Fluoride releasing dental primer composition and method

Abstract: The invention provides a fluoride releasing dental primer composition which includes a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride. This fluoride releasing dental primer composition is used by applying it to dentin and illuminating it with visible light to polymerize the polymerizable acrylic compound. The invention provides a method of priming dentin by applying a fluoride releasing dental primer composition. The fluoride releasing dental primer composition has a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride having from about 2 to about 30 carbon atoms. The polymerizable acrylic compound is adapted to polymerize to form polymeric material. The organic amino hydrofluoride is adapted to leach from the polymeric material, chelate to dentin and release fluoride.

Description: The invention relates to dental compositions which release fluoride. The invention provides a fluoride releasing dental primer composition. Plymale in U.S. Patent 3,997,504 discloses composition and method for treating teeth. Rawls et al in U.S. patent 4,515,910 discloses interpolymeric resin for treatment of teeth. Rawls et al in U.S. Patent 4,572,920 discloses fluoride interpolymeric resin. Aasen et al in U.S. Patent 4,871,786 discloses organic fluoride sources. Hamer et al in U.S. Patent 5,037,638 discloses fluoride release agent copolymer prepared using morpholinoethyl methacrylate hydrofluoride comonomer. Tsunekawa et al in U.S. Patent 5,112,880 discloses light-curable orthodontic bracket adhesive. Tanada et al in U.S. Patent 5,174,989 discloses oral composition. Blackwell in U.S. Patent 5,218,070 discloses dental/medical composition and use. The prior art does not provide a fluoride releasing dental primer composition which includes a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride as is provided by the present invention. It is an object of the invention to provide a fluoride releasing dental primer composition which includes a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride. It is an object of the invention to provide a method of priming dentin which includes applying to dentin a fluoride releasing dental primer composition containing a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride. "Monomer" as used herein refers to monomer and/or oligomer. BRIEF SUMMARY OF THE INVENTION The invention provides a fluoride releasing dental primer composition as defined by claim 1. This fluoride releasing dental primer composition is used by applying it to dentin and illuminating it with visible light to polymerize the polymerizable acrylic compound. A method of priming dentin by applying the fluoride releasing dental primer composition of the invention is also provided. The fluoride releasing dental primer composition has a polymerizable acrylic compound, a light activated catalyst, an organic amino hydrofluoride having from 2 to 30 carbon atoms, and a solvent. The polymerizable acrylic compound is adapted to polymerize to form polymeric material. The organic amino hydrofluoride is adapted to leach from the polymeric material, chelate to dentin and release fluoride. DETAILED DESCRIPTION OF THE INVENTION In accordance with the invention a fluoride releasing dental primer composition is provided which includes a polymerizable acrylic compound, a catalyst, an organic amino hydrofluoride, and a solvent as defined by Claim 1. The polymerizable acrylic compound is adapted to polymerize to form polymeric material. The organic amino hydrofluoride is adapted to leach from the polymeric material, chelate to dentin and release fluoride. The fluoride releasing primer composition is applied to dentin of a tooth in the mouth (oral cavity) of a patient. Preferably the patient is a human being. This fluoride releasing primer composition is brushed as a thin coating onto a prepared dentin surface, and cured for ten seconds by exposure to visible light before applying a composite. The primer coating on the dentin bonds thereto with an adhesion preferably of at least 9 MPa. A preferred fluoride releasing dental primer composition includes a polymerizable acrylic compound, a light activated catalyst, and an organic amino hydrofluoride. The organic amino hydrofluoride is an alkyl amino hydrofluoride having from 2 to 30 carbon atoms. The concentration of organic amine fluoride is from 0.1 to 5 percent by weight of the primer composition, and is completely soluble in the resin. Accordingly, the primer composition is shelf stable and does not separate during storage. Thus, no mixing or shaking of the primer is needed before use. When the fluoride leaches out of the cured resin, no voids are left. This provides better aesthetics and a reduced possibility of staining than prior art compositions. The adhesive layer formed is continuous and does not include solid particles which potentially interfere with adhesion. The amines useful in accordance with the invention preferably chelate to the dentin and/or enamel, thereby preventing bacteria from adhering and causing decay. Chelation to dentin and/or enamel does not occur in prior art primers which include inorganic fluorides, such as sodium fluoride. Cetylamine hydrofluoride is a preferred organic amine hydrofluoride for use in the composition of the invention as it has no adverse effect on the properties of the primer. The six months data in Table 2 relates to adhesion using a primer solution which has been stored at room temperature for six months before use. The amine does not separate from primer composition in accordance with the invention stored at 4°C. The fluoride releasing dental primer composition of the invention preferably releases at least 0.1 µg of fluoride per square cm per week measured using a selective fluoride ion electrode in 10% TISAB IV buffer. TISAB IV buffer is made by stirring together sodium chloride (58 g), ethylenediaminetetracarboxylic acid (EDTA, 5 g), and distilled water (500 ml), and adding just enough 32% sodium hydroxide solution to cause complete dissolution of the EDTA, glacial acetic acid (57 ml) is then added, followed by enough 32% sodium hydroxide solution to raise the pH of the mixture to between 5 and 5.5. The invention is now described in the following specific examples. The procedure of Example 1, part A is in accordance with U.S. Patent 4,814,423 assigned to Dentsply Research and Development Corporation. Example 1 A) To a mechanically-stirred mixture of 28.59 weight parts of trimethylhexamethylene diisocyanate and 0.04 weight part of stannous octoate in a reactor and purged with dry air, there is added 44.80 weight parts of polytetramethylene ether glycol, while maintaining the reaction temperature at 50° to 60°C. After the addition is complete, the mixture is heated to 70° to 80°C and held for 3 hours. A 26.58 weight parts of hydroxyethyl methacrylate (HEMA) is added and the mixture is stirred at 70° to 80°C until the percent NCO assay is below 0.01%. B) 5 g of dipentaerythritol pentaacrylate phosphoric acid ester (PENTA), 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.2 g of cetylamine hydrofluoride, and 79.0 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin and fluoride released from the primer coating are shown in Table 1. Example 2 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.1 g of cetylamine hydrofluoride, and 79.1 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin and fluoride released from the primer coating are shown in Table 1. Example 3 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.02 g of cetylamine hydrofluoride, and 79.18 g of Acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin and fluoride released from the primer coating are shown in Table 1. Fluoride releasing primer formulations, adhesion and fluoride release Example 1 Percent by weight 2 Percent by weight 3 Percent by weight PENTA 5.0 5.0 5.0 Triethylene glycol dimethacrylate 5.0 5.0 5.0 urethane diacrylate Monomer 10.0 10.0 10.0 Camphorquinone 0.2 0.2 0.2 4-Dimethylaminoethyl benzoate (DMABE) 0.6 0.6 0.6 Cetylamine hydrofluoride 0.2 0.1 0.02 Acetone 79.0 79.1 79.18 Adhesion to dentin (MPa) Using fresh primer samples stored 24 hours at 37° C samples thermocycled 11.6(2) 16.3(2.0) 13.2(2.7) Fluoride release per week (µg F-) Weeks 1 62.5 23.8 6.0 2 8.7 1.8 0.4 3 1.7 0.1 0.1 4 0.6 0.1 0.1 5 0.3 0.1 0.1 6 0.2 0.1 0.1 7 0.2 0.1 0.1 9 0.1 0.1 0.1 11 0.1 0.1 0.1 15 0.1 0.1 0.1 Example 4 (REFERENCE) 2.5 g of PENTA, 2.5 g of triethylene glycol dimethacrylate, 5 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.02 g of camphorquinone, 0.06 g of 4-dimethylaminoethyl benzoate (DMABE), 0.005 g of BHT and 0.3 g of a 33 percent solution of bis(hydroxethyl)-aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride in propanediol are mixed to form a dental primer composition. The dental primer composition is shaped in molds and illuminated with visible light for forty seconds to form cylindrical samples which are 4 mm in diameter and 6 mm in length. The elastic modulus is shown in Table 2. Example 5 (REFERENCE) 2.5 g of PENTA, 2.5 g of triethylene glycol dimethacrylate, 5 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.02 g of camphorquinone, 0.06 g of 4-dimethylaminoethyl benzoate (DMABE), 0.005 g of BHT, and 0.6 g of a 33 percent solution of bis(hydroxethyl)-aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride in propanedial dental primer composition. The dental primer composition is shaped in molds and illuminated with visible light for forty seconds to form cylindrical samples which are 4 mm in diameter and 6 mm in length. The elastic modulus is shown in Table 2. Example 6 1.0 g of PENTA, 1.0 g of triethylene glycol dimethacrylate, 2.0 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.04 g of camphorquinone, 0.12 g of 4-dimethylaminoethyl benzoate (DMABE), 0.01 g of BHT, 0.12 g of a 33 percent solution of bis(hydroxethyl)-aminopropyl-N-hydroxyethyl-octadecylamine dihydrofluoride in propanediol and 15.84 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 7 1.0 g of PENTA, 1.0 g of triethylene glycol dimethacrylate, 2.0 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.04 g of camphorquinone, 0.12 g of 4-dimethylaminoethyl benzoate (DMABE), 0.01 g of BHT, and 0.24 g of a 33 percent solution of bis(hydroxethyl)-aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride in propandiol and 15.84 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 8 (REFERENCE) 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), and 0.5 g of cetylamine hydrofluoride are mixed to form a dental primer composition. The dental primer composition was shaped in molds 4 mm diameter and 6 mm long and illuminated with visible light for forty seconds to form cylindrical samples. The elastic modulus is shown in Table 2. Example 9 (REFERENCE) 24.5 g of PENTA, 24.5 g of triethylene glycol dimethacrylate, 49.05 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), and 1 g of cetylamine hydrofluoride are mixed to form a dental primer composition. The dental primer composition is shaped in molds and illuminated with visible light for forty seconds to form rods which are 4 mm in diameter and 6 mm in length, the rods having an elastic modulus of 568.7 as shown in Table 2. Example 10 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.1 g of cetylamine hydrofluoride and 79.1 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The adhesion to dentin is shown in Table 2. Example 11 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.5 g of cetylamine hydrofluoride and 78.1 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 12 1.5 g of PENTA, 1.5 g of triethylene glycol dimethacrylate, 3 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.06 g of camphorquinone, 0.18 g of 4-dimethylaminoethyl benzoate (DMABE), 0.3 g of cetylamine hydrofluoride and 23.5 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin and is shown in Table 2. Example 13 10 g of dental primer composition prepared by following the procedure of Example 11 is stored for six months at 23°C. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 14 (COMPARATIVE) Amine-free Comparative Composition 2.45 g of PENTA, 2.45 g of triethylene glycol dimethacrylate, 4.9 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.02 g of camphorquinone, and 0.06 g of 4-dimethylaminoethyl benzoate (DMABE) are mixed to form a dental primer composition. The dental primer composition was shaped in molds to form rods 4 mm in diameter and 5 mm long and illuminated with visible light for forty seconds to form cylindrical samples. The elastic modulus are shown in Table 2. Example 15 (COMPARATIVE) Amine-free Comparative Composition 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE) and 79.2 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 16 (COMPARATIVE) 2.5 g of PENTA, 2.5 g of triethylene glycol dimethacrylate, 5 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), and 0.01 g of ammonium fluoride are mixed to form a dental primer composition. The dental primer composition is shaped in molds to form rods 4 mm diameter and 6 mm long and illuminated with visible light for forty seconds to form cylindrical samples. The elastic modulus is shown in Table 2. Example 17 (COMPARATIVE) 2.4 g of PENTA, 2.4 g of triethylene glycol dimethacrylate, 4.8 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.96 g of camphorquinone, 0.29 g of 4-dimethylaminoethyl benzoate (DMABE), 0.01 g of ammonium fluoride and 38.0 g of Acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The strength of adhesion of this primer coating to dentin is shown in Table 2. Example 18 (COMPARATIVE) 5 g of PENTA, 5 g of triethylene glycol dimethacrylate, 10 g of the urethane dimethacrylate Monomer prepared as described in Example 1, part A, 0.2 g of camphorquinone, 0.6 g of 4-dimethylaminoethyl benzoate (DMABE), 0.2 g of ammonium fluoride and 79.2 g of acetone are mixed to form a dental primer composition. The dental primer composition is applied to dentin and illuminated with visible light for ten seconds to form a primer coating. The adhesion to dentin is shown in Table 2. Examples 4-18 Amine type Amine % in resin part Elastic modulus Adhesion to dentin thermocycled MPa 4 BEAP 1.0 454.40 5 BEAP 2.0 360.20 6 BEAP 1.0 15.3±2.1 7 BEAP 2.0 13.0±2.6 8 CAF 0.5 662.6 9 CAF 1.0 568.70 10 CAF 0.1 10.9±3.0 11 CAF 0.5 10.5+3.8 12 CAF 1.0 13.0±5.2 13 CAF 0.5 15.8+2.1 six months old 14 NONE 0.0 611.80 15 NONE 0.0 14.5±2.1 16 NHF 0.1 631.30 17 NHF 0.1 14.9±3.6 18 NHF 0.2 12.8±3.2 The amines used in Examples 4-18 are cetylamine hydrofluoride (CAF), a 30% solution of bis(hydroxyethyl)-aminopropyl-N-hydroxyethyloctadecylamine dihydrofluoride in propylenediol (BEAP) and ammonium fluoride (NHF). In Table 3 are shown the adhesion to dentin and cumulative fluoride release in µg for the products of Examples 1, 3, 6, 7, 11 and 17. Example 1 11 3 17 6 7 Adhesion to dentin after thermocycling (and standard deviation) 13.1 5.2 10.5 3.8 10.9 3.0 14.9 3.6 15.3 2.1 13.0 2.6 Cumulative fluoride (µg) release in weeks 1 62.5 23.8 6.0 21.1 57.7 70.4 2 71.2 25.6 6.4 22.2 63.1 74.9 3 72.9 25.7 6.5 22.4 63.6 4 73.5 25.8 6.6 22.5 5 73.8 25.9 6.7 6 74.0 26.0 6.8 7 74.2 26.1 6.9 8 74.3 26.2 7.0 9 74.4 26.3 7.1 10 74.5 26.4 7.2

Claims: A fluoride releasing liquid dental primer composition, comprising: (a) a polymerizable acrylic compound, (b) a catalyst, (c) 0.1 to 5 % by weight based on the primer composition of alkyl amino hydrofluoride having from 2 to 30 carbon atoms, and (d) at least 50% by weight based on said composition of acetone, wherein said alkyl amino hydrofluoride is completely soluble in the resin, and wherein said composition may be polymerized on dentin to form a polymeric primer with an adhesion to said dentin of at least 9 MPa. The composition of claim 1, wherein said alkyl amino hydrofluoride is cetylamine hydrofluoride. The composition of any one of claims 1 and 2, wherein said catalyst is camphorquinone and said polymerizable acrylic compound is triethyleneglycol dimethacrylate. The composition of any one of claims 1 to 3, wherein said polymerizable acrylic compound is dipentaerythritol pentaacrylate phosphoric acid ester. The composition of claim 1 wherein said polymeric primer releases fluoride. The composition of claim 5, wherein said polymeric primer releases at least 0.1 µg of fluoride per square cm per week for at least nine weeks. The composition of any one of claims 1 to 6, wherein said polymerizable acrylic compound is a urethane dimethacrylate. The composition of any one of claims 1 to 7, wherein said catalyst is a light activated catalyst. The composition of any one of claims 1 to 8 wherein said alkyl amino hydrofluoride is free of any polymerizable acrylic or acrylate moiety. The composition of any one of claims 1 to 9, wherein the polymerization of said polymerizable compound is initiated by illuminating said dental primer composition with visible light.

Inventors: BLACKWELL GORDON, BLACKWELL, GORDON
Applicants: DENTSPLY DETREY GMBH
Application year: 1995
Main classification: A61K6
IPC codes: C08K5, A61K6, C08L33