US4251565A
Expired / Lapsed
US
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Use of a polyfunctional surface-active comonomer and other agents to improve adhesion between a resin or composite material and a substrate
Assignee: American Dental Association
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Filing: 1979-02-09
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Granted: 1981-02-17
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Expires: 1999-02-09
Abstract
Abstract A family of polyfunctional surface-active comonomers which act to improve the adhesion between a resin or composite material and solid surfaces capable of binding polyvalent cations is described. These polyfunctional surface-active comonomers, or "PolySACs", are preferably the reaction product of an epoxy acrylate or methacrylate and an aminobenzoate. The adhesion of the resin or composite material to certain solid surfaces is also improved by the preparatory treatment of these surfaces with a monobasic acid of intermediate strength followed by treatment with a mordant. In its most preferred form the invention is employed in reconstructive dental work to improve the adhesion between a resin or composite material and dentin. The dentin is cleansed with isotonic formic acid, treated with an isotonic ferric chloride mordant and then treated with a PolySAC which is the reaction product of an oligomeric diglycidyl ether, acrylic acid and lithium ortho-aminobenzoate. The resin or composite material is then applied.
Inventors
- 👤 Rafael L. Bowen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 15:37
CPC Classifications
A; A61; A61K; A61K6/00; A61K6/30; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31511; Y10T428/31515; Y10T428/31518; Y10T428/31522; Y10T428/31529; Y10T428/31536; Y10T428/31551; Y10T428/31645; Y10T428/31855
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
97 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material a polyfunctional surface-active comonomer comprising a compound of the formula ##STR6## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR7## represents ortho-, meta- or para-aminobenzoate.
Claim 2
Independent Claim
97 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material a polyfunctional surface-active comonomer comprising a compound of the formula ##STR6## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR7## represents ortho-, meta- or para-aminobenzoate.
Claim 3
Dependent Claim
91 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material a reaction product of (a) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (b) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 1.
Claim 4
Independent Claim
103 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material (a) a mordant solution, and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR8## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR9## represents ortho-, meta- or para-aminobenzoate.
Claim 5
Independent Claim
103 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material (a) a mordant solution, and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR8## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR9## represents ortho-, meta- or para-aminobenzoate.
Claim 6
Dependent Claim
97 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to application of the resin or composite material (a) a mordant solution, and (b) a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 3.
Claim 7
Independent Claim
118 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to application of the resin or composite material (a) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR10## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR11## represents ortho-, meta- or para-aminobenzoate.
Claim 8
Independent Claim
118 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to application of the resin or composite material (a) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR10## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR11## represents ortho-, meta- or para-aminobenzoate.
Claim 9
Dependent Claim
112 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to application of the resin or composite material (a) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (b) a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 5.
Claim 10
Independent Claim
105 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR12## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR13## represents ortho-, meta- or para-aminobenzoate.
Claim 11
Independent Claim
105 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, and (b) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR12## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR13## represents ortho-, meta- or para-aminobenzoate.
Claim 12
Dependent Claim
104 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, and (b) a polyfunctional surface-active comonomer comprising a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 7.
Claim 13
Independent Claim
131 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, (b) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR14## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR15## represents ortho-, meta- or para-aminobenzoate.
Claim 14
Independent Claim
131 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, (b) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR14## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR15## represents ortho-, meta- or para-aminobenzoate.
Claim 15
Dependent Claim
130 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of a monobasic acid of intermediate strength, (b) an isotonic mordant solution wherein the mordant is selected from the group consisting of iron (III), zinc, copper (II), aluminum, cobalt (II) and chromium (III), and (c) a polyfunctional surface-active comonomer comprising a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 9.
Claim 16
Independent Claim
109 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of formic acid, (b) an isotonic, aqueous solution of ferric chloride, and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR16## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR17## represents ortho-, meta- or para-aminobenzoate.
Claim 17
Independent Claim
109 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of formic acid, (b) an isotonic, aqueous solution of ferric chloride, and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR16## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR17## represents ortho-, meta- or para-aminobenzoate.
Claim 18
Dependent Claim
108 words
A method of improving the adhesion of a resin or composite material to dentin which comprises applying to the surface prior to the application of the resin or composite material (a) an isotonic, aqueous solution of formic acid, (b) an isotonic, aqueous solution of ferric chloride, and (c) a polyfunctional surface-active comonomer comprising a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 11.
Claim 19
Independent Claim
111 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to the application of the resin or composite material (a) an aqueous solution of an acid, (b) a mordant solution, and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR18## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR19## represents ortho-, meta- or para-aminobenzoate.
Claim 20
Independent Claim
111 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to the application of the resin or composite material (a) an aqueous solution of an acid, (b) a mordant solution, and (c) a polyfunctional surface-active comonomer comprising a compound of the formula ##STR18## where A is a monomer polymerizable by free radical polymerization, X is a univalent metal cation or hydrogen, m is an integer which may vary between 0 and 10, n is an integer which may vary between 0 and 2, and the aminobenzoate structure ##STR19## represents ortho-, meta- or para-aminobenzoate.
Claim 21
Dependent Claim
105 words
A method of improving the adhesion of a resin or composite material to a solid surface capable of binding polyvalent cations which comprises applying to the surface prior to the application of the resin or composite material (a) an aqueous solution of an acid, (b) a mordant solution, and (c) a reaction product of (i) the addition of a monomer polymerizable by free radical polymerization to all but one of the epoxy groups of a polyepoxide to form an intermediate, (ii) followed by the reaction of this intermediate with an aminobenzoate thereby forming a reaction product comprising a comonomer as set forth in claim 13.
Claim 22
Dependent Claim
41 words
A method as in claim 1 wherein the solid surface is selected from the group consisting of metals or alloys with oxide surfaces, glasses, microcrystalline glasses, ceramics, natural and synthetic minerals, calcified tissues, hard tissues, hard tooth tissues, enamel and dentin.
Claim 23
Dependent Claim
41 words
A method as in claim 2 wherein the solid surface is selected from the group consisting of metals or alloys with oxide surfaces, glasses, microcrystalline glasses, ceramics, natural and synthetic minerals, calcified tissues, hard tissues, hard tooth tissues, enamel and dentin.
Claim 24
Dependent Claim
12 words
A method as in claim 1 wherein the solid surface is dentin.
Claim 25
Dependent Claim
12 words
A method as in claim 2 wherein the solid surface is dentin.
Claim 26
Dependent Claim
21 words
A method as in claim 9 wherein the monobasic acid has a pK a within the range of 2.5 to 3.8.
Claim 27
Dependent Claim
21 words
A method as in claim 10 wherein the monobasic acid has a pK a within the range of 2.5 to 3.8.
Claim 28
Dependent Claim
22 words
A method as in claim 1, 3, 5, 7, 9, 11, 13, 15, 17 or 19 wherein A is acrylate or methacrylate.
Claim 29
Dependent Claim
21 words
A method as in claim 1, 3, 5, 7, 9, 11, 13, 15, 17 or 19 wherein the aminobenzoate is ortho-aminobenzoate.
Claim 30
Dependent Claim
25 words
A method as in claim 1, 3, 5, 7, 9, 11, 13, 15, 17 or 19 wherein A is acrylate and the aminobenzoate is ortho-aminobenzoate.
Claim 31
Dependent Claim
27 words
A method as in claim 1, 3, 5, 7, 8, 13, 15, 17 or 19 wherein A is acrylate, X is lithium and the aminobenzoate is ortho-aminobenzoate.
Claim 32
Dependent Claim
30 words
A method as in claim 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 wherein the monomer polymerizable by free radical polymerization is acrylic acid or methacrylic acid.
Claim 33
Dependent Claim
61 words
A method as in claim 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 wherein the polyepoxide is selected from the group consisting of the diglycidyl ether of a bisphenol A oligomer, the diglycidyl ether of resorcinol, ortho-glycidyl phenyl glycidyl ether, polyglycidyl ether of ortho-cresolformaldehyde novolac, polyglycidyl ether of phenol formaldehyde novolac and di(2-methyl) glycidyl ether of ethylene glycol.
Claim 34
Dependent Claim
21 words
A method as in claim 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 wherein the aminobenzoate is ortho-aminobenzoate.
Claim 35
Dependent Claim
28 words
A method as in claim 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 wherein the polyepoxide is the diglycidyl ether of a bisphenol A oligomer.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-02-17 | 1984-08-18 | 1985-02-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-02-17 | 1988-08-18 | 1989-02-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-02-17 | 1992-08-18 | 1993-02-17 | $7700.00 | Window Closed / Lapsed |