# US 8,785,518 B2 · Curable zirconia adhesive compositions for dental restorations

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- Number: US 8,785,518 B2
- Document ID: US8785518B2
- Status: Granted
- Kind: B2
- Application number: 12/412,937
- Filed: 2009-03-27
- Published: 2010-09-30
- Granted: 2014-07-22
- Earliest claimed: 2009-03-27
- Applicants: Byoung I. Suh; Liang Chen
- Inventors: Byoung I. Suh; Liang Chen
- Web page: https://patentgrep.com/patent/US8785518B2

## CPC

- C08F 2/48: by ultraviolet or visible light
- A61K 6/30: Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
- C08F 222/1025: {of aromatic dialcohols}
- C08L 43/02: Homopolymers or copolymers of monomers containing phosphorus
- C08L 75/16: having terminal carbon-to-carbon unsaturated bonds
- C09J 4/00: Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16}
- C08F 230/02: containing phosphorus
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)

## Abstract

The present application relates to a polymerizable dental adhesive system formulated for effective and durable bonding of zirconia based materials and restorations to dental resins and dental surfaces. According to one embodiment, a polymerizable dental adhesive system comprises a first acidic monomer comprising an ethylenically unsaturated polymerizable group or moiety of the general formula CH2═CX—C(O)— wherein X is hydrogen, methyl or a lower alkyl group, and the first polymerizable monomer further comprises a phosphoric or phosphonic acid group of general formula —OP(O)(OH)2, —OP(O)(OH), —C—P(O)(OH)2 and —C—P(O)(OH), and a second polymerizable acidic monomer comprises an ethylenically unsaturated polymerizable group or moiety of the general formula CH2═CX—C(O)— wherein X is hydrogen, methyl or a lower alkyl group, and wherein the second polymerizable acidic monomer further comprises a carboxylic acid group of the general formula —C(O)OH.

## Claims

### Claim 1

A dental adhesive system comprising:
a zirconia-based ceramic; and
an adhesive composition applied to the surface of the zirconia-based ceramic, comprising:
(a) a first acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R wherein X is hydrogen, methyl or a lower alkyl group, and wherein R comprises a phosphoric acid group or phosphonic acid group having the general formula —OP(O)(OH)2, —OP(O)(OH), —C—P(O)(OH)2 or —C—P(O)(OH);
(b) a second acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R1 wherein X is hydrogen, methyl or a lower alkyl group, and wherein R1 comprises a carboxylic acid group having the general formula —C(O)OH;
(c) wherein the first acidic monomer comprises about 1% to about 5% of the dental adhesive system by weight; and
(d) wherein the second acidic monomer comprises about 2% to about 10% of the dental adhesive system by weight.

### Claim 2 (depends on 1)

The dental adhesive system of claim 1, wherein the first acidic monomer is selected from the group consisting of CH2═C(CH3)COO(CH2)nOP(O)(OH)2 and CH2═C(CH3)COO(CH2)nP(O)(OH)2, wherein n is an integer from 2 to 20.

### Claim 3 (depends on 1)

The dental adhesive system of claim 1, wherein the second acidic monomer is selected from the group consisting of tetrahydrofurfuryl cyclohexene dimethacrylate, the reaction product of 3,3′4,4′-diphenylsulfone tetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, and biphenyl dimethacrylate.

### Claim 4 (depends on 1)

The dental adhesive system of claim 1, further comprising at least one comonomer selected from the group consisting of 2-hydroxyethyl methacrylate, bisphenol A diglycidyl methacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A diglycidyl methacrylate, and urethane dimethacrylate.

### Claim 5 (depends on 3)

The dental adhesive system of claim 3, further comprising an initiator.

### Claim 6 (depends on 5)

The dental adhesive system of claim 5, wherein the initiator comprises at least one photosensitive ketone and at least one tertiary amine.

### Claim 7 (depends on 1)

The dental adhesive system of claim 1, wherein neither of the acidic monomers contain a halogen group.

### Claim 8 (depends on 1)

The dental adhesive system of claim 1, wherein the ratio of the first acidic monomer to the second acidic monomer is between about 1:10 and 3:1, respectively.

### Claim 9 (depends on 1)

The dental adhesive system of claim 1, wherein the ratio of the first acidic monomer to the second acidic monomer is between about 1:5 and 2:1, respectively.

### Claim 10

A dental adhesive system comprising:
a zirconia-based ceramic; and
an adhesive composition applied to the surface of the zirconia-based ceramic, comprising:
(a) a first acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R wherein X is hydrogen, methyl or a lower alkyl group, and wherein R is a phosphoric acid group or phosphonic acid group having the general formula —OP(O)(OH)2, —OP(O)(OH), —C—P(O)(OH)2 or —C—P(O)(OH), the first acidic monomer comprising about 1% to about 5% of the composition by weight;
(b) a second acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R1 wherein X is hydrogen, methyl or a lower alkyl group, and wherein R1 comprises a carboxylic acid group having the general formula —C(O)OH, the second acidic monomer comprising about 2% to about 10% of the composition by weight;
(c) at least one comonomer selected from the group consisting of 2-hydroxyethyl methacrylate, bisphenol A diglycidyl methacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A diglycidyl methacrylate, and urethane dimethacrylate;
(d) an initiator comprising at least one photosensitive ketone and at least one tertiary amine; and
(e) wherein the ratio of the first acidic monomer to the second acidic monomer is between about 1:10 and 3:1, respectively.

### Claim 11 (depends on 10)

The dental adhesive system of claim 10, wherein the comonomer comprises about 2% to about 40% of the dental adhesive system by weight.

### Claim 12 (depends on 10)

The dental adhesive system of claim 10, wherein the at least one comonomer comprises two comonomers selected from the group consisting of 2-hydroxyethyl methacrylate, bisphenol A diglycidyl methacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A diglycidyl methacrylate, and urethane dimethacrylate.

### Claim 13 (depends on 10)

The dental adhesive system of claim 10, wherein the initiator comprises about 0.05% to about 2% of the dental adhesive system by weight.

### Claim 14 (depends on 11)

The dental adhesive system of claim 11, further comprising at least one solvent.

### Claim 15 (depends on 12)

The dental adhesive system of claim 12, wherein the adhesive system displays an initial bond strength to zirconia that is greater than 10 MPa as measured with the #5 gel cap method when polymerized.

### Claim 16 (depends on 12)

The dental adhesive system of claim 12, wherein the adhesive system displays an initial bond strength to zirconia that is at least about 14 MPa as measured with the #5 gel cap method when polymerized.

### Claim 17

A method of bonding zirconia to a surface, comprising:
(a) providing a first acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R wherein X is hydrogen, methyl or a lower alkyl group, and wherein R is a phosphoric acid group or phosphonic acid group having the general formula —OP(O)(OH)2, —OP(O)(OH), —C—P(O)(OH)2 or —C—P(O)(OH), the first acidic monomer comprising about 1% to about 5% of the provided materials by weight;
(b) providing a second acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R1 wherein X is hydrogen, methyl or a lower alkyl group, and wherein R1 comprises a carboxylic acid group having the general formula —C(O)OH, the second acidic monomer comprising about 2% to about 10% of the provided materials by weight;
(c) providing at least one comonomer selected from the group consisting of 2-hydroxyethyl methacrylate, bisphenol A diglycidyl methacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethoxylated bisphenol A diglycidyl methacrylate, and urethane dimethacrylate;
(d) providing an initiator comprising at least one photosensitive ketone and at least one tertiary amine;
(e) combining all provided materials and applying those materials to a zirconia dental appliance; and
(f) polymerizing the combined materials applied to the zirconia dental appliance such that the initial bond between the polymerized materials and the zirconia is at least about 10 MPa as measured with the #5 gel cap method.

### Claim 18 (depends on 17)

The method of claim 17, wherein the comonomer comprises about 4% to about 36% of the provided materials by weight; the initiator comprises about 0.05% to about 3% of the dental adhesive system by weight; and further providing a solvent that comprises about 40% to about 90% of the provided materials by weight.

### Claim 19 (depends on 18)

The method of claim 18, wherein none of the provided monomers comprise a halogen group.

### Claim 20 (depends on 17)

The method of claim 17, wherein the initial bond between the polymerized materials and the zirconia is at least about 14 MPa as measured with the #5 gel cap method.

### Claim 21 (depends on 17)

The method of claim 17, wherein the provided materials are polymerized via light curing.

### Claim 22 (depends on 17)

The method of claim 17, wherein the bond between the polymerized materials and the zirconia is at least about 10 MPa as measured with the #5 gel cap method when exposed to water at 100° C. for 72 hours.

### Claim 23 (depends on 1)

The dental adhesive system of claim 1, further comprising at least one solvent.

### Claim 24

A dental restoration comprising:
a zirconia based restoration having a surface prepared by application of an adhesive comprising,
(a) a first acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R wherein X is hydrogen, methyl or a lower alkyl group, and wherein R comprises a phosphoric acid group or phosphonic acid group having the general formula —OP(O)(OH)2, —OP(O)(OH), —C—P(O)(OH)2 or —C—P(O)(OH), the first acidic monomer comprising about 1% to about 5% of the adhesive by weight; and
(b) a second acidic monomer having an ethylenically unsaturated polymerizable group of the general formula CH2═CX—C(O)—R1 wherein X is hydrogen, methyl or a lower alkyl group, and wherein R1 comprises a carboxylic acid group having the general formula —C(O)OH, the second acidic monomer comprising about 2% to about 10% of the adhesive by weight;
wherein the prepared surface of the zirconia based restoration is adhered to a tooth.

### Claim 25 (depends on 24)

The dental restoration of claim 24, wherein the prepared surface further comprises a dental restorative resin applied over the adhesive, the dental restorative resin selected from the group consisting of: a cement, composite, luting composite or combination thereof.