US4669983A
Expired / Lapsed
US
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Dentin and enamel adhesive
Assignee: 3M Co
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Filing: 1984-10-29
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Granted: 1987-06-02
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Expires: 2004-10-29
Abstract
Abstract Organic esters of chlorine-containing or bromine-containing phosphorus acids and BIS-GMA, as well as organic esters of phosphorus acids having chlorine or bromine bonded directly to phosphorus, the organic radical of said esters containing at least one polymerizable functional group. Also described are dental liner, restorative, composite, and adhesive compositions containing such organic esters, as well as methods for using such compositions to repair or veneer dental tissue.
Inventors
- 👤 James E. Bunker
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 12:47
CPC Classifications
C; C07; C07F; C07F9/00; C07F9/02; C07F9/06; C07F9/08; C07F9/09; C07F9/14; C07F9/141; C07F9/146; C09; C09J; C09J4/00
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
61 words
A method for repairing or veneering hard dental tissue, without the necessity for acid etching said tissue, comprising the steps of: (a) applying to said tissue a polymerizable composition comprising the reaction product of a chlorine-containing or bromine-containing phosphorus acid with a polymerizable monomer having at least one reactive hydroxyl group, and (b) causing said composition to harden on said tissue.
Claim 2
Independent Claim
61 words
A method for repairing or veneering hard dental tissue, without the necessity for acid etching said tissue, comprising the steps of: (a) applying to said tissue a polymerizable composition comprising the reaction product of a chlorine-containing or bromine-containing phosphorus acid with a polymerizable monomer having at least one reactive hydroxyl group, and (b) causing said composition to harden on said tissue.
Claim 3
Dependent Claim
12 words
A method according to claim 1, wherein said polymerizable monomer comprises BIS-GMA.
Claim 4
Dependent Claim
13 words
A method according to claim 1, wherein said polymerizable monomer comprises hydroxyethyl methacrylate.
Claim 5
Dependent Claim
41 words
A method according to claim 2, wherein said tissue comprises dentin, said phosphorus acid comprises phosphorus oxychloride, and said reaction product was made from about 0.25 to 20% by weight of said phosphorus oxychloride, based on the weight of said BIS-GMA.
Claim 6
Dependent Claim
49 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising the reaction product of a chlorine-containing or bromine-containing phosphorus acid with a polymerizable monomer having at least one reactive hydroxyl group, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 7
Dependent Claim
49 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising the reaction product of a chlorine-containing or bromine-containing phosphorus acid with a polymerizable monomer having at least one reactive hydroxyl group, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 8
Dependent Claim
12 words
Compositions according to claim 5, further comprising tertiary amine and free-radical initiator.
Claim 9
Dependent Claim
9 words
Compositions according to claim 5, further comprising light-activatable catalyst.
Claim 10
Dependent Claim
11 words
Compositions according to claim 5, wherein said polymerizable monomer comprises BIS-GMA.
Claim 11
Dependent Claim
12 words
Compositions according to claim 5, wherein said phosphorus acid comprises phosphorus oxychloride.
Claim 12
Dependent Claim
35 words
Compositions according to claim 5, wherein said polymerizable compound comprises the reaction product of BIS-GMA in a diluent with about 0.25 to 10% by weight phosphorus oxychloride, and said sulfur compound comprises alkali benzene sulfinate.
Claim 13
Dependent Claim
19 words
Compositions according to claim 5, wherein said polymerizable compound comprises the reaction product of hydroxyethyl methacrylate and phosphorus oxychloride.
Claim 14
Dependent Claim
29 words
Compositions according to claim 11, wherein said hydroxyethyl methacrylate and said phosphorus oxychloride are combined in a ratio of hydroxyl group to hydrogen atom between about 1.5:1 to 0.0375:1.
Claim 15
Dependent Claim
13 words
Compositions according to claim 5, wherein said phosphorus acid comprises PBr 3 .
Claim 16
Dependent Claim
32 words
Dentin and enamel adhesive compositions, comprising an adduct derived by addition to the BIS-GMA of a chlorine-containing or bromine-containing phosphorus acid, and a sulfur compound in the +2 or +4 oxidation state.
Claim 17
Dependent Claim
32 words
Dentin and enamel adhesive compositions, comprising an adduct derived by addition to the BIS-GMA of a chlorine-containing or bromine-containing phosphorus acid, and a sulfur compound in the +2 or +4 oxidation state.
Claim 18
Dependent Claim
27 words
Compositions according to claim 14, wherein said phosphorus acid comprises POCl 3 , C 6 H 5 OP(O)Cl 2 , PCl 3 , or PBr 3 .
Claim 19
Dependent Claim
17 words
Compositions according to claim 14, wherein said adduct contains chlorine and said phosphorus acid comprises phosphorus oxychloride.
Claim 20
Dependent Claim
34 words
Compositions according to claim 16, wherein said composition is covered with a polymerizable dental restorative or composite, and has an average measured shear strength on unetched dentin of at least 25 kg/cm 2 .
Claim 21
Dependent Claim
9 words
Compositions according to claim 14, further comprising light-activatable catalyst.
Claim 22
Dependent Claim
63 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound having the formulae R 5 OPOCl 2 , (R 5 O) 2 POCl or (R 5 O) 3 PO where R 5 O is the radical remaining after removal of a hydroxyl hydrogen atom from BIS-GMA, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 23
Dependent Claim
63 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound having the formulae R 5 OPOCl 2 , (R 5 O) 2 POCl or (R 5 O) 3 PO where R 5 O is the radical remaining after removal of a hydroxyl hydrogen atom from BIS-GMA, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 24
Dependent Claim
54 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more of the moieties ##STR11## with the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 25
Dependent Claim
54 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more of the moieties ##STR11## with the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) a liquid solution comprising sulfur compound in the +2 or +4 oxidation state.
Claim 26
Dependent Claim
52 words
A two-part polymerizable composition for use in dentistry, one part of which comprises the reaction product of BIS-GMA in a diluent with about 0.25 to 10 percent by weight phosphorus oxychloride, and a free-radical initiator, and the second part of which is a liquid solution comprising tertiary amine and alkali benzene sulfinate.
Claim 27
Dependent Claim
52 words
A two-part polymerizable composition for use in dentistry, one part of which comprises the reaction product of BIS-GMA in a diluent with about 0.25 to 10 percent by weight phosphorus oxychloride, and a free-radical initiator, and the second part of which is a liquid solution comprising tertiary amine and alkali benzene sulfinate.
Claim 28
Dependent Claim
66 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more acids of phosphorus, said ester having chlorine or bromine bonded directly to phosphorus, and the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) about 0.5 to 10 percent by weight sulfur compound in the +2 or +4 oxidation state.
Claim 29
Dependent Claim
66 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more acids of phosphorus, said ester having chlorine or bromine bonded directly to phosphorus, and the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) about 0.5 to 10 percent by weight sulfur compound in the +2 or +4 oxidation state.
Claim 30
Dependent Claim
26 words
Compositions according to claim 22 further comprising about 0.5 to 10 percent by weight tertiary amine and about 0.05 to 5 percent by weight free-radical initiator.
Claim 31
Dependent Claim
16 words
Compositions according to claim 22, wherein said ester comprises compounds containing groups of the formulae: ##STR12##
Claim 32
Dependent Claim
20 words
Compositions according to claim 22, wherein said free-radically polymerizable functional group comprises a monofunctional, or difunctional acryl or methacryl radical.
Claim 33
Dependent Claim
22 words
Compositions according to claim 22, wherein said free-radically polymerizable functional group comprises a monofunctional or difunctional vinyl, allyl, crotyl, or cinnamyl radical.
Claim 34
Dependent Claim
9 words
Compositions according to claim 22, further comprising light-activatable catalyst.
Claim 35
Dependent Claim
68 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more acids of phosphorus, said ester having chlorine or bromine bonded directly to phosphorus, and the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) about 0.5 to 5 percent by weight free-radical initiator or photoinitiator, said composition being bonded to a tooth.
Claim 36
Dependent Claim
68 words
Compositions for use in dentistry, comprising: (a) at least one polymerizable compound comprising an organic ester of one or more acids of phosphorus, said ester having chlorine or bromine bonded directly to phosphorus, and the organic radical of said ester containing at least one free-radically polymerizable functional group, and (b) about 0.5 to 5 percent by weight free-radical initiator or photoinitiator, said composition being bonded to a tooth.
Claim 37
Dependent Claim
16 words
Compositions according to claim 28, wherein said ester comprises compounds containing groups of the formulae: ##STR13##
Claim 38
Independent Claim
70 words
A method for repairing or veneering hard dental tissue, without the necessity for acid etching said tissue, comprising the steps of: (a) applying to said tissue a polymerizable composition comprising organic ester of one or more acids of phosphorus having chlorine or bromine bonded directly to phosphorus, the organic radical of said ester containing at least one polymerizable functional group, and (b) causing said composition to harden on said tissue.
Claim 39
Independent Claim
70 words
A method for repairing or veneering hard dental tissue, without the necessity for acid etching said tissue, comprising the steps of: (a) applying to said tissue a polymerizable composition comprising organic ester of one or more acids of phosphorus having chlorine or bromine bonded directly to phosphorus, the organic radical of said ester containing at least one polymerizable functional group, and (b) causing said composition to harden on said tissue.
Claim 40
Dependent Claim
17 words
A method according to claim 30, wherein said composition comprises compounds containing groups of the formulae: ##STR14##
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1990-06-01 | 1990-12-01 | 1991-06-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-06-01 | 1994-12-01 | 1995-06-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-06-01 | 1998-12-01 | 1999-06-02 | $7700.00 | Window Closed / Lapsed |