US3940362A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Cross-linked cyanoacrylate adhesive compositions
Assignee: Dentsply Research and Development Corp
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Filing: 1972-05-25
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Granted: 1976-02-24
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Expires: 1992-05-25
Abstract
Abstract New polymerizable adhesive compositions comprising a monomeric ester of α-cyanoacrylic acid and a difunctional monomeric cross-linking agent which is a diester of acrylic or methacrylic acid and an alcohol having at least two esterifiable hydroxyl group, are found to develop increased cohesive bond strength upon polymerization. The compositions, if desired, can contain a finely divided aggregate, preferred aggregates being alumina and quartz. In addition, the compositions can advantageously contain sodium fluoride. The monomeric compounds of these adhesive compositions are polymerized in a cross-linked mode by means of an amine activated free radical initiator. The compositions can be applied to either wet or dry surfaces of a variety of materials. They are suitable for application to animal tissue, e.g., bone and flesh, and are particularly suitable for the treatment of teeth, such as for use as temporary fillings, the preparation of dental restorations and especially for filling and sealing pits and fissures in prophylactic dentistry.
Inventors
- 👤 Wendell C. Overhults
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 04:26
CPC Classifications
A; A61; A61L; A61L24/00; A61L24/04; A61L24/06; A61K; A61K6/00; A61K6/80; A61K6/884; A61K6/887; C; C09; C09J; C09J4/00; Y; Y10; Y10S; Y10S528/00; Y10S528/92
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
113 words
An adhesive composition comprising a cement portion and a catalyst portion, the cement portion comprising from 5 to 95% by weight of a monomeric ester of an α-cyanoacrylic acid and from 95 to 5% by weight of a difunctional monomer diester of an acid from the group consisting of acrylic and methacrylic acid and a polyfunctional alcohol having at least two esterifiable hydroxy groups, and the catalyst portion comprising from about 2 to 15 parts by weight of a free radical catalyst for each hundred parts by weight of the total cement portion, and an amine activator therefor in the amount of from 5 to 150 mole percent of the free radical catalyst.
Claim 2
Dependent Claim
113 words
An adhesive composition comprising a cement portion and a catalyst portion, the cement portion comprising from 5 to 95% by weight of a monomeric ester of an α-cyanoacrylic acid and from 95 to 5% by weight of a difunctional monomer diester of an acid from the group consisting of acrylic and methacrylic acid and a polyfunctional alcohol having at least two esterifiable hydroxy groups, and the catalyst portion comprising from about 2 to 15 parts by weight of a free radical catalyst for each hundred parts by weight of the total cement portion, and an amine activator therefor in the amount of from 5 to 150 mole percent of the free radical catalyst.
Claim 3
Dependent Claim
39 words
An adhesvie composition according to claim 1 wherein the monomeric ester of α-cyanoacrylic acid is of the formula ##EQU4## where R is a straight or branched chain alkyl group of from 1 to 16 carbon atoms, cyclohexyl and phenyl.
Claim 4
Dependent Claim
65 words
A composition according to claim 1 wherein the difunctional monomer is of the formula ##EQU5## wherein R 1 is methyl or hydrogen and A is --R 2 -O] n where R 2 is methylene, propylene, isopropylene, butylene, and isobutylene, and n is an integer of from 1 to 3, or --R.sub.3 --CH.sub.2 --O--φ--C(CH.sub.3).sub.2 --φ--O--CH.sub.2 --R.sub.3 --O-- wherein R 3 are --CH 2 --CH-- and ##EQU6##
Claim 5
Dependent Claim
32 words
A composition according to claim 1 wherein the cement portion comprises from about 10 to 80% of the ester of α-cyanoacrylic acid and from about 80 to 10% of the difunctional monomer.
Claim 6
Dependent Claim
14 words
A composition according to claim 1 wherein said free radical catalyst is an organo-peroxide.
Claim 7
Dependent Claim
14 words
A composition according to claim 5 wherein said free radical catalyst is benzoyl peroxide.
Claim 8
Dependent Claim
24 words
A composition according to claim 1 wherein the amine activator is an amine having a pK b in water of from 1 to 12.
Claim 9
Dependent Claim
34 words
A composition according to claim 7 wherein the amine is selected from the group consisting of N,N-dimethyl-p-toluidine; N,N-dimethylaniline, N,N-diethylaniline, N-methylbenzylamine, triethanolamine, diethanolamine, 2-picoline, 4-picoline, tributylamine, 4-ethylpyridine, pyridine, N,N-diethyl-1-naphthylamine, hexamethylenediamine, N,N-diethylethylenediamine, N,N-dimethyl-p-toluidine, N,N-dimethylaniline, and N,N-di-β-hydroxyethyl-p-toluidine.
Claim 10
Dependent Claim
30 words
A composition according to claim 1 wherein said ester of α-cyanoacrylic acid is selected from the group consisting of isobutyl-2-cyanoacrylate; methyl-2-cyanoacrylate; ethyl-2-cyanoacrylate; propyl-2-cyanoacrylate; n-butyl-2-cyanoacrylate; n-amyl-2-cyanoacrylate; isoamyl-2-cyanoacrylate; n-hexyl-2-cyanoacrylate; n-heptyl-2-cyanoacrylate; and n-octyl-2-cyanoacrylate.
Claim 11
Dependent Claim
49 words
A composition according to claim 1 wherein the difunctional monomer is selected from the group consisting of 1,3-ethyleneglycol dimethacrylate; bisphenol A diglycidyl dimethacrylate; 1,3-butyleneglycol diacrylate; ethyleneglycol dimethacrylate; ethyleneglycol diacrylate; diethyleneglycol dimethacrylate; diethyleneglycol diacrylate; 1,3-propanediol dimethacrylate; 1,3-propanedial diacrylate; 2,2-dimethyl propanediol diacrylate; tripropyleneglycol dimethacrylate; tripropyleneglycol diacrylate; triethyleneglycol diacrylate; and triethyleneglycol dimethacrylate.
Claim 12
Dependent Claim
27 words
A composition according to claim 1 wherein said free radical catalyst is present in an amount of from 3 to 8% by weight of the cement portion.
Claim 13
Dependent Claim
33 words
A composition according to claim 1 wherein said amine activator is N,N dimethyl-p-toluidine and is present in substantially an amount of 100 mole percent as based on the moles of free radical catalyst.
Claim 14
Dependent Claim
12 words
A composition according to claim 1 wherein there is included a filler.
Claim 15
Dependent Claim
29 words
A composition according to claim 13 wherein the filler is from 1 to 4 parts by weight per each part by weight of the combined cement and catalyst portions.
Claim 16
Dependent Claim
22 words
A composition according to claim 13 in which said filler is selected from the group consisting of alumina, quartz and fused silica.
Claim 17
Dependent Claim
16 words
A composition according to claim 13 wherein the filler carries an undercoat of a trialkoxysilyl compound.
Claim 18
Dependent Claim
17 words
A composition according to claim 16 wherein the coated filler carries a coating of an amine activator.
Claim 19
Dependent Claim
19 words
A composition according to claim 1 wherein there is included from 5 to 25% by weight of sodium fluoride.
Claim 20
Dependent Claim
39 words
A composition according to claim 4 in which the ester of α-cyanoacrylic acid is isobutyl-2-cyanoacrylate, the difunctional monomer is 1,3-butyleneglycol dimethacrylate, the free radical catalyst is benzoyl peroxide, and the amine activator for the free radical catalyst is N,N-di-β-hydroxyethyl-p-toluidine.
Claim 21
Independent Claim
147 words
A system for obtaining a hard cohesive crosslinked mass having distributed between a first component and a second component thereof a cement portion comprising from 5 to 95% by weight of a monomeric ester of an α-cyanoacrylic acid and from 95 to 5% by weight of a difunctional monomer diester of an acid from the group consisting of acrylic and methacrylic acid and a polyfunctional alcohol having at least two esterifiable hydroxy groups, and a catalyst portion comprising a free radical catalyst in the amount of from 2 to 15 parts by weight for each hundred parts by weight of the total cement portion, and an amine activator in the amount of from 5 to 150 mole percent of the free radical catalyst wherein all the amine activator is in the first component, and all the monomeric ester of the α-cyanoacrylic acid is in the second component.
Claim 22
Independent Claim
147 words
A system for obtaining a hard cohesive crosslinked mass having distributed between a first component and a second component thereof a cement portion comprising from 5 to 95% by weight of a monomeric ester of an α-cyanoacrylic acid and from 95 to 5% by weight of a difunctional monomer diester of an acid from the group consisting of acrylic and methacrylic acid and a polyfunctional alcohol having at least two esterifiable hydroxy groups, and a catalyst portion comprising a free radical catalyst in the amount of from 2 to 15 parts by weight for each hundred parts by weight of the total cement portion, and an amine activator in the amount of from 5 to 150 mole percent of the free radical catalyst wherein all the amine activator is in the first component, and all the monomeric ester of the α-cyanoacrylic acid is in the second component.
Claim 23
Dependent Claim
38 words
A system according to claim 20 wherein the monomeric ester of α-cyanoacrylic acid is of the formula ##EQU7## where R is a straight or branched chain alkyl group of from 1 to 16 carbon atoms, cyclohexyl and phenyl.
Claim 24
Dependent Claim
65 words
A system according to claim 20 wherein the difunctional monomer is of the formula ##EQU8## wherein R 1 is methyl or hydrogen and A is --R 2 -O] n where R 2 is methylene, propylene, isopropylene, butylene, and isobutylene, and n is an integer of from 1 to 3, or --R.sub.3 --CH.sub.2 --O--φ--C(CH.sub.3).sub.2 --φ--O--CH.sub.2 --R.sub.3 --O-- wherein R 3 are CH 2 --CH and ##EQU9##
Claim 25
Dependent Claim
35 words
A system according to claim 20 wherein there is included a filler in an amount of from 1 to 4 parts by weight per each part by weight of the combined cement and catalyst portions.
Claim 26
Dependent Claim
31 words
A system according to claim 20 wherein the first component comprises the amine activator and the difunctional monomer; and the second component comprises the free radical catalyst and the monofunctional monomer.
Claim 27
Dependent Claim
30 words
A system according to claim 20 wherein the first component comprises the amine activator, the free radical catalyst, and the difunctional monomer; and the second component comprises the monofunctional monomer.
Claim 28
Dependent Claim
31 words
A system according to claim 20 wherein the first component comprises the amine activator and the free radical catalyst; and the second component comprises the monofunctional monomer and the difunctional monomer.
References Cited (Backward Citations)
US2558139A
Cited
US2833753A
Cited
US3527729A
Cited
US3442851A
Cited
GB1122439A
Cited
US3539533A
Cited
US3663501A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-02-23 | 1979-08-25 | 1980-02-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-02-23 | 1983-08-25 | 1984-02-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-02-23 | 1987-08-25 | 1988-02-24 | $7700.00 | Window Closed / Lapsed |