adhesive bonding of composites to dentin, enamel and other substrates
Assignee: American Dental Association
•
Filing: 1986-02-03
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Granted: 1987-04-21
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Expires: 2006-02-03
Abstract
Abstract Materials and methods for improving the adhesion of composite materials and resins to dentin, enamel and other substrates are disclosed. Preferably, the substrate surface is treated with an aqueous solution of (1) at least one acid (preferably nitric acid), (2) at least one polyvalent cation (preferably an aluminum cation) which can bind to dentin or enamel, and (3) at least one compound (preferably oxalic acid) which forms relatively water-insoluble precipitates with calcium and with polyvalent cations at pH values above that of the acidic treatment solution, and (4) a composition preferably comprising N-phenylglycine and/or other amino acids. Then, a solution is applied which contains at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate ("PMDM"), (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate ("BTDA-HEMA"), (3) 4-methacryloxyethyltrimellitic anhydride ("4-META"), and (4) other monomers. Alternative embodiments are also set forth.
Inventors
- 👤 Rafael L. Bowen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 19:21
CPC Classifications
C; C09; C09J; C09J5/00; C09J5/02; A; A61; A61K; A61K6/00; A61K6/40; C09J4/00
Claims Analysis
Total Claims: 53
Claim 1
Independent Claim
169 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising (1) at least one strong acid and (2) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N (p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (b) then contacting with the surface a solution comprising at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization.
Claim 2
Independent Claim
169 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising (1) at least one strong acid and (2) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N (p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (b) then contacting with the surface a solution comprising at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization.
Claim 3
Dependent Claim
20 words
A method as in claim 1 wherein the concentration of the strong acid is from about 0.1% to about 50%.
Claim 4
Dependent Claim
19 words
A method as in claim 1 wherein the concentration of the strong acid is from about 2 to 5%.
Claim 5
Dependent Claim
13 words
A method as in claim 1 wherein the strong acid is nitric acid.
Claim 6
Dependent Claim
13 words
A method as in claim 1 wherein the strong acid is phosphoric acid.
Claim 7
Dependent Claim
57 words
A method as in claim 1 wherein the concentration of the solution comprising at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids is from about 0.1% to a saturated solution.
Claim 8
Dependent Claim
26 words
A method as in claim 1 wherein the concentration of the monomer in the solution of subpart (b) is from about 0.1% to a saturated solution.
Claim 9
Dependent Claim
17 words
A method as in claim 1 wherein the solvent for the solution of subpart (b) is acetone.
Claim 10
Dependent Claim
32 words
A method as in claim 1 wherein the aqueous solution of subpart (a) contains compatible organic water-soluble solvents sufficient to maintain the compound or compounds and their strong acid salts in solution.
Claim 11
Dependent Claim
21 words
A method as in claim 1 wherein the strong acid is nitric acid and the compound of subpart (a)(2) is N-phenylglycine.
Claim 12
Dependent Claim
14 words
A method as in claim 1 wherein the compound of subpart (a)(2) is N-phenylalanine.
Claim 13
Independent Claim
177 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising at least one strong acid; (b) then contacting with the surface a solution comprising a solvent and at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; and (c) then contacting with the surface a solution comprising at least one monomer selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhyride and 2-hydroxyethyl methcrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interefere with free radical polymerization.
Claim 14
Independent Claim
177 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising at least one strong acid; (b) then contacting with the surface a solution comprising a solvent and at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; and (c) then contacting with the surface a solution comprising at least one monomer selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhyride and 2-hydroxyethyl methcrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interefere with free radical polymerization.
Claim 15
Dependent Claim
20 words
A method as in claim 12 wherein the concentration of the strong acid is from about 0.1% to around 50%.
Claim 16
Dependent Claim
19 words
A method as in claim 12 wherein the concentration of the strong acid is from about 2 to 5%.
Claim 17
Dependent Claim
13 words
A method as in claim 12 wherein the strong acid is nitric acid.
Claim 18
Dependent Claim
13 words
A method as in claim 12 wherein the strong acid is phosphoric acid.
Claim 19
Dependent Claim
26 words
A method as in claim 12 wherein the concentration of the compound in subpart (b) in the solvent is from about 0.1% to a saturated solution.
Claim 20
Dependent Claim
25 words
A method as in claim 12 wherein the concentration of the solution of at least one monomer is from about 0.1% to a saturated solution.
Claim 21
Dependent Claim
17 words
A method as in claim 12 wherein the solvent for the solution of subpart (b) is acetone.
Claim 22
Dependent Claim
17 words
A method as in claim 12 wherein the solvent for the solution of subpart (c) is acetone.
Claim 23
Independent Claim
202 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising (1) at least one strong acid or acidic salt, (2) at least one polyvalent cation, (3) at least one polyfunctional acid which can form relatively water-insoluble precipitates with calcium or polyvalent cations at pH values above that of the aqueous solution, and (4) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (b) then contacting with the surface a solution comprising at least one monomer 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, (3) 4-methacryloxyethyltrimelliticanhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization.
Claim 24
Independent Claim
202 words
A method for preparing the surface of dentin, enamel, or other natural or industrial substrates containing or capable of binding metallic ions, for adhesion of composite materials or resins, which method comprises: (a) first contacting with the surface an aqueous solution or solutions comprising (1) at least one strong acid or acidic salt, (2) at least one polyvalent cation, (3) at least one polyfunctional acid which can form relatively water-insoluble precipitates with calcium or polyvalent cations at pH values above that of the aqueous solution, and (4) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (b) then contacting with the surface a solution comprising at least one monomer 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, (3) 4-methacryloxyethyltrimelliticanhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization.
Claim 25
Dependent Claim
23 words
A method as in claim 21 wherein the strong acid is nitric acid and its concentration is from about 0.1% to about 20%.
Claim 26
Dependent Claim
22 words
A method as in claim 21 wherein the strong acid is nitric acid and its concentration is from about 2 to 5%.
Claim 27
Dependent Claim
33 words
A method as in claim 21 wherein the polyvalent cation is selected from the group consisting of aluminum and ferric ions, used separately or together, and in concentration between about 0.00001% and saturation.
Claim 28
Dependent Claim
21 words
A method as in claim 24 wherein the concentration of aluminum and ferric ions is between about 1% and about 5%.
Claim 29
Dependent Claim
38 words
A method as in claim 21 wherein the polyfunctional acid is selected from the group consisting of oxalic, citric, pyruvic, tartaric, and other oligocarboxylic acids, used separately or in combinations, and in concentrations between about 0.0001% and saturation.
Claim 30
Dependent Claim
19 words
A method as in claim 26 wherein the concentration of polyfunctional acid is between about 1% and about 10%.
Claim 31
Dependent Claim
87 words
A method as in claim 21 wherein at least one compound of subpart (a)(4) is selected from the group consisting of N-phenylglycine, N(p-tolyl) glycine, N-phenylalanine, sarkosine, N-lauroylsarkosine, glycine, N,N-dimethylglycine, 3(N-phenyl) amino propionic acid, 3(N-p-tolyl) amino propionic acid, omega-amino fatty acids, N-substituted-omega-amino fatty acids, the addition reaction product of N-phenyl glycine and glycidyl reagents, the reaction product of N(substituted phenyl) glycine and glycidyl reagents, and other amino acids; and wherein such compound or compounds, used separately or in combinations, are used in concentrations between about 0.1% and saturation.
Claim 32
Dependent Claim
22 words
A method as in claim 28 wherein the concentration of the compound of subpart (a)(4) is between about 1% and about 10%.
Claim 33
Dependent Claim
30 words
A method as in claim 28 wherein the concentration of the compound of subpart (a)(4) is equal to or less than the normality of the strong acid of subpart (a)(1).
Claim 34
Dependent Claim
18 words
A method as in claim 1 wherein the substrate surface is a dentin surface or an enamel surface.
Claim 35
Dependent Claim
18 words
A method as in claim 12 wherein the substrate surface is a dentin surface or an enamel surface.
Claim 36
Dependent Claim
18 words
A method as in claim 21 wherein the substrate surface is a dentin surface or an enamel surface.
Claim 37
Dependent Claim
25 words
A structure comprising a composite material or resin bonded to a dentin or enamel surface which has been prepared by the method of claim 1.
Claim 38
Dependent Claim
25 words
A structure comprising a composite material or resin bonded to a dentin or enamel surface which has been prepared by the method of claim 12.
Claim 39
Dependent Claim
25 words
A structure comprising a composite material or resin bonded to a dentin or enamel surface which has been prepared by the method of claim 21.
Claim 40
Dependent Claim
28 words
A structure comprising a composite material or resin bonded to the surface of a natural or industrial substrate which has been prepared by the method of claim 1.
Claim 41
Dependent Claim
28 words
A structure comprising a composite material or resin bonded to the structure of a natural or industrial substrate which has been prepared by the method of claim 12.
Claim 42
Dependent Claim
28 words
A structure comprising a composite material or resin bonded to the surface of a natural or industrial substrate which has been prepared by the method of claim 21.
Claim 43
Dependent Claim
152 words
An article of manufacture comprising in combination; (a) a first container containing a composition comprising (1) at least one strong acid and (2) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; and (b) a second container containing a composition comprising at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second containers being packaged together in said article of manufacture.
Claim 44
Dependent Claim
152 words
An article of manufacture comprising in combination; (a) a first container containing a composition comprising (1) at least one strong acid and (2) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; and (b) a second container containing a composition comprising at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second containers being packaged together in said article of manufacture.
Claim 45
Dependent Claim
20 words
An article of manufacture as in claim 40 wherein the contents of the first and second containers are in solutions.
Claim 46
Dependent Claim
147 words
An article of manufacture comprising in combination: (a) a first container containing at least one strong acid; (b) a second container containing at least one compound selected from the group consisting of (1)N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (c) a third container at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second and third containers being packaged together in said article of manufacture.
Claim 47
Dependent Claim
147 words
An article of manufacture comprising in combination: (a) a first container containing at least one strong acid; (b) a second container containing at least one compound selected from the group consisting of (1)N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate, and (4) other amino acids; (c) a third container at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second and third containers being packaged together in said article of manufacture.
Claim 48
Dependent Claim
21 words
An article of manufacture as in claim 42 wherein the contents of the first, second and third containers are in solutions.
Claim 49
Dependent Claim
181 words
An article of manufacture comprising in combination: (a) a first container containing (1) at least one strong acid or acidic salt, (2) at least one polyvalent cation, (3) at least one polyfunctional acid which can form relatively water-insoluble precipitates with calcium or polyvalent cations at pH values above that of the aqueous solution, and (4) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methyacrylate, and (4) other amino acids; and (b) a second container containing at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second containers being packaged together in said article of manufacture.
Claim 50
Dependent Claim
181 words
An article of manufacture comprising in combination: (a) a first container containing (1) at least one strong acid or acidic salt, (2) at least one polyvalent cation, (3) at least one polyfunctional acid which can form relatively water-insoluble precipitates with calcium or polyvalent cations at pH values above that of the aqueous solution, and (4) at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl) glycine and glycidyl methacrylate, (3) the addition reaction product of N-phenylglycine and glycidyl methyacrylate, and (4) other amino acids; and (b) a second container containing at least one monomer 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, (3) 4-methacryloxyethyltrimellitic anhydride, and (4) other compounds containing at least one group or moiety capable of free radical polymerization and at least one aromatic ring or moiety containing electron-withdrawing substituents that do not interfere with free radical polymerization; said first and second containers being packaged together in said article of manufacture.
Claim 51
Dependent Claim
20 words
An article of manufacture as in claim 44 wherein the contents of the first and second containers are in solution.
Claim 52
Dependent Claim
47 words
An article of manufacture comprising in combination: (a) a first container containing an acidic aqueous solution of aluminum nitrate, oxalic acid, and N-phenylglycine; and (b) a second container containing an acetone solution of PMDM; said first and second containers being packaged together in said aritcle of manufacture.
Claim 53
Dependent Claim
47 words
An article of manufacture comprising in combination: (a) a first container containing an acidic aqueous solution of aluminum nitrate, oxalic acid, and N-phenylglycine; and (b) a second container containing an acetone solution of PMDM; said first and second containers being packaged together in said aritcle of manufacture.
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| 7.5 Years (Year 8) | 1994-04-20 | 1994-10-20 | 1995-04-21 | $3760.00 | Window Closed / Lapsed |
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