Single-solution adhesive resin formulations

• US 6,210,759 B1
• Filed: 03/15/2000
• Issued: 04/03/2001
• Est. Priority Date: 02/06/1998
• Status: Expired due to Term

• Current Assignee: ADA Foundation
• Original Assignee: American Dental Association Health Foundation
• Inventors: Dickens, Sabine H.
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): McClendon, Sanza L.
• Application Number:
  US09/525,688
• Time in Patent Office: 384 Days
• Field of Search: 427/516, 427/517, 427/508, 433/217.1, 433/222.1, 433/226, 433/228.1, 522/64, 522/908, 522/182, 522/48, 522/183, 522/28, 522/7, 522/46, 522/12, 522/30, 522/38, 523/116, 523/115, 523/118, 523/109, 523/300, 106/35
• US Class Current: 427/516
• CPC Class Codes: A61K 6/30 Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• CPC Class Codes: C08F 220/281 and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: Y10S 522/908 Dental utility

Abstract

Single-solution adhesive resin formulations are made of predominantly dimethacrylates or diacrylates containing predominantly) two carboxyl groups and a functionalized methacrylate or acrylate diluent monomer. A novel light-activated initiator can be used for photopolymerization of such adhesives.

Claims

1. A method of bonding a composite resin to enamel, dentin or nonprecious metal, comprising the steps of:

applying a single-solution adhesive resin formulation onto a prepared surface selected from the group consisting of enamel, dentin or nonprecious metal;

air drying the adhesive resin formulation;

repeating the steps of applying and air drying between 0 and 2 times;

photopolymerizing the adhesive resin formulation;

contacting the formulation with a composite resin;

photopolymerizing the composite resin to form a bond having a shear bond strength of at least 20 MPa

wherein the formulation comprises not more than two monomers and an initiator consisting of a photoinitiator, wherein a first of the two monomers is an acidic monomer and the second of the two monomers is a diluent monomer.

2. The method of claim 1 wherein the acidic monomer is carboxylic acid monomer.

3. The method of claim 1 wherein the formulation comprises two monomers, wherein a first of the two monomers is pyromellitic glycerol dimethacrylate PMGDM monomer, the second of the two monomers is 2-hydroxyethlmethacrylate 2-HEMA monomer.

4. The method of claim 1 wherein the formulation comprises two monomers, a solvent, and a photoinitiator, wherein a first of the two monomers is PMGDM monomer, the second of the two monomers is 2-hydroxyethlmethacrylate 2-HEMA monomer, and the photoinitiator is 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide.

5. The method of claim 3 wherein the pyromellitic glycerol dimethacrylate (PMGDM) adhesive resin is made by a process comprising:

reacting 1 part pyromellitic dianhydride (PMDA) and greater than 2 parts glycerol dimethyacrylate (GDM) to form PMGDM.

11. The method of claim 1, wherein said photoinitiator is 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, said acidic monomer is selected from the group consisting of pyromellitic dianhydride-HEMA adduct (PMDM), pyromellitic glycerol dimethacrylate (PMGDM), biphenyl dianhydride-HEMA adduct (BPDM), 3,3′

-4,4′

-tetracarboxylic dianhydride-glycerol dimethacrylate adduct (BDGDM), and 5-(2,5-dioxotetrahydro-3-furanyl)-3-cyclohexene-1,2-dicarboxylic anhydride-glycerol dimethacrylate adduct (B4400-GDM), said diluent monomer is selected from the group consisting of 2-hydroxymethacrylate (2-HEMA), glycerol dimethacrylate (GDM), ethyl-α

-hydroxymethacrylate (EHMA), and tetrahydro furfurylmethacrylate (THFM).

6. A method of bonding a composite resin to enamel, dentin or nonprecious metal, comprising the steps of:

applying a single-solution adhesive resin formulation onto a prepared surface selected from the group consisting of enamel, dentin or nonprecious metal;

air drying the adhesive resin formulation;

repeating the steps of applying and air drying between 0 and 2 times;

photopolymerizing the adhesive resin formulation;

contacting the formulation with a composite resin;

photopolymerizing the composite resin to form a bond having a shear bond strength of at least 20 MPa;

wherein the formulation comprises not more than two polymerizable monomers and an initiator consisting of a photoinitiator and a tertiary amine, wherein a first of the two monomers is an acidic monomer and the second of the two monomer is a diluent monomer.

7. The method of claim 6, wherein said photoinitiator is selected from the group consisting of 2,4,6-timethylbenzoyldiphenylphosphine oxide and camphorquinone.

8. The method of claim 6, wherein said tertiary amine is 4-N,N-(dimethylamino) benzoate, said photoinitiator is camphorquinone, said acidic monomer is pyromellitic glycerol dimethacrylate (PMGDM), said diluent monomer is 2-hydroxyethlmethacrylate (2-HEMA).

9. The method of claim 6, wherein said photoinitiator is selected from the group consisting of 2,4,6-trimethylbenzoyldiphenyl phosphine oxide and camphorquinone, said tertiary amine is 4-N,N-(dimethylamino) benzoate (4-EDMAB), said acidic monomer is selected from the group consisting of pyromellitic dianhydride-HEMA adduct (PMDM), pyromellitic glycerol dimethacrylate (PMGDM), biphenyl dianhydride-HEMA adduct (BPDM), 3,3′

-4,4′

-tetracarboxylic dianhydride-glycerol dimethacrylate adduct (BDGDM), and 5-(2,5-dioxotetrahydro-3-furanyl)-3-cyclohexene-1,2-dicarboxylic anhydride-glycerol dimethacrylate adduct (B4400-GDM), said diluent monomer is selected from the group consisting of 2-hydroxymethacrylate (2-HEMA), glycerol dimethacrylate (GDM), ethyl-α

-hydroxymethacrylate (EHMA) and tetrahydro furfurylmethacrylate (THFM).

10. The method of claim 6 wherein the photoinitiator is camphorquinone and the tertiary amine is 4-N,N-(dimethylamino) benzoate.