CA2495934A1 - Non-volatile dental compositions - Google Patents
Non-volatile dental compositions Download PDFInfo
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- CA2495934A1 CA2495934A1 CA002495934A CA2495934A CA2495934A1 CA 2495934 A1 CA2495934 A1 CA 2495934A1 CA 002495934 A CA002495934 A CA 002495934A CA 2495934 A CA2495934 A CA 2495934A CA 2495934 A1 CA2495934 A1 CA 2495934A1
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- composition
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- multiacrylate
- initiator
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
Abstract
Dental composite formulations containing an initiator and a multiacrylate compound are disclosed. The formulations lack methyl methacrylate, a volatile, irritating, and potentially hazardous material commonly found in dental formulations. The multiacrylate compound has at least three acrylate functionalities per molecule. The formulations cure to form a surface lacking an oxygen inhibition layer. The formulations can be used as dental sealants, dental coatings, and in fingernail/toenail repair applications.
Description
NON-VOLATILE DENTAL COMPOSITIONS
FIELD OF THE INVENTION
[0001] The invention relates to dental composite materials, and more specifically, to dental composite materials containing multifunctional acrylate compounds while lacking volatile compounds such as methyl methacrylate.
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The invention relates to dental composite materials, and more specifically, to dental composite materials containing multifunctional acrylate compounds while lacking volatile compounds such as methyl methacrylate.
BACKGROUND OF THE INVENTION
[0002] Dental sealants and adhesives are widely used in clinical settings.
Desirable properties include safety, efficacy, durability, and favorable cosmetic properties. It is preferred that dental compositions be shelf stable, easy to formulate, and that they do not set so rapidly as to make them difficult to apply to a patient.
Desirable properties include safety, efficacy, durability, and favorable cosmetic properties. It is preferred that dental compositions be shelf stable, easy to formulate, and that they do not set so rapidly as to make them difficult to apply to a patient.
[0003] Dental compositions frequently contain monomers which are polymerized by the dentist or technician (e.g. by light, self cure, or dual-cure). However, many dental compositions form a problematic "oxygen inhibited layer" (OIL) or "uncured layer" on their surface. This layer's polymerization is inhibited due to the presence of molecular oxygen radicals in ambient air. As a result, incomplete polymerization occurs. Such layer often render the surface sticky or tacky, making the dental composition more difficult to mold or shape. Such incomplete polymerization also tends to lead to lower hardness of the surface and/or no curing if a thin surface is present.
[0004] Extoral is a visible-light cured dental resin formulation sold by AFR
Imaging Corp.
(Portland, Oregon). Extoral can be used for surface treatment or as a denture resin. Extoral cures rapidly and produces a glossy, hard surface upon irradiation with normal dental light.
Extoral is significant in that it does not have an "oxygen inhibited layer", even when cured with low intensity light. One difficulty with using Extoral is its volatility, leading to a very strong odor. The smell is objectionable to both patients and dentists/technicians, making it difficult to use in a laboratory, and nearly impossible to use in a clinical setting.
Another difficulty is the very brittle surface created by Extoral, which may limit its use in certain dental applications such as surfaces subject to compressive forces.
Imaging Corp.
(Portland, Oregon). Extoral can be used for surface treatment or as a denture resin. Extoral cures rapidly and produces a glossy, hard surface upon irradiation with normal dental light.
Extoral is significant in that it does not have an "oxygen inhibited layer", even when cured with low intensity light. One difficulty with using Extoral is its volatility, leading to a very strong odor. The smell is objectionable to both patients and dentists/technicians, making it difficult to use in a laboratory, and nearly impossible to use in a clinical setting.
Another difficulty is the very brittle surface created by Extoral, which may limit its use in certain dental applications such as surfaces subject to compressive forces.
[0005] Extoral's odor is suggestive of the presence of methyl methacrylate.
Methyl methacrylate is a volatile compound used in several dental products. In addition to its unpleasant smell, exposure to methyl methacrylate has been linked to various health concerns. Numbness, paraesthesia, reduced pulmonary function, and reduced respiratory function have been observed in dental technicians who have been chronically exposed to methyl methacrylate (Sadoh, D.R. et al., British Dental J. 186(8): 380-381, 1999; Nishiwaki, Y. et al., J. Occup.
Health 43: 375-378, 2001). The U.S. Environmental Protection Agency describes methyl methacrylate as an irritant of the nose and throat, and mentions that exposure for short periods of time can cause headache and fatigue (EPA 749-F-95-014 Fact Sheet, November 1994).
Methyl methacrylate is a volatile compound used in several dental products. In addition to its unpleasant smell, exposure to methyl methacrylate has been linked to various health concerns. Numbness, paraesthesia, reduced pulmonary function, and reduced respiratory function have been observed in dental technicians who have been chronically exposed to methyl methacrylate (Sadoh, D.R. et al., British Dental J. 186(8): 380-381, 1999; Nishiwaki, Y. et al., J. Occup.
Health 43: 375-378, 2001). The U.S. Environmental Protection Agency describes methyl methacrylate as an irritant of the nose and throat, and mentions that exposure for short periods of time can cause headache and fatigue (EPA 749-F-95-014 Fact Sheet, November 1994).
[0006] It would be of great value to develop a dental composition that does not have an "oxygen inhibited layer" and that does not contain methyl methacrylate or other volatile compounds that are irritating and potentially dangerous to dentists, dental technicians, and their patients.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0007] An embodiment of the invention is directed towards dental acrylic compositions containing a multiacrylate compound and an initiator. Curing of the compositions results in surfaces lacking an oxygen inhibition layer ("OIL"). The formulations do not contain methyl methacrylate, an irritating and potentially harmful material found in many dental formulations.
The multiacrylate compound contains at least three acrylate units per molecule. The formulations can further comprise other acrylate compounds, solvents, fillers, nanofillers, diluents, or other materials useful in dental formulations. The formulations are useful in applications such as dental coatings, dental sealants, and fingernail /
toenail repair.
DETAILED DESCRIPTION OF THE INVENTION
The multiacrylate compound contains at least three acrylate units per molecule. The formulations can further comprise other acrylate compounds, solvents, fillers, nanofillers, diluents, or other materials useful in dental formulations. The formulations are useful in applications such as dental coatings, dental sealants, and fingernail /
toenail repair.
DETAILED DESCRIPTION OF THE INVENTION
[0008] An embodiment of the invention is directed towards dental acrylic material compositions that cure to form surfaces that lack an oxygen inhibition layer ("OIL"). The compositions preferably do not contain methyl methacrylate. The compositions preferably cure rapidly to form stable, hard, glossy surfaces.
[0009] One embodiment of the invention is a dental composition comprising a multiacrylate compound and an initiator. The multiacrylate compound is a chemical compound comprising at least three acrylate functionalities per molecule. The composition preferably does not contain methyl methacrylate. The composition, upon curing, preferably does not form an oxygen inhibition layer.
[0010] Presently preferred initiators are phosphine oxide photoinitiators and camphorquinone.
Examples of such initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), TPO-L, Irgacure 819, Darocure 4265, and camphorquinone. It is expected that other initiators capable of photocleavage with or without the need for amine co-initiators will have utility according to the present invention. The initiator can generally be present at any concentration in the composition. The initiator is preferably present at a concentration that will not noticeably discolor the cured composition. Example concentration ranges of the initiator include about 1 weight percent of the composition or less, at least about 1 weight percent of the composition, at least about 2 weight percent of the composition, at least about 3 weight percent of the composition, at least about 4 weight percent of the composition, at least about 5 weight percent of the composition, at least about 6 weight percent of the composition, or at least about 7 weight percent of the composition up to saturation levels of initiator in the composition. Example concentrations of the initiator include about 3 weight percent of the composition, about 6 weight percent of the composition, and about 7 weight percent of the composition up to saturation levels of initiator in the composition. It is also expected that lower concentrations can be provided in the presence of a volatile dental solvent such as acetone that, upon evaporation, provides the desired higher effective initiator concentration in the composition.
Examples of such initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), TPO-L, Irgacure 819, Darocure 4265, and camphorquinone. It is expected that other initiators capable of photocleavage with or without the need for amine co-initiators will have utility according to the present invention. The initiator can generally be present at any concentration in the composition. The initiator is preferably present at a concentration that will not noticeably discolor the cured composition. Example concentration ranges of the initiator include about 1 weight percent of the composition or less, at least about 1 weight percent of the composition, at least about 2 weight percent of the composition, at least about 3 weight percent of the composition, at least about 4 weight percent of the composition, at least about 5 weight percent of the composition, at least about 6 weight percent of the composition, or at least about 7 weight percent of the composition up to saturation levels of initiator in the composition. Example concentrations of the initiator include about 3 weight percent of the composition, about 6 weight percent of the composition, and about 7 weight percent of the composition up to saturation levels of initiator in the composition. It is also expected that lower concentrations can be provided in the presence of a volatile dental solvent such as acetone that, upon evaporation, provides the desired higher effective initiator concentration in the composition.
[0011] The multiacrylate compound can generally be any multiacrylate compound having at least three acrylate functionalities per molecule in relatively close spatial proximity to one another. Examples of such multiacrylate compounds include a hexafunctional aromatic urethane acrylate oligomer, a caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, di-trimethylolpropane tetraacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate. Other multiacrylate compounds comprising three acrylate functionalities per molecule, compounds comprising four acrylate functionalities per molecule, compounds comprising five acrylate functionalities per molecule, compounds comprising six acrylate functionalities per molecule, compounds comprising seven acrylate functionalities per molecule, compounds comprising eight acrylate functionalities per molecule, compounds comprising nine acrylate functionalities per molecule, and compounds comprising ten acrylate functionalities per molecule in relatively close spatial proximity to one another are also expected to have utility according to the present invention. Larger number of oligo-acrylates or polyacrylates could be added to the compositions.
[0012] The multiacrylate compound can generally be present at any concentration of the composition. Example concentration ranges include at least about 20 weight percent of the composition and at least about 30 weight percent of the composition. Specific concentration examples include about 20 weight percent, about 30 weight percent, about 40 weight percent, about 50 weight percent, about 60 weight percent, about 70 weight percent, about 80 weight percent, about 90 weight percent, and about 95 weight percent of the composition.
[0013] The compositions can further comprise a co-monomer. The co-monomer preferably polymerizes with the multiacrylate compound. The co-monomer can generally be any type of co-monomer, and preferably is a non-volatile acrylate compound with a surface tension that is similar to or higher than that of the selected multifunctional acrylate compounds) present in the composition. Presently preferred co-monomers include a monoacrylate compound, diacrylate compound, a triacrylate compound, or a tetraacrylate compound. An example monoacrylate is caprolactone acrylate. Example diacrylate compounds are tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol diacrylate, epoxy diacrylate, urethane dimethacrylate, and urethane diacrylate. An example triacrylate compound is trimethylolpropane triacrylate. An example tetraacrylate is ditrimethylolpropane tetraacrylate.
Ethoxylated forms of such acrylates may be preferred due to their relatively higher surface tension.
Ethoxylated forms of such acrylates may be preferred due to their relatively higher surface tension.
[0014] The composition can further include a volatile, non-reactive solvent.
Examples of such solvents include acetone, ethanol and mixtures of acetone and water, ethanol and water and/or acetone, ethanol and water.
Examples of such solvents include acetone, ethanol and mixtures of acetone and water, ethanol and water and/or acetone, ethanol and water.
[0015] The compositions can further comprise fillers, nanofillers, glass particles, or other dental materials. Examples of such fillers include Ox-50, silane-treated Ox-50, glass ionomer powder IXG 1944 RGW from Ferro, which is also a fluoride release agent.
[0016] An additional embodiment of the invention is directed towards methods of using the above-described compositions. A method of sealing a surface can comprise obtaining a surface;
applying to the surface a composition comprising a multiacrylate compound and an initiator; and curing the composition to obtain a sealed surface. The sealed surface preferably does not contain an oxygen inhibition layer.
applying to the surface a composition comprising a multiacrylate compound and an initiator; and curing the composition to obtain a sealed surface. The sealed surface preferably does not contain an oxygen inhibition layer.
[0017] The surface can generally be any surface to be sealed, and is presently preferred to be a dental surface, a tooth, a dental implant, an artificial tooth, a bone, a fingernail, or a toenail.
Additionally, the surface may be that of a previously applied dental composition such as a dental composite.
Additionally, the surface may be that of a previously applied dental composition such as a dental composite.
[0018] The curing can generally be performed by any means sufficient to rapidly cure the composition to form a non-oxygen inhibited layer (MOIL). The curing step is presently preferred to comprise light curing. The light curing can be performed at low light intensity or at high light intensity. The intensity of light is preferably an intensity suitable for use in a dental laboratory or in a dentist's office. Examples of light intensity ranges include less than about 50 mW/cm2, less than about 100 mW/cm2, about 200 mW/cm2 or less, about 300 mW/cm2 or less, about 400 mW/cm2 or less, about 500 mW/cm2 or less, about 600 mW/cmaor less, about 800 mWlcm2 or less, and about 2000 mW/cma or less, it being understood that higher light intensities can also be employed. Specific examples of light intensities include about 50 mW/cm2, about 100 mW/cm2, about 150 mW/cm2, about 200 mW/cm2, about 250 mW/cm2, about 300 mW/cm2, about mW/cm2, about 400 mW/cma, about 450 mW/cm2, about 500 mW/cm2, about 600 mW/cm2°
about 800 mW/cmz, and about 2000 mW/cm2. Higher light intensities may also be used. For example, Bisco's VIPT"" Dental Light Curing system using a blue wavelength light source may be employed by the dentist. Light-curing systems for dental laboratories such as the Jeneric-Pentron Cure-Lite Plus light box system or the Triad light box system from Dentsply, Inc. may also be used for dental appliances. Bisco's NTLT"" System utilizing its light source without the nitrogen environment may also be used. The time of light curing can generally be any time.
Presently preferred time ranges include about two minutes or less, about one minute or less, less than about 30 seconds, less than about 20 seconds, less than about 15 seconds, less than about 10 seconds, and less than about 5 seconds. Specific examples of light curing times include about one minute, about 30 seconds, about 20 seconds, about 15 seconds, about 10 seconds, about 5 seconds, about 3 seconds, about 2 seconds, and about 1 second. Shorter light cure times are generally preferably to shorten patient time for the procedure and for the convenience of the dental practitioner.
about 800 mW/cmz, and about 2000 mW/cm2. Higher light intensities may also be used. For example, Bisco's VIPT"" Dental Light Curing system using a blue wavelength light source may be employed by the dentist. Light-curing systems for dental laboratories such as the Jeneric-Pentron Cure-Lite Plus light box system or the Triad light box system from Dentsply, Inc. may also be used for dental appliances. Bisco's NTLT"" System utilizing its light source without the nitrogen environment may also be used. The time of light curing can generally be any time.
Presently preferred time ranges include about two minutes or less, about one minute or less, less than about 30 seconds, less than about 20 seconds, less than about 15 seconds, less than about 10 seconds, and less than about 5 seconds. Specific examples of light curing times include about one minute, about 30 seconds, about 20 seconds, about 15 seconds, about 10 seconds, about 5 seconds, about 3 seconds, about 2 seconds, and about 1 second. Shorter light cure times are generally preferably to shorten patient time for the procedure and for the convenience of the dental practitioner.
[0019] The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
EXAMPLES
Example 1: Abbreviations used in the Examples [0020] The following table lists the chemical compounds and abbreviations used throughout the Examples section.
Abbreviation / Chemical name Commercial source product BZ Benzophenone Sartomer (Eaton, PA) CQ Camphorquinone Aldrich Chemical CTXO 2-Chlorotioxanthen-9-oneAldrich Chemical EDMAB Ethyl (4-dimethylamino)benzoateEsschem Company MEHQ Methylhydroquinone, a Aldrich Chemical polymerization inhibitor MMA Methyl methacrylate Aldrich Chemical OX-50 Fumed silicon dioxide Degussa filler TMPTMA Trimethylopropane Esschem Company trimethacrylate TPO Lucirin TPO photoinitiator;BASF (Mount Olive, 2,4,6- NJ) trimethylbenzoyldiphenylphosphi ne oxide UDMA Urethane dimethacrylate Esschem CD 9052 Trifunctional acid esterSartomer (Eaton, PA) CN 120 Epoxy diacrylate Sartomer (Eaton, PA) CN 383 Monofunctional acrylatedSartomer (Eaton, amine PA) coinitiator CN 975 Hexafunctional aromatic Sartomer (Eaton, urethane PA) acrylate oligomer CN 983 Urethane diacrylate Sartomer (Eaton, PA) l~ayarad DPCA20 Caprolactone modified Sartomer (Eaton, (DP20) dipentaerythritol hexaacrylatePA) I~ayarad DPCA60 Caprolactone modified Sartomer (Eaton, (DP60) dipentaerythritol hexaacrylatePA) SR 259 Polyethylene glycol (200)Sartomer (Eaton, diacrylate PA) SR 306 Tripropylene glycol diacrylateSartomer (Eaton, PA) SR 344 Polyethylene glycol 400 Sartomer (Eaton, diacrylate PA) SR 349 Ethoxylated bisphenol Sartomer (Eaton, A PA) diacrylate SR 350 Trimethylolpropane Sartomer (Eaton, trimethacrylate PA) SR 351 Trimethylolpropane triacrylateSartomer (Eaton, PA) SR 355 Ditrimethylolpropane Sartomer (Eaton, tetraacrylate PA) SR 399 Dipentaerythritol pentaacrylateSartomer (Eaton, PA) SR 459 Caprolactone acrylate Sartomer (Eaton, PA) SR 495 Caprolactone acrylate Sartomer (Eaton, PA) SR 502 Ethoxylated trimethylolpropaneSartomer (Eaton, triacrylate PA) SR 610 Polyethylene glycol (600)Sartomer (Eaton, diacrylate PA) Example 2: Analysis of Extoral composition [0021] While Extoral is a commercial product, its composition and ingredients are not publicly known. The strong objectionable odor suggested that Extoral contains methyl methacrylate. The following analytical experiments were performed in an attempt to determine the chemical composition of Extoral.
EXAMPLES
Example 1: Abbreviations used in the Examples [0020] The following table lists the chemical compounds and abbreviations used throughout the Examples section.
Abbreviation / Chemical name Commercial source product BZ Benzophenone Sartomer (Eaton, PA) CQ Camphorquinone Aldrich Chemical CTXO 2-Chlorotioxanthen-9-oneAldrich Chemical EDMAB Ethyl (4-dimethylamino)benzoateEsschem Company MEHQ Methylhydroquinone, a Aldrich Chemical polymerization inhibitor MMA Methyl methacrylate Aldrich Chemical OX-50 Fumed silicon dioxide Degussa filler TMPTMA Trimethylopropane Esschem Company trimethacrylate TPO Lucirin TPO photoinitiator;BASF (Mount Olive, 2,4,6- NJ) trimethylbenzoyldiphenylphosphi ne oxide UDMA Urethane dimethacrylate Esschem CD 9052 Trifunctional acid esterSartomer (Eaton, PA) CN 120 Epoxy diacrylate Sartomer (Eaton, PA) CN 383 Monofunctional acrylatedSartomer (Eaton, amine PA) coinitiator CN 975 Hexafunctional aromatic Sartomer (Eaton, urethane PA) acrylate oligomer CN 983 Urethane diacrylate Sartomer (Eaton, PA) l~ayarad DPCA20 Caprolactone modified Sartomer (Eaton, (DP20) dipentaerythritol hexaacrylatePA) I~ayarad DPCA60 Caprolactone modified Sartomer (Eaton, (DP60) dipentaerythritol hexaacrylatePA) SR 259 Polyethylene glycol (200)Sartomer (Eaton, diacrylate PA) SR 306 Tripropylene glycol diacrylateSartomer (Eaton, PA) SR 344 Polyethylene glycol 400 Sartomer (Eaton, diacrylate PA) SR 349 Ethoxylated bisphenol Sartomer (Eaton, A PA) diacrylate SR 350 Trimethylolpropane Sartomer (Eaton, trimethacrylate PA) SR 351 Trimethylolpropane triacrylateSartomer (Eaton, PA) SR 355 Ditrimethylolpropane Sartomer (Eaton, tetraacrylate PA) SR 399 Dipentaerythritol pentaacrylateSartomer (Eaton, PA) SR 459 Caprolactone acrylate Sartomer (Eaton, PA) SR 495 Caprolactone acrylate Sartomer (Eaton, PA) SR 502 Ethoxylated trimethylolpropaneSartomer (Eaton, triacrylate PA) SR 610 Polyethylene glycol (600)Sartomer (Eaton, diacrylate PA) Example 2: Analysis of Extoral composition [0021] While Extoral is a commercial product, its composition and ingredients are not publicly known. The strong objectionable odor suggested that Extoral contains methyl methacrylate. The following analytical experiments were performed in an attempt to determine the chemical composition of Extoral.
[0022] Evaporation of the volatile components of Extoral produced a viscous resin. About 40%
by weight of the composition evaporated. This was assumed to be primarily methyl methacrylate.
_g_ [0023] FTIR assays of pre- and post-evaporation Extoral revealed several transitions. A peak at 1620 cm 1 grows larger upon evaporation of methyl methacrylate. This peak is present in butyl acrylate, but not in butyl methacrylate. An aliphatic double-bond peak shifts from 1635.0 cm 1 to 1633.8 cm 1 upon evaporation, indicating a transition from a methacrylate-like character to a more acrylate-like character. The FTIR spectrum of Extoral does not suggest the presence of amines.
by weight of the composition evaporated. This was assumed to be primarily methyl methacrylate.
_g_ [0023] FTIR assays of pre- and post-evaporation Extoral revealed several transitions. A peak at 1620 cm 1 grows larger upon evaporation of methyl methacrylate. This peak is present in butyl acrylate, but not in butyl methacrylate. An aliphatic double-bond peak shifts from 1635.0 cm 1 to 1633.8 cm 1 upon evaporation, indicating a transition from a methacrylate-like character to a more acrylate-like character. The FTIR spectrum of Extoral does not suggest the presence of amines.
[0024] UV/Vis spectra comparing Extoral with a TPO standard allowed estimated identification and quantification of TPO in Extoral to be about 4%.
Example 3: Addition of a hexafunctional acrylate [0025] Compositions were prepared using CN-975, a hexafunctional aromatic urethane acrylate, MMA, and other compounds. Numbers represent the amount of each compound in the composition by weight percent.
Composition Compound AC-10 AC-l0A AC-11 AC-11A
CN 975 17.2 16.7 68.7 67.0 CN 120Z 51.5 50.3 MMA 29.5 28.7 29.5 28.7 TPO 1.8 4.3 1.8 4.3 [0026] Compositions AC-10 and AC-11 had sticky surfaces upon curing at 500 mW/cm2 for 5 seconds. FTIR showed that the surface conversion was 47.3% for AC-10 and 47.5%
for AC-11, about 16% lower than for Extoral (63.2%). The higher TPO concentration in AC-l0A and AC-11A enhanced the curability. The surface conversion was 65.7% for AC-l0A and 58.7% for AC-1 lA.
Example 3: Addition of a hexafunctional acrylate [0025] Compositions were prepared using CN-975, a hexafunctional aromatic urethane acrylate, MMA, and other compounds. Numbers represent the amount of each compound in the composition by weight percent.
Composition Compound AC-10 AC-l0A AC-11 AC-11A
CN 975 17.2 16.7 68.7 67.0 CN 120Z 51.5 50.3 MMA 29.5 28.7 29.5 28.7 TPO 1.8 4.3 1.8 4.3 [0026] Compositions AC-10 and AC-11 had sticky surfaces upon curing at 500 mW/cm2 for 5 seconds. FTIR showed that the surface conversion was 47.3% for AC-10 and 47.5%
for AC-11, about 16% lower than for Extoral (63.2%). The higher TPO concentration in AC-l0A and AC-11A enhanced the curability. The surface conversion was 65.7% for AC-l0A and 58.7% for AC-1 lA.
[0027] The surface of cured AC-11A resembles cured Extoral: non-sticky, slick, hard, and glossy.
Example 4: Preparation of "no oxygen inhibited layer" (MOIL) compositions [0028] NOIL compositions contain at least two components: a multifunctional acrylate and a photo-initiator (such as phosphine oxide). A diluent (such as ethoxylated di-or tri-acrylate) may also be added to enhance handling of the multiacrylate and / or solubility of the initiator. The compositions can contain additional materials such as solvents, polymerizable co-monomers, inhibitors, surfactants, glass filler, fluorescent or phosphorescent compounds, dyes, colorants, fluoride compounds, and other materials used in the dental and orthodontic fields.
Examples: Preparation of unfilled resin compositions [0029] A mixture of multifunctional-acrylate, diluents, TPO or other initiator, and optionally MEHQ are blended together. The mixture may be heated at 60 °C - 62 °C for four hours with stirring or shaking to afford a clear or hazy solution. The haziness, if any, will fade over a few days.
Example 6: Preparation of filled resin compositions [0030] Unfilled resin and filler such as OX 50 are combined as a slurry. The slurry is ground for 30 minutes. The grinding process often introduces air bubbles into the mixture. The bubbles can be removed by centrifugation at >1000 x g for 30 minutes to afford an essentially clear solution.
Example 7: Monomers for use in "No Oxygen Inhibited Layer" (MOIL) compositions [0031 ] Multifunctional acrylates and acrylated diluent co-monomers have been found to be effective ingredients in NOIL compositions. The following table lists exemplary compounds that have been found to be useful.
Trade name Chemical descriptionCharacteristics Multifunctional Acrylates CN 975 Hexafunctional axomaticFast curing, high urethane acrylate hardness I~ayarad DPCA20 (DP20)Acrylate of caprolactoneFast curing, lower modified dipentaerythritolviscosity I~ayarad DPCA60 (DP60)Acrylate of caprolactoneFast curing, flexibility modified dipentaerythritol Acrylated Co-Monomers SR 344 Polyethylene glycol Hydrophobicity, hardness diacrylate SR 349 Ethoxylated bisphenolHydrophobicity, hardness A
diacrylate esters SR 610 Polyethylene glycol Low viscosity, flexibility (600) diacrylate SR 459 Caprolactone acrylateFlexibility, hydrophobicity CN 383 Monofunctional acrylatedVery low viscosity, amine polymerizing rate promoter CD 9052 Trifunctional acid Adhesion promoter ester Example 8: Preparation of volatile MMA compositions containing a tetrafunctional acrd AC-23 and -33 [0032] A composition containing 3g SR355 (ditrimethylolpropane tetraacrylate), 2g MMA
volatile co-monomer, 0.25g TPO, and 3.Smg MEHQ was prepared ("AC-23"). The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). The composition was coated on white paper and exposed to VIP light source set at 600 mW/cm2 intensity for an exposure time of 30 seconds. An oxygen inhibition layer was detected by finger touch, which revealed a soft surface even after waiting 10 minutes after exposure to the light source. These results suggest that a tetrafunctional acrylate in the presence of a volatile co-monomer MMA was insufficient to prevent formation of an oxygen inhibition layer.
[0033] An additional composition containing lg CN975, 4g SR355 (ditrimethylolpropane tetraacrylate), 0.35g TPO, and 2.Smg MEHQ was prepared ("AC-33"). The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). This composition could not be cured tack-free in less than 60 seconds exposure to the VIP light gun set at 600 mW/cm2, and was easily scratchable even after exposure to that intensity light for 60 seconds.
Example 9: Preparation of a volatile MMA composition containin~i a pentafunctional acrylate [0034] A composition containing 3g SR399 (dipentaerythritol pentaacrylate esters), 2g MMA
volatile co-monomer, 0.25g TPO, and 3.Smg MEHQ was prepared. The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). The composition was coated on Pyramid composite, shade 3.5 (Bisco, Inc.) and cured by exposure to the VIP light gun output for 10 seconds at 300 mW/cm2. No oxygen inhibition layer was detected by finger touch, suggesting that a pentafunctional acrylate in the presence of a volatile co-monomer MMA is sufficient to prevent formation of an oxygen inhibition layer.
Example 10: Preparation of non-volatile NOIL compositions AC-15C and filled and colored AC-[0035] A composition containing 2.7g CN975, 3.3g SR344, 0.333g TPO, and 3mg MEHQ was prepared ("AC-15C"). A filled mixture of 75% AC-15C and 25% OX50 filler by weight was also prepared. The AC-15C compositions contain a hexafunctional diacrylate (CN
975) and no MMA. No MMA odor or other appreciable odor was detected. AC-15C exhibited better light curing sensitivity than Extoral, with twice the double-bond conversion rate.
AC-15 was curable scratch-free and mar free after 20 seconds exposure to 500 mW/cm2 light source using VIP, or 40 seconds at 200 mW/cm2 using the same curing light source. Addition of 10%
methyl blue colorant in ethanol did not adversely affect the curing. The conversion rate of AC-15C in air and in a nitrogen environment was the same, indicating that it lacked an OIL
layer. The Barcol hardness of AC-15C was 77 after curing 40 seconds at 200 mW/cm2 exposure using the Cure-Lite Plus light box system.
Example 11: Preparation of non-volatile, NOIL composition AC-35 [0036] A composition containing 3.22g CN975, 1.38g CN383, 0.4g TPO, and 2.Smg MEHQ
was prepared. AC-35 formed a scratch-free to human fingernail and tack-free surface to touch after 10 seconds cured at 300 mW/cm2 on Pyramid shade 3.5 composite using the VIP system.
AC-36, prepared containing the same amounts of TPO and MEHQ but 2.76g CN 975 and 1.848 CN 383, was curable scratch-free to fingernail scratching and tack-free to touch using the same composite base and light cure system after 20 seconds exposure at 300 mW/cm2.
Example 12: Preparation of non-volatile NOIL compositions AC-40 and AC-40A
[0037] A composition containing 8.9g CN975, 10.3g SR349, 7.8g SR610, 0.9g CD9052, 2.1g TPO, and l5mg MEHQ was prepared. The composition cured into a scratch-free surface after 20 seconds exposure on Pyramid shade 3.5 composite using the VIP curing system set at 500 mW/cm2. The AC-40 composition also exhibited good stability after storage under water at 60 °C, curing in 20 seconds at 300 mW/cm2 on Pyramid composite shade 3.5 after 30 days and 47 days, the latter being comparable to storage for 472 days at 20 °C.
Addition of 5% CN 383 to the composition (AC-40A) caused a scratch-free surface to form after curing at 300 mW/cm2 for 15-20 seconds, or 10 seconds at 500 mW/cma exposure on Pyramid composite using the VIP
curing light system. In addition to sealing applications, this composition may also be attractive as a deep cavity filler due to its relatively high viscosity (around 1200 cps at 22 °C).
[0038] AC-40 also exhibits good compressive strength of about 282MPa +/- 27 MPa.
Compressive strength is determined by preparing a sample in a 6mm high by 4rrun diameter stainless steel split mold. The sample is cured at 500 ~ 50 mW/cm2 for 60 seconds per side. The disc is heated at 37 °C for 15 minutes. The disc is placed in a 30 ml Nalgene bottle filled with deionized water, and heated for 23 hours at 37 °C. The disc is removed, blotted dry, and cooled to room temperature for one hour. An Instron Universal Testing Instrument (model 4465) is used to determine the load reading (kg) at which the sample breaks. The compressive strength is calculated as (load reading (kg) x 0.0624) / sample diameter (cm).
[0039] AC-40 passed a cytotoxicity assay performed with mouse fibroblast cells on a solid agarose surface. Toxicity, or the lack thereof, was determined by measuring the zone of lysis (if any) around the test sample after incubation at 37 °C in 5% carbon dioxide for 24 hours.
Example 13: Preparation of a non-volatile NOIL composition DP20-5 [0040] A composition containing 5.2g DP20, l.Sg CN383, 2.1g SR610, O.Sg CD9052, 0.7g TPO, and 4.4mg MEHQ was prepared. The composition cured very rapidly, forming a scratch-free surface after 3-6 seconds at 500 mW/cm2, 5-10 seconds at 300 mW/cm2, and 60 seconds at 50-100 mW/cm2 on white paper using the VIP curing light system The DP-20-5 compound also had good compressive strength (51 +/-9 MPa as determined using the Instron test system described in the previous Example). It also exhibits a relatively lower viscosity (410cps at 22 °C) than AC-40. This composition is attractive for use as a protective coating under and around orthodontic application on enamel, or as a margin sealant where rapid curing and flowablity are important considerations Example 14: Preparation of non-volatile, NOIL composition filled DP20-5 [0041] Compositions of 10% filler, 20% filler, 30% filler, and 40% filler, and 90%, 80%, 70%
and 60% DP-20-5 were made by mixing the appropriate weight amount of filler with the DP20-5 composition described in Example 13 above. The filler used was OX-50 or silanated OX-50.
The sample containing 20% OX-50 filled DP20-5 was scratch free after irradiation for 5 seconds at 300 mW/cm2 or for 2 seconds at 500 mW/cm2. The pencil hardness was > SH.
These results are similar to those obtained with the neat resin lacking filler. The filler had no noticeable effect on the curability of the resin.
Example 15: Preparation of non-volatile, NOIL composition DP60-5 [0042] A composition containing 15g DP60, 4.Sg SR349, 4.Sg SR459, 3g CN383, 0.9g CD9052, 2.1 g TPO, and 1 Smg MEHQ was prepared. The composition cured to a scratch-free surface in 15 seconds at 500 mW/cma and 20 seconds at 300 mW/cm2 exposure using the VIP
light gun and after coating the composition on Pyramid shade 3.5 composite. This composition can be used as a flexible coating on dental prosthetic devices, or on dentures. The composition can also be used as a narrow gap filler, where flexibility is desirable.
Example 16: Preparation of non-volatile NOIL compositions AC-25 containing pentaacrylate and AC-26 [0043] A pentaacrylate and two diacrylate composition containing 3g SR 399, 3g SR349, 3g SR610, 0.3g CD9052, 0.7g TPO, and Smg MEHQ was prepared (AC-25). A similar composition containing a hexaacrylate and two diacrylates was prepared by combining 3g CN975, 3g SR349, 3g SR610, 0.3g CD9052, 0.7g TPO, and Smg MEHQ (AC-26). Both compositions AC-25 and AC-26 were scratch free after irradiation at 300 mW/cm2 for 20 seconds, or 500 mW/cm2 for 10 seconds. The pencil hardness of both materials was 1H.
Example 17: Evaluation of di-, tri-, and tetra-acrylates in preparation of NOIL surfaces [0044] Five resins were selected to compare the ability of diacrylates, triacrylates, and tetraacrylates to prepare NOIL surfaces. Monomer resins were solubilized in acetone at a l:l ratio by weight. TPO initiator was added, and the acetone was allowed to evaporate in air for about 60 seconds or more. After 20 seconds evaporation, the acetone was not detectable in terms of weight loss. The compositions were irradiated using either a blue light at 500 mW/cm2 or a bright white light at 200 mW/cm2. The produced surfaces were evaluated as described in the following Table.
Monomer (# TPO Irradiation time and Coating surface intensity acrylates/molecule)weight SR-355 (4) 5.6 120 sec., 500 mW/cm2 Marrable 120 sec., 200 mW/cm2 Almost scratch free SR-355 (4) 7 120 seconds, 500 mW/cm2Scratchable 60 sec., 200 mW/cm2 Scratch free SR-351 (3) 6 100 seconds, 500 mW/cm2Scratch free 40 sec., 200 mW/cm2 Scratch free SR-502 (3) 6 120 seconds, 500 mW/cm2Scratch free 60 sec., 200 mW/cm2 Scratch free SR-350 (3) 8 120 seconds, 500 mW/cm2Thick OIL
120 sec., 200 mW/cm2 Thick OIL
SR-259 (2) 10 120 seconds, 500 mW/cm2Slightly tacky, thin OIL
[0045] As used in this table, "Scratch free" also indicates that the surface was mar free and tack free; "Mar free" also indicates that the surface was tack free but was scratchable. The actual concentration of the TPO is double that shown in the table due to the evaporation of the acetone solvent. Resins made from tri-acrylates or tetra-acrylates could be polymerized to prepare a surface lacking an oxygen inhibition layer. The triacrylate and diacrylate tested under these conditions were not able to produce an acceptable surface.
Example 18: Scratch resistance assay of non-volatile NOIL sealants [0046] The suitability of NOIL sealants as orthodontic sealants was evaluated using a scratch resistance assay. A surface is rubbed using pencils containing graphite of different hardnesses in an attempt to scratch the surface. The surface is evaluated by what hardness of graphite is required to create a detectable scratch.
[0047] This assay is based on ASTM D 3383-00. The sealant was brushed onto a composite disc, and was cured. The pencils were obtained from a Kimberly Graphite Drawing Kit, and had hardnesses according to the following table.
II Softest Hardest II
[0048] The assay further distinguishes between gouges and scratches.
Scratching refers to the hardness needed to indent the surface. Gouging refers to the hardness required to scrape the adhesive from the surface. Oxygen inhibition layers often are easier to scratch than the rest of the cured adhesive, so the scratch/gouge assay is useful to detect the presence of an air inhibition layer on a surface.
[0049] The following adhesive compositions were evaluated: (DP20-5, DP-20-5 with a fluorescing agent (DP-20-SF), DP-20-5 with a fluorescing agent and 20% glass ionomer (DP-20-5-FG), Bisco One Step Adhesive System, Filled L/C Sealant, and L/C Sealant.
The adhesive compositions were brushed on composite disks made from Bisco Renew Shade A2 Translucent and cured for 2, 5, 10, 20 30, and 40 seconds using the VIP curing light system before evaluating. The first value in the table is for gouging, the second value is for scratching.
Product 2 sec 5 sec 10 sec 20 sec 30 sec 40 sec DP-20-5 >SH / >SH / >SH / >SH l >SH / >SH /
>SH >SH >SH >SH >SH >SH
DP-20-SF >SH / >SH / >SH / >SH / >SH / >SH l >SH >SH >SH >SH >SH >SH
DP-20- >SH / >SH / >SH / >SH / >SH / >SH /
SFG >SH >SH >SH >SH >SH >SH
One Step <8B / >SH / >SH / >SH / >SH / >SH /
<8B <8B <8B <8B <8B <8B
Filled <8B / <8B / >SH / >SH / >SH l >SH /
L/C <8B <8B <8B <8B <8B <8B
Sealant L/C <8B / HB / <8B SH / <8B >SH / >SH / >SH /
<8B <8B <8B <8B
Sealant [0050] Conventional adhesives had significant oxygen inhibition at the surface since the softest pencil used (8B) was able to scratch it. The NOIL DP-20-5 compositions did not have oxygen inhibition layers since even the hardest pencil used (SH) had difficulty scratching the surface.
The addition of a fluorescing agent and glass ionomer filler did not detrimentally affect the hardness of the DP-20-5 compositions. These NOIL compositions light cured very quickly, as evidenced by their consistent assay results across the range of time periods tested.
Example 19: Evaluation of photoinitiators for the preparation of a NOIL
surface [0051] Six photoinitiators were individually added to a common resin containing SOg CN-795 (hexafunctional acrylate), SOg acetone (volatile solvent), O.lg Flourad FC-431 (surfactant for leveling), and 0.02g MEHQ (inhibitor for storage). The following Table lists the initiators.
Initiator Chemical name Absorbance x 10-3 Lucirin TPO (TPO) 2,4,6-trimethylbenzoyl-6 diphenylphosphinate Lucirin TPO-L (TPOL) ethyl-2,4,6- 4 trimethylbenzoyl-phenylphosphinate Irgacure 819 (819) bis(2,4,6-trimethylbenzoyl)-23 phenylphosphineoxide Camphorquinone (CQ) camphorquinone 11 H-Nu 470 (HNu) 5,7-diiodo-3-butoxy-6-2960 fluorone PAQ phenanthrenequinone 466 [0052] The absorptivity is the absorbance in the range of 400-500 nm in acetonitrile normalized by mass. The higher the value, the higher the absorption in the visible light range. The first three initiators undergo unimolecular bond cleavage upon irradiation. The last three initiators require a co-initiator, such as an amine, to undergo a bimolecular reaction.
The initiators (and EDMAB amine if required) were added to the resin. Samples were coated on a white mixing pad, evaporated for greater than 60 seconds, and irradiated at 500 mWlcm2 using a Bisco VIP
light curing system. Samples were irradiated for 5 seconds, 10 seconds, 30 seconds, and 10 seconds in the absence of air. The "no air" cure was performed between two Mylar slips, each 0.25mm thick. The actual concentration of initiator in the resin was double that shown in the table due to the evaporation of the acetone. The surface was evaluated for percent degree of conversion as indicated in the following table.
DC, InitiatorInitiator,EDMAB % 5 sec 10 sec 30 sec 10 sec (no % air) 819 1.5 0 44 47 47 57 HNu 0.2 1 0 0 0 23 PAQ 0.2 1 0 0 0 33 [0053] To confirm the observation that the presence of air leads to lower DC
values, triplicate samples of resin containing TPO at 3% were irradiated in the presence and absence of air.
Average DC values, and the standard deviation were determined as shown in the following Table.
Irradiation time Air DC (std. dev.) seconds Present 46.9% (3.0%) 30 seconds Present 51.6% (4.3%) 10 seconds Absent 57.4% (1.3%) [0054] Resins were prepared and coated on composite disks. After evaporation of the acetone for greater than 60 seconds, the coatings were irradiated for 30 seconds at 300 mW/cma bright light. The pencil hardness was measured, as shown in the following Table. All surfaces were found to be tack and fingernail scratch free.
InitiatorInitiator,EDMAB % Pencil hardness %
CQ 3 3 > SH
819 1.5 0 4H
819 3 0 > SH
[0055] These results show that initiators other than phosphine oxide, such as camphorquinone, can be used to successfully prepare a NOIL surface.
Example 20: Ortho Shear Bond Stren_ h assay [0056] DP-20-5 NOIL compositions and L/C Bonding resins were evaluated for their shear strength. NOIL DP20-5 was prepared with and without 0.75 Lumilux Blue (a fluorescent additive) and 20% glass ionomer (X1B44RWG). Bond strength was compared against unfilled and filled L/C Bonding resins.
[0057] Human tooth enamel was etched with 37% phosphoric acid semi-gel for 15 seconds. The etchant was washed away with a jet of water, and dried thoroughly with a stream of air. One coat of the aforementioned compositions was applied as a sealant over the etched area by brushing onto the etched enamel surface, and was light cured for 10 seconds at 500 mW/cm2 intensity using the Bisco VIP curing light system. An orthodontic bracket was bonded to the sealed area using bracket adhesive (Lightbond or Phase II) and cured. Bonded samples were placed in a 37 °C deionized water bath for two hours before testing.
The shear test results are shown in the following table.
Bracket LlC Sealant Filled L/C Unfilled Filled DP-20-5 adhesive Sealant DP-20-5 with Flourescer Lightbond 22.85 2.0 23.04 6.4 23.08 1.7 20.96 1.3 MPa MPa MPa MPa Phase II 23.23 5.7 25.02 5.9 20.27 2.8 21.12 1.8 MPa MPa MPa MPa [0058] Bond strengths of the tested samples were fairly similar. These results indicate that unfilled and filled NOIL compositions display shear bond strength values suitable for use in orthodontic applications.
Example 21: Fluoride release assay [0059] The fluoride release properties of NOIL compositions were compared against L/C
sealants. The NOIL sample was DP20-5 containing 20% glass ionomer for fluoride release and 0.75% Lumilux blue for phosphorescence.
[0060] Shade disks of DP-20-5 and LC Sealant were prepared as follows. A round stainless steel mold held between polyethylene sheets and glass slabs were used to prepare discs of a fixed size.
The discs were cured using two light guns set at 500 ~ 50 mW/cm2. A single light gun was positioned over the center of the disc, and irradiated the disc for 20 seconds. Next, the two light guns were positioned at opposing ends of the circle (across the diameter), and irradiated the disc for 10 seconds. The two light guns were moved around the circle to irradiate the disc for a total of four times of 10 seconds (position of the two light guns around the circular discs: 0 and 180 degrees, then 90 and 270 degrees, then 135 and 315 degrees, and finally 45 and 225 degrees), in addition to the 20 second irradiation in the center). The top glass plate was removed, and the curing process repeated. The specimen was heated at 37 ~ 3 °C for 15 ~
1 minutes. A diamond burr was used to drill a hole near the edge of the disks. The disk was sonicated in acetone to remove any air inhibited layer that may be present. The diameter and height of the disk was measured with a caliper, and the mass of the disk was determined using an analytical balance. A
wire was threaded through the hole and twisted/turned such that the disk can be propped upright within a vial. An aqueous solution of sodium chloride (0.2M, 10 ml) was added to each vial, the vials were capped, and placed at 37 °C for 1 hour. Fluoride release was determined using a fluoride sensitive electrode immersed in a 50/50 TISAB/sample mixture. Three tests of each sample were performed. The results are shown in the following table.
Sample Fluoride release (~,g/cma) L/C Sealant test #1 0.178 L/C Sealant test #2 0.172 L/C Sealant test #3 0.153 DP-20-Stest #1 0.286 DP-20-Stest #2 0.262 DP-20-Stest #3 0.280 [0061] These results show that the NOIL sealants such as DP-20-5 with fluoride glass can release significantly more fluoride than the conventional L/C sealant. NOIL
sealants can therefore be used in applications where fluoride release is desirable or required.
Example 22: Use of NOIL as a top surface over a composite [0062] A composite can be placed appropriately in a dental restoration procedure according to the manufacturer's instructions. The final layer of composite is placed and adapted to the cavosurface margin, shaped, and contoured to the desired final form. A thin coating of a NOIL
composition such as AC-40 or DP-20-5 is gently applied using a soft brush over the surface of the composite and the surrounding enamel. The NOIL-coated surface is then light cured using an appropriate light source and time of irradiation (e.g. visible blue light from a VIP light gun at 600 mW/sec2 for 20-40 seconds or less). The produced surface will have a smooth, glossy surface. Further, such surface can be obtained without the need for shaping the composite with burs or abrasives as required in conventional composite applications, thereby avoiding potential damage to surrounding tooth tissue structure while also further minimizing patient time in the treatment room.
Example 23: Use of NOIL over a low viscosity composite [0063] A low viscosity or flowable composite can be placed appropriately in a dental restoration procedure. The final layer of composite is placed and adapted to the cavosurface margin, shaped, and contoured to the desired final form. The composite is light cured for a short period of time such as 5 seconds to eliminate flow of the composite material. A thin coating of NOIL
(such as DP-20-5) is gently applied using a soft brush over the surface of the composite and the surrounding enamel. The surface is then light cured using an appropriate light source and time of irradiation (e.g. visible blue light at 600 mW/sec2). The produced surface will have a smooth, glossy surface.
Example 24: Use of NOIL as a root surface coatin [0064] A root surface requiring desensitization can be isolated, and scrubbed with a pumice and cavity cleanser slurry using a cotton pellet, foam pellet, or microbrush. The root surface can additionally be etched with phosphoric acid for 15 seconds if desired. A thin coating of NOIL
(such as DP-20-5) or a filled sample for non-slumping purposes is gently applied using a soft brush over the root surface. The NOIL surface is thinned with a gentle stream of air, and light cured using an appropriate light source and time of irradiation (e.g. for 10 seconds with visible blue light at 600 mW/sec2 using the VIP curing light system) Example 25: Use of NOIL on Dental Annliances [0065] Shear bond strength (SBS) of NOIL formulas AC-40 and DP20-5 were tested and compared to that of Fortify Plus. The following substrates were tested:
enamel, dentin, composite, uncured composite, Rex III, porcelain, amalgam, acrylic, and Itself. The following techniques were used.
[0066] Enamel -- Enamel was pumiced, rinsed and dried. Enamel was etched with 37%
phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cm~. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0067] Dentin -- Dentin was polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Dentin was etched for 15 seconds using 32% phosphoric acid semi-gel. Dentin was rinsed and kept moist. 5-7 coats of All Bond 2 Primer A&B mixture were applied to moist dentin. Primed surface was lightly air-dried. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds at 500 mW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0068] Amalgam and RexIII -- Amalgam and Rex III were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cm2.
Post was bonded and sheared after being stored in 37 °C water for two hours.
[0069] Composite and Acrylic -- Composite and acrylic were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. Surface was etched with 32% phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20s, 20s and Ss respectively at 500 mWlcm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0070] Porcelain -- Porcelain was polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. The surface was microetched using the Accuprep to achieve a uniform surface.
The surface was etched with 4% hydrofluoric acid semi gel for 4 minutes, rinsed and dried.
Generous amounts of porcelain primer was applied to the surface and allowed to air-dry. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cma. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0071 ] Uncured composite -- A preparation was done in acrylic using a high speed handpiece and burr. The preparation was etched with Accuprep and 32% phosphoric acid semi-gel. Etched surface was treated with One Step according to manufacturers instructions.
Renew A2 Translucent was filled into the preparation. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 40s at 500 mW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0072] Itself - Substrates of cured Fortify Plus, AC-40 and DP20-5 were set into acrylic.
Composite and acrylic were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. Surface was etched with 32% phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied to their respective substrates and light cured for 20 seconds, 20 seconds and 5 seconds respectively at SOOmW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0073] The results of the shear bond strength (SBS) assays are shown in the following table, where numerical values are in MPa. A #5 gel cap (bonding area 0.1684 cm2) was used in each of the foregoing tests along with an Instron (Model 4466) shear bond machine set to a crosshead speed of Smm/min, and the shear bond strength (SBS) was calculated in MPa by dividing the peak load by bonding area. The mean and standard deviations were calculated for five replications (N=5) for each test.
Substrate DP20-5 AC-40 Fortify +
Dentin 13.81 2.9 19.122.7 14.829.5 Enamel 21.58 4.4 25.51 3.3 24.25 3.1 Acrylic 11.81 4.5 17.62 2.0 12.82 1.8 RexIII 12.631.2 17.800.1 11.411.9 Amalgam 11.84 1.4 14.98 2.3 11.47 1.9 Itself 9.21 3.2 14.97 3.7 18.28 3.3 Composite 17.37 3.1 15.35 7.7 16.83 4.7 Porcelain 17.72 1.7 17.58 3.2 14.50 1.2 Uncured composite16.74 3.1 13.69 3.0 22.13 7.5 [0074] In general, DP20-5 and AC-40 performed as well or better than Fortify +, within experimental error.
[0075] The location of failure has been of particular interest in comparing the performance of dental products. Sample sets consisted of 5 specimens. Most failures occurred in the substrate (SUB) or at the interface of the substrate and sealant (S/S). There are a few occasions where it appears that there was failure at the sealant layer (SEAL). There is one case in which there appears to be a failure at the sealant and post interface (S/P). These observations are summarized in the following table.
Substrate DP20-5 AC-40 Fortify +
Dentin 1 SEAL;4S/S 2SUB;2S/S;1 SEAL1 SUB;4S/S
Enamel 1SUB;4S/S 2SUB;3S/S 3SUB;2S/S
Acrylic 3S/S;2SEAL 4S/S;1SEAL SS/S
Rex III SS/S SS/S SS/S
Amalgam SSIS 3SUB;2S/S 1SUB;4S/S
Itself 4SUB;1 S/S 4SUB;1 S/S 5 SUB
Composite 5 SUB 5 SUB 5 SUB
Porcelain SSUB SSUB SSUB
Uncured composite5 SUB 3 SUB; l S/S; 5 SUB
l S/P
Example 26: Use of NOIL in fingernail or toenail repair applications [0076] DP-20-5 was tested as a fingernail repair composition as follows. A
thin layer of DP20-5 was coated on a human fingernail with brushing until a smooth surface was obtained. The composition was exposed to 500 mW/cm2 light intensity using VIP curing light system for about seconds. The composition cured into a smooth shiny surface that was hard to the touch.
[0077] All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure.
While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the ant that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention.
Examples: Preparation of unfilled resin compositions [0029] A mixture of multifunctional-acrylate, diluents, TPO or other initiator, and optionally MEHQ are blended together. The mixture may be heated at 60 °C - 62 °C for four hours with stirring or shaking to afford a clear or hazy solution. The haziness, if any, will fade over a few days.
Example 6: Preparation of filled resin compositions [0030] Unfilled resin and filler such as OX 50 are combined as a slurry. The slurry is ground for 30 minutes. The grinding process often introduces air bubbles into the mixture. The bubbles can be removed by centrifugation at >1000 x g for 30 minutes to afford an essentially clear solution.
Example 7: Monomers for use in "No Oxygen Inhibited Layer" (MOIL) compositions [0031 ] Multifunctional acrylates and acrylated diluent co-monomers have been found to be effective ingredients in NOIL compositions. The following table lists exemplary compounds that have been found to be useful.
Trade name Chemical descriptionCharacteristics Multifunctional Acrylates CN 975 Hexafunctional axomaticFast curing, high urethane acrylate hardness I~ayarad DPCA20 (DP20)Acrylate of caprolactoneFast curing, lower modified dipentaerythritolviscosity I~ayarad DPCA60 (DP60)Acrylate of caprolactoneFast curing, flexibility modified dipentaerythritol Acrylated Co-Monomers SR 344 Polyethylene glycol Hydrophobicity, hardness diacrylate SR 349 Ethoxylated bisphenolHydrophobicity, hardness A
diacrylate esters SR 610 Polyethylene glycol Low viscosity, flexibility (600) diacrylate SR 459 Caprolactone acrylateFlexibility, hydrophobicity CN 383 Monofunctional acrylatedVery low viscosity, amine polymerizing rate promoter CD 9052 Trifunctional acid Adhesion promoter ester Example 8: Preparation of volatile MMA compositions containing a tetrafunctional acrd AC-23 and -33 [0032] A composition containing 3g SR355 (ditrimethylolpropane tetraacrylate), 2g MMA
volatile co-monomer, 0.25g TPO, and 3.Smg MEHQ was prepared ("AC-23"). The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). The composition was coated on white paper and exposed to VIP light source set at 600 mW/cm2 intensity for an exposure time of 30 seconds. An oxygen inhibition layer was detected by finger touch, which revealed a soft surface even after waiting 10 minutes after exposure to the light source. These results suggest that a tetrafunctional acrylate in the presence of a volatile co-monomer MMA was insufficient to prevent formation of an oxygen inhibition layer.
[0033] An additional composition containing lg CN975, 4g SR355 (ditrimethylolpropane tetraacrylate), 0.35g TPO, and 2.Smg MEHQ was prepared ("AC-33"). The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). This composition could not be cured tack-free in less than 60 seconds exposure to the VIP light gun set at 600 mW/cm2, and was easily scratchable even after exposure to that intensity light for 60 seconds.
Example 9: Preparation of a volatile MMA composition containin~i a pentafunctional acrylate [0034] A composition containing 3g SR399 (dipentaerythritol pentaacrylate esters), 2g MMA
volatile co-monomer, 0.25g TPO, and 3.Smg MEHQ was prepared. The composition had the characteristic strong odor of a composition containing methyl methacrylate (MMA). The composition was coated on Pyramid composite, shade 3.5 (Bisco, Inc.) and cured by exposure to the VIP light gun output for 10 seconds at 300 mW/cm2. No oxygen inhibition layer was detected by finger touch, suggesting that a pentafunctional acrylate in the presence of a volatile co-monomer MMA is sufficient to prevent formation of an oxygen inhibition layer.
Example 10: Preparation of non-volatile NOIL compositions AC-15C and filled and colored AC-[0035] A composition containing 2.7g CN975, 3.3g SR344, 0.333g TPO, and 3mg MEHQ was prepared ("AC-15C"). A filled mixture of 75% AC-15C and 25% OX50 filler by weight was also prepared. The AC-15C compositions contain a hexafunctional diacrylate (CN
975) and no MMA. No MMA odor or other appreciable odor was detected. AC-15C exhibited better light curing sensitivity than Extoral, with twice the double-bond conversion rate.
AC-15 was curable scratch-free and mar free after 20 seconds exposure to 500 mW/cm2 light source using VIP, or 40 seconds at 200 mW/cm2 using the same curing light source. Addition of 10%
methyl blue colorant in ethanol did not adversely affect the curing. The conversion rate of AC-15C in air and in a nitrogen environment was the same, indicating that it lacked an OIL
layer. The Barcol hardness of AC-15C was 77 after curing 40 seconds at 200 mW/cm2 exposure using the Cure-Lite Plus light box system.
Example 11: Preparation of non-volatile, NOIL composition AC-35 [0036] A composition containing 3.22g CN975, 1.38g CN383, 0.4g TPO, and 2.Smg MEHQ
was prepared. AC-35 formed a scratch-free to human fingernail and tack-free surface to touch after 10 seconds cured at 300 mW/cm2 on Pyramid shade 3.5 composite using the VIP system.
AC-36, prepared containing the same amounts of TPO and MEHQ but 2.76g CN 975 and 1.848 CN 383, was curable scratch-free to fingernail scratching and tack-free to touch using the same composite base and light cure system after 20 seconds exposure at 300 mW/cm2.
Example 12: Preparation of non-volatile NOIL compositions AC-40 and AC-40A
[0037] A composition containing 8.9g CN975, 10.3g SR349, 7.8g SR610, 0.9g CD9052, 2.1g TPO, and l5mg MEHQ was prepared. The composition cured into a scratch-free surface after 20 seconds exposure on Pyramid shade 3.5 composite using the VIP curing system set at 500 mW/cm2. The AC-40 composition also exhibited good stability after storage under water at 60 °C, curing in 20 seconds at 300 mW/cm2 on Pyramid composite shade 3.5 after 30 days and 47 days, the latter being comparable to storage for 472 days at 20 °C.
Addition of 5% CN 383 to the composition (AC-40A) caused a scratch-free surface to form after curing at 300 mW/cm2 for 15-20 seconds, or 10 seconds at 500 mW/cma exposure on Pyramid composite using the VIP
curing light system. In addition to sealing applications, this composition may also be attractive as a deep cavity filler due to its relatively high viscosity (around 1200 cps at 22 °C).
[0038] AC-40 also exhibits good compressive strength of about 282MPa +/- 27 MPa.
Compressive strength is determined by preparing a sample in a 6mm high by 4rrun diameter stainless steel split mold. The sample is cured at 500 ~ 50 mW/cm2 for 60 seconds per side. The disc is heated at 37 °C for 15 minutes. The disc is placed in a 30 ml Nalgene bottle filled with deionized water, and heated for 23 hours at 37 °C. The disc is removed, blotted dry, and cooled to room temperature for one hour. An Instron Universal Testing Instrument (model 4465) is used to determine the load reading (kg) at which the sample breaks. The compressive strength is calculated as (load reading (kg) x 0.0624) / sample diameter (cm).
[0039] AC-40 passed a cytotoxicity assay performed with mouse fibroblast cells on a solid agarose surface. Toxicity, or the lack thereof, was determined by measuring the zone of lysis (if any) around the test sample after incubation at 37 °C in 5% carbon dioxide for 24 hours.
Example 13: Preparation of a non-volatile NOIL composition DP20-5 [0040] A composition containing 5.2g DP20, l.Sg CN383, 2.1g SR610, O.Sg CD9052, 0.7g TPO, and 4.4mg MEHQ was prepared. The composition cured very rapidly, forming a scratch-free surface after 3-6 seconds at 500 mW/cm2, 5-10 seconds at 300 mW/cm2, and 60 seconds at 50-100 mW/cm2 on white paper using the VIP curing light system The DP-20-5 compound also had good compressive strength (51 +/-9 MPa as determined using the Instron test system described in the previous Example). It also exhibits a relatively lower viscosity (410cps at 22 °C) than AC-40. This composition is attractive for use as a protective coating under and around orthodontic application on enamel, or as a margin sealant where rapid curing and flowablity are important considerations Example 14: Preparation of non-volatile, NOIL composition filled DP20-5 [0041] Compositions of 10% filler, 20% filler, 30% filler, and 40% filler, and 90%, 80%, 70%
and 60% DP-20-5 were made by mixing the appropriate weight amount of filler with the DP20-5 composition described in Example 13 above. The filler used was OX-50 or silanated OX-50.
The sample containing 20% OX-50 filled DP20-5 was scratch free after irradiation for 5 seconds at 300 mW/cm2 or for 2 seconds at 500 mW/cm2. The pencil hardness was > SH.
These results are similar to those obtained with the neat resin lacking filler. The filler had no noticeable effect on the curability of the resin.
Example 15: Preparation of non-volatile, NOIL composition DP60-5 [0042] A composition containing 15g DP60, 4.Sg SR349, 4.Sg SR459, 3g CN383, 0.9g CD9052, 2.1 g TPO, and 1 Smg MEHQ was prepared. The composition cured to a scratch-free surface in 15 seconds at 500 mW/cma and 20 seconds at 300 mW/cm2 exposure using the VIP
light gun and after coating the composition on Pyramid shade 3.5 composite. This composition can be used as a flexible coating on dental prosthetic devices, or on dentures. The composition can also be used as a narrow gap filler, where flexibility is desirable.
Example 16: Preparation of non-volatile NOIL compositions AC-25 containing pentaacrylate and AC-26 [0043] A pentaacrylate and two diacrylate composition containing 3g SR 399, 3g SR349, 3g SR610, 0.3g CD9052, 0.7g TPO, and Smg MEHQ was prepared (AC-25). A similar composition containing a hexaacrylate and two diacrylates was prepared by combining 3g CN975, 3g SR349, 3g SR610, 0.3g CD9052, 0.7g TPO, and Smg MEHQ (AC-26). Both compositions AC-25 and AC-26 were scratch free after irradiation at 300 mW/cm2 for 20 seconds, or 500 mW/cm2 for 10 seconds. The pencil hardness of both materials was 1H.
Example 17: Evaluation of di-, tri-, and tetra-acrylates in preparation of NOIL surfaces [0044] Five resins were selected to compare the ability of diacrylates, triacrylates, and tetraacrylates to prepare NOIL surfaces. Monomer resins were solubilized in acetone at a l:l ratio by weight. TPO initiator was added, and the acetone was allowed to evaporate in air for about 60 seconds or more. After 20 seconds evaporation, the acetone was not detectable in terms of weight loss. The compositions were irradiated using either a blue light at 500 mW/cm2 or a bright white light at 200 mW/cm2. The produced surfaces were evaluated as described in the following Table.
Monomer (# TPO Irradiation time and Coating surface intensity acrylates/molecule)weight SR-355 (4) 5.6 120 sec., 500 mW/cm2 Marrable 120 sec., 200 mW/cm2 Almost scratch free SR-355 (4) 7 120 seconds, 500 mW/cm2Scratchable 60 sec., 200 mW/cm2 Scratch free SR-351 (3) 6 100 seconds, 500 mW/cm2Scratch free 40 sec., 200 mW/cm2 Scratch free SR-502 (3) 6 120 seconds, 500 mW/cm2Scratch free 60 sec., 200 mW/cm2 Scratch free SR-350 (3) 8 120 seconds, 500 mW/cm2Thick OIL
120 sec., 200 mW/cm2 Thick OIL
SR-259 (2) 10 120 seconds, 500 mW/cm2Slightly tacky, thin OIL
[0045] As used in this table, "Scratch free" also indicates that the surface was mar free and tack free; "Mar free" also indicates that the surface was tack free but was scratchable. The actual concentration of the TPO is double that shown in the table due to the evaporation of the acetone solvent. Resins made from tri-acrylates or tetra-acrylates could be polymerized to prepare a surface lacking an oxygen inhibition layer. The triacrylate and diacrylate tested under these conditions were not able to produce an acceptable surface.
Example 18: Scratch resistance assay of non-volatile NOIL sealants [0046] The suitability of NOIL sealants as orthodontic sealants was evaluated using a scratch resistance assay. A surface is rubbed using pencils containing graphite of different hardnesses in an attempt to scratch the surface. The surface is evaluated by what hardness of graphite is required to create a detectable scratch.
[0047] This assay is based on ASTM D 3383-00. The sealant was brushed onto a composite disc, and was cured. The pencils were obtained from a Kimberly Graphite Drawing Kit, and had hardnesses according to the following table.
II Softest Hardest II
[0048] The assay further distinguishes between gouges and scratches.
Scratching refers to the hardness needed to indent the surface. Gouging refers to the hardness required to scrape the adhesive from the surface. Oxygen inhibition layers often are easier to scratch than the rest of the cured adhesive, so the scratch/gouge assay is useful to detect the presence of an air inhibition layer on a surface.
[0049] The following adhesive compositions were evaluated: (DP20-5, DP-20-5 with a fluorescing agent (DP-20-SF), DP-20-5 with a fluorescing agent and 20% glass ionomer (DP-20-5-FG), Bisco One Step Adhesive System, Filled L/C Sealant, and L/C Sealant.
The adhesive compositions were brushed on composite disks made from Bisco Renew Shade A2 Translucent and cured for 2, 5, 10, 20 30, and 40 seconds using the VIP curing light system before evaluating. The first value in the table is for gouging, the second value is for scratching.
Product 2 sec 5 sec 10 sec 20 sec 30 sec 40 sec DP-20-5 >SH / >SH / >SH / >SH l >SH / >SH /
>SH >SH >SH >SH >SH >SH
DP-20-SF >SH / >SH / >SH / >SH / >SH / >SH l >SH >SH >SH >SH >SH >SH
DP-20- >SH / >SH / >SH / >SH / >SH / >SH /
SFG >SH >SH >SH >SH >SH >SH
One Step <8B / >SH / >SH / >SH / >SH / >SH /
<8B <8B <8B <8B <8B <8B
Filled <8B / <8B / >SH / >SH / >SH l >SH /
L/C <8B <8B <8B <8B <8B <8B
Sealant L/C <8B / HB / <8B SH / <8B >SH / >SH / >SH /
<8B <8B <8B <8B
Sealant [0050] Conventional adhesives had significant oxygen inhibition at the surface since the softest pencil used (8B) was able to scratch it. The NOIL DP-20-5 compositions did not have oxygen inhibition layers since even the hardest pencil used (SH) had difficulty scratching the surface.
The addition of a fluorescing agent and glass ionomer filler did not detrimentally affect the hardness of the DP-20-5 compositions. These NOIL compositions light cured very quickly, as evidenced by their consistent assay results across the range of time periods tested.
Example 19: Evaluation of photoinitiators for the preparation of a NOIL
surface [0051] Six photoinitiators were individually added to a common resin containing SOg CN-795 (hexafunctional acrylate), SOg acetone (volatile solvent), O.lg Flourad FC-431 (surfactant for leveling), and 0.02g MEHQ (inhibitor for storage). The following Table lists the initiators.
Initiator Chemical name Absorbance x 10-3 Lucirin TPO (TPO) 2,4,6-trimethylbenzoyl-6 diphenylphosphinate Lucirin TPO-L (TPOL) ethyl-2,4,6- 4 trimethylbenzoyl-phenylphosphinate Irgacure 819 (819) bis(2,4,6-trimethylbenzoyl)-23 phenylphosphineoxide Camphorquinone (CQ) camphorquinone 11 H-Nu 470 (HNu) 5,7-diiodo-3-butoxy-6-2960 fluorone PAQ phenanthrenequinone 466 [0052] The absorptivity is the absorbance in the range of 400-500 nm in acetonitrile normalized by mass. The higher the value, the higher the absorption in the visible light range. The first three initiators undergo unimolecular bond cleavage upon irradiation. The last three initiators require a co-initiator, such as an amine, to undergo a bimolecular reaction.
The initiators (and EDMAB amine if required) were added to the resin. Samples were coated on a white mixing pad, evaporated for greater than 60 seconds, and irradiated at 500 mWlcm2 using a Bisco VIP
light curing system. Samples were irradiated for 5 seconds, 10 seconds, 30 seconds, and 10 seconds in the absence of air. The "no air" cure was performed between two Mylar slips, each 0.25mm thick. The actual concentration of initiator in the resin was double that shown in the table due to the evaporation of the acetone. The surface was evaluated for percent degree of conversion as indicated in the following table.
DC, InitiatorInitiator,EDMAB % 5 sec 10 sec 30 sec 10 sec (no % air) 819 1.5 0 44 47 47 57 HNu 0.2 1 0 0 0 23 PAQ 0.2 1 0 0 0 33 [0053] To confirm the observation that the presence of air leads to lower DC
values, triplicate samples of resin containing TPO at 3% were irradiated in the presence and absence of air.
Average DC values, and the standard deviation were determined as shown in the following Table.
Irradiation time Air DC (std. dev.) seconds Present 46.9% (3.0%) 30 seconds Present 51.6% (4.3%) 10 seconds Absent 57.4% (1.3%) [0054] Resins were prepared and coated on composite disks. After evaporation of the acetone for greater than 60 seconds, the coatings were irradiated for 30 seconds at 300 mW/cma bright light. The pencil hardness was measured, as shown in the following Table. All surfaces were found to be tack and fingernail scratch free.
InitiatorInitiator,EDMAB % Pencil hardness %
CQ 3 3 > SH
819 1.5 0 4H
819 3 0 > SH
[0055] These results show that initiators other than phosphine oxide, such as camphorquinone, can be used to successfully prepare a NOIL surface.
Example 20: Ortho Shear Bond Stren_ h assay [0056] DP-20-5 NOIL compositions and L/C Bonding resins were evaluated for their shear strength. NOIL DP20-5 was prepared with and without 0.75 Lumilux Blue (a fluorescent additive) and 20% glass ionomer (X1B44RWG). Bond strength was compared against unfilled and filled L/C Bonding resins.
[0057] Human tooth enamel was etched with 37% phosphoric acid semi-gel for 15 seconds. The etchant was washed away with a jet of water, and dried thoroughly with a stream of air. One coat of the aforementioned compositions was applied as a sealant over the etched area by brushing onto the etched enamel surface, and was light cured for 10 seconds at 500 mW/cm2 intensity using the Bisco VIP curing light system. An orthodontic bracket was bonded to the sealed area using bracket adhesive (Lightbond or Phase II) and cured. Bonded samples were placed in a 37 °C deionized water bath for two hours before testing.
The shear test results are shown in the following table.
Bracket LlC Sealant Filled L/C Unfilled Filled DP-20-5 adhesive Sealant DP-20-5 with Flourescer Lightbond 22.85 2.0 23.04 6.4 23.08 1.7 20.96 1.3 MPa MPa MPa MPa Phase II 23.23 5.7 25.02 5.9 20.27 2.8 21.12 1.8 MPa MPa MPa MPa [0058] Bond strengths of the tested samples were fairly similar. These results indicate that unfilled and filled NOIL compositions display shear bond strength values suitable for use in orthodontic applications.
Example 21: Fluoride release assay [0059] The fluoride release properties of NOIL compositions were compared against L/C
sealants. The NOIL sample was DP20-5 containing 20% glass ionomer for fluoride release and 0.75% Lumilux blue for phosphorescence.
[0060] Shade disks of DP-20-5 and LC Sealant were prepared as follows. A round stainless steel mold held between polyethylene sheets and glass slabs were used to prepare discs of a fixed size.
The discs were cured using two light guns set at 500 ~ 50 mW/cm2. A single light gun was positioned over the center of the disc, and irradiated the disc for 20 seconds. Next, the two light guns were positioned at opposing ends of the circle (across the diameter), and irradiated the disc for 10 seconds. The two light guns were moved around the circle to irradiate the disc for a total of four times of 10 seconds (position of the two light guns around the circular discs: 0 and 180 degrees, then 90 and 270 degrees, then 135 and 315 degrees, and finally 45 and 225 degrees), in addition to the 20 second irradiation in the center). The top glass plate was removed, and the curing process repeated. The specimen was heated at 37 ~ 3 °C for 15 ~
1 minutes. A diamond burr was used to drill a hole near the edge of the disks. The disk was sonicated in acetone to remove any air inhibited layer that may be present. The diameter and height of the disk was measured with a caliper, and the mass of the disk was determined using an analytical balance. A
wire was threaded through the hole and twisted/turned such that the disk can be propped upright within a vial. An aqueous solution of sodium chloride (0.2M, 10 ml) was added to each vial, the vials were capped, and placed at 37 °C for 1 hour. Fluoride release was determined using a fluoride sensitive electrode immersed in a 50/50 TISAB/sample mixture. Three tests of each sample were performed. The results are shown in the following table.
Sample Fluoride release (~,g/cma) L/C Sealant test #1 0.178 L/C Sealant test #2 0.172 L/C Sealant test #3 0.153 DP-20-Stest #1 0.286 DP-20-Stest #2 0.262 DP-20-Stest #3 0.280 [0061] These results show that the NOIL sealants such as DP-20-5 with fluoride glass can release significantly more fluoride than the conventional L/C sealant. NOIL
sealants can therefore be used in applications where fluoride release is desirable or required.
Example 22: Use of NOIL as a top surface over a composite [0062] A composite can be placed appropriately in a dental restoration procedure according to the manufacturer's instructions. The final layer of composite is placed and adapted to the cavosurface margin, shaped, and contoured to the desired final form. A thin coating of a NOIL
composition such as AC-40 or DP-20-5 is gently applied using a soft brush over the surface of the composite and the surrounding enamel. The NOIL-coated surface is then light cured using an appropriate light source and time of irradiation (e.g. visible blue light from a VIP light gun at 600 mW/sec2 for 20-40 seconds or less). The produced surface will have a smooth, glossy surface. Further, such surface can be obtained without the need for shaping the composite with burs or abrasives as required in conventional composite applications, thereby avoiding potential damage to surrounding tooth tissue structure while also further minimizing patient time in the treatment room.
Example 23: Use of NOIL over a low viscosity composite [0063] A low viscosity or flowable composite can be placed appropriately in a dental restoration procedure. The final layer of composite is placed and adapted to the cavosurface margin, shaped, and contoured to the desired final form. The composite is light cured for a short period of time such as 5 seconds to eliminate flow of the composite material. A thin coating of NOIL
(such as DP-20-5) is gently applied using a soft brush over the surface of the composite and the surrounding enamel. The surface is then light cured using an appropriate light source and time of irradiation (e.g. visible blue light at 600 mW/sec2). The produced surface will have a smooth, glossy surface.
Example 24: Use of NOIL as a root surface coatin [0064] A root surface requiring desensitization can be isolated, and scrubbed with a pumice and cavity cleanser slurry using a cotton pellet, foam pellet, or microbrush. The root surface can additionally be etched with phosphoric acid for 15 seconds if desired. A thin coating of NOIL
(such as DP-20-5) or a filled sample for non-slumping purposes is gently applied using a soft brush over the root surface. The NOIL surface is thinned with a gentle stream of air, and light cured using an appropriate light source and time of irradiation (e.g. for 10 seconds with visible blue light at 600 mW/sec2 using the VIP curing light system) Example 25: Use of NOIL on Dental Annliances [0065] Shear bond strength (SBS) of NOIL formulas AC-40 and DP20-5 were tested and compared to that of Fortify Plus. The following substrates were tested:
enamel, dentin, composite, uncured composite, Rex III, porcelain, amalgam, acrylic, and Itself. The following techniques were used.
[0066] Enamel -- Enamel was pumiced, rinsed and dried. Enamel was etched with 37%
phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cm~. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0067] Dentin -- Dentin was polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Dentin was etched for 15 seconds using 32% phosphoric acid semi-gel. Dentin was rinsed and kept moist. 5-7 coats of All Bond 2 Primer A&B mixture were applied to moist dentin. Primed surface was lightly air-dried. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds at 500 mW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0068] Amalgam and RexIII -- Amalgam and Rex III were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cm2.
Post was bonded and sheared after being stored in 37 °C water for two hours.
[0069] Composite and Acrylic -- Composite and acrylic were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. Surface was etched with 32% phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20s, 20s and Ss respectively at 500 mWlcm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0070] Porcelain -- Porcelain was polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. The surface was microetched using the Accuprep to achieve a uniform surface.
The surface was etched with 4% hydrofluoric acid semi gel for 4 minutes, rinsed and dried.
Generous amounts of porcelain primer was applied to the surface and allowed to air-dry. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 20 seconds, 20 seconds and 5 seconds respectively at 500 mW/cma. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0071 ] Uncured composite -- A preparation was done in acrylic using a high speed handpiece and burr. The preparation was etched with Accuprep and 32% phosphoric acid semi-gel. Etched surface was treated with One Step according to manufacturers instructions.
Renew A2 Translucent was filled into the preparation. One coat of Fortify Plus, AC-40 or DP20-5 was applied and light cured for 40s at 500 mW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0072] Itself - Substrates of cured Fortify Plus, AC-40 and DP20-5 were set into acrylic.
Composite and acrylic were polished on moistened 600 grit sanding paper for 30 seconds, rinsed and dried. Surface was microetched using the Accuprep to achieve a uniform surface. Surface was etched with 32% phosphoric acid semi-gel for 15 seconds before rinsing and drying. One coat of Fortify Plus, AC-40 or DP20-5 was applied to their respective substrates and light cured for 20 seconds, 20 seconds and 5 seconds respectively at SOOmW/cm2. Post was bonded and sheared after being stored in 37 °C water for two hours.
[0073] The results of the shear bond strength (SBS) assays are shown in the following table, where numerical values are in MPa. A #5 gel cap (bonding area 0.1684 cm2) was used in each of the foregoing tests along with an Instron (Model 4466) shear bond machine set to a crosshead speed of Smm/min, and the shear bond strength (SBS) was calculated in MPa by dividing the peak load by bonding area. The mean and standard deviations were calculated for five replications (N=5) for each test.
Substrate DP20-5 AC-40 Fortify +
Dentin 13.81 2.9 19.122.7 14.829.5 Enamel 21.58 4.4 25.51 3.3 24.25 3.1 Acrylic 11.81 4.5 17.62 2.0 12.82 1.8 RexIII 12.631.2 17.800.1 11.411.9 Amalgam 11.84 1.4 14.98 2.3 11.47 1.9 Itself 9.21 3.2 14.97 3.7 18.28 3.3 Composite 17.37 3.1 15.35 7.7 16.83 4.7 Porcelain 17.72 1.7 17.58 3.2 14.50 1.2 Uncured composite16.74 3.1 13.69 3.0 22.13 7.5 [0074] In general, DP20-5 and AC-40 performed as well or better than Fortify +, within experimental error.
[0075] The location of failure has been of particular interest in comparing the performance of dental products. Sample sets consisted of 5 specimens. Most failures occurred in the substrate (SUB) or at the interface of the substrate and sealant (S/S). There are a few occasions where it appears that there was failure at the sealant layer (SEAL). There is one case in which there appears to be a failure at the sealant and post interface (S/P). These observations are summarized in the following table.
Substrate DP20-5 AC-40 Fortify +
Dentin 1 SEAL;4S/S 2SUB;2S/S;1 SEAL1 SUB;4S/S
Enamel 1SUB;4S/S 2SUB;3S/S 3SUB;2S/S
Acrylic 3S/S;2SEAL 4S/S;1SEAL SS/S
Rex III SS/S SS/S SS/S
Amalgam SSIS 3SUB;2S/S 1SUB;4S/S
Itself 4SUB;1 S/S 4SUB;1 S/S 5 SUB
Composite 5 SUB 5 SUB 5 SUB
Porcelain SSUB SSUB SSUB
Uncured composite5 SUB 3 SUB; l S/S; 5 SUB
l S/P
Example 26: Use of NOIL in fingernail or toenail repair applications [0076] DP-20-5 was tested as a fingernail repair composition as follows. A
thin layer of DP20-5 was coated on a human fingernail with brushing until a smooth surface was obtained. The composition was exposed to 500 mW/cm2 light intensity using VIP curing light system for about seconds. The composition cured into a smooth shiny surface that was hard to the touch.
[0077] All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure.
While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the ant that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention.
Claims (45)
1. A dental composition comprising a multiacrylate compound and an initiator, wherein:
the multiacrylate compound comprises at least three acrylate functionalities per molecule;
and the composition does not comprise methyl methacrylate.
the multiacrylate compound comprises at least three acrylate functionalities per molecule;
and the composition does not comprise methyl methacrylate.
2. The composition of claim 1, wherein the composition cures to form a surface lacking an oxygen inhibition layer.
3. The composition of claim 1, wherein the initiator is a photoinitiator.
4. The composition of claim 1, wherein the initiator is a phosphine oxide compound.
5. The composition of claim 1, wherein the initiator is 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO).
6. The composition of claim 1, wherein the initiator is present at a concentration of about 1 weight percent of the composition or less.
7. The composition of claim 1, wherein the initiator is present at a concentration of at least about 3 weight percent of the composition.
8. The composition of claim 1, wherein the initiator is present at a concentration of at least about 6 weight percent of the composition.
9. The composition of claim 1, wherein the initiator is present at a concentration of at least about 7 weight percent of the composition.
10. The composition of claim 1, wherein the multiacrylate compound comprises three acrylate functionalities per molecule.
11. The composition of claim 1, wherein the multiacrylate compound comprises four acrylate functionalities per molecule.
12. The composition of claim 1, wherein the multiacrylate compound comprises five acrylate functionalities per molecule.
13. The composition of claim 1, wherein the multiacrylate compound comprises six acrylate functionalities per molecule.
14. The composition of claim 1, wherein the multiacrylate compound is a hexafunctional aromatic urethane acrylate oligomer, a caprolactone modified dipentaerythritol hexaacrylate, or dipentaerythritol pentaacrylate.
15. The composition of claim 1, wherein the multiacrylate compound is present at a concentration of at least about 20 weight percent of the composition.
16. The composition of claim 1, wherein the multiacrylate compound is present at a concentration of at least about 30 weight percent of the composition.
17. The composition of claim 1, further comprising a co-monomer.
18. The composition of claim 1, further comprising a monoacrylate compound, diacrylate compound, a triacrylate compound, or a tetraacrylate compound.
19. The composition of claim 18, wherein the monoacrylate compound is caprolactone acrylate.
20. The composition of claim 18, wherein the diacrylate compound is tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, or polyethylene glycol diacrylate.
21. The composition of claim 18, wherein the triacrylate compound is trimethylolpropane triacrylate.
22. The composition of claim 18, wherein the tetraacrylate compound is ditrimethylolpropane tetraacrylate.
23. The composition of claim 1, further comprising a filler.
24. The composition of claim 1, further comprising a nanofiller.
25. The composition of claim 1, further comprising glass particles.
26. The composition of claim 1, further comprising an acrylated amine compound.
27. The composition of claim 1, further comprising a diluent.
28. The composition of claim 27, wherein the diluent is acetone, ethanol, water, a mixture of acetone and water, a mixture of ethanol and water, a mixture of ethanol and acetone, and a mixture of ethanol, water, and acetone.
29. A method of sealing a surface, the method comprising:
obtaining a surface;
applying to the surface a composition comprising a multiacrylate compound and an initiator;
and curing the composition to obtain a sealed surface, wherein:
the multiacrylate compound comprises at least three acrylate functionalities per molecule;
the composition does not comprise methyl methacrylate; and the sealed surface does not comprise an oxygen inhibition layer.
obtaining a surface;
applying to the surface a composition comprising a multiacrylate compound and an initiator;
and curing the composition to obtain a sealed surface, wherein:
the multiacrylate compound comprises at least three acrylate functionalities per molecule;
the composition does not comprise methyl methacrylate; and the sealed surface does not comprise an oxygen inhibition layer.
30. The method of claim 29, wherein the surface is a dental surface.
31. The method of claim 29, wherein the surface is a dental prosthesis.
32. The method of claim 29, wherein the surface is a tooth.
33. The method of claim 29, wherein the surface is an artificial tooth.
34. The method of claim 29, wherein the surface is a fingernail or toenail.
35. The method of claim 29, wherein the multiacrylate compound comprises three acrylate functionalities per molecule.
36. The method of claim 29, wherein the multiacrylate compound comprises four acrylate functionalities per molecule.
37. The method of claim 29, wherein the multiacrylate compound comprises five acrylate functionalities per molecule.
38. The method of claim 29, wherein the multiacrylate compound comprises six acrylate functionalities per molecule.
39. The method of claim 29, wherein the curing step comprises light curing.
40. The method of claim 29, wherein the curing step comprises light curing at a light intensity of about 100 mW/cm2 or less.
41. The method of claim 29, wherein the curing step comprises light curing at a light intensity of about 300 mW/cm2 or less.
42. The method of claim 29, wherein the curing step comprises light curing at a light intensity of about 500 mW/cm2 or less.
43. The method of claim 29, wherein the curing step comprises light curing at a light intensity of about 800 mW/cm2 or less.
44. The method of claim 29, wherein the curing step comprises light curing at a light intensity of about 2000 mW/cm2 or less.
45. The method of claim 29, wherein the curing step comprises light curing for less than about 15 seconds.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/026560 WO2004017928A1 (en) | 2002-08-21 | 2002-08-21 | Non-volatile dental compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2495934A1 true CA2495934A1 (en) | 2004-03-04 |
Family
ID=31945411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002495934A Abandoned CA2495934A1 (en) | 2002-08-21 | 2002-08-21 | Non-volatile dental compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1534211A1 (en) |
| JP (1) | JP4401959B2 (en) |
| CN (1) | CN1668269A (en) |
| AU (1) | AU2002331653B2 (en) |
| CA (1) | CA2495934A1 (en) |
| WO (1) | WO2004017928A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070100945A (en) * | 2005-02-10 | 2007-10-15 | 산메디카루 가부시키가이샤 | Dental restoration material composition |
| JP4773824B2 (en) * | 2005-03-18 | 2011-09-14 | 株式会社トクヤマ | Curable composition |
| DE602006010127D1 (en) | 2005-03-18 | 2009-12-17 | Tokuyama Corp | Curable composition |
| CA2621018C (en) * | 2005-09-02 | 2014-06-10 | Dentsply International Inc. | Dental compositions containing nanometer-sized silica particles for use as sealants |
| EP2548546A1 (en) | 2008-08-13 | 2013-01-23 | Ernst Mühlbauer GmbH & Co.KG | X-ray opaque infiltrant |
| EP2226061B2 (en) | 2009-03-06 | 2017-01-25 | Ernst Mühlbauer GmbH & Co.KG | Infiltrant for dental application |
| US8394464B2 (en) * | 2009-03-31 | 2013-03-12 | Schlumberger Technology Corporation | Lining of wellbore tubing |
| ES2738010T3 (en) * | 2012-06-04 | 2020-01-17 | Oreal | Fast curing cosmetic compositions for surface curing free from sticking of polymerizable resins radically with UV LED |
| ES2671909B1 (en) * | 2016-12-09 | 2019-04-10 | Bardina Manuel Enrique Toral | False nail |
| CN109044879A (en) * | 2018-06-28 | 2018-12-21 | 吉林省登泰克牙科材料有限公司 | A kind of manicure composition and preparation method thereof |
| WO2021070875A1 (en) | 2019-10-08 | 2021-04-15 | クラレノリタケデンタル株式会社 | Dental composition |
| US20230363982A1 (en) * | 2020-09-18 | 2023-11-16 | Mitsui Chemicals, Inc. | Dental coating composition |
| US20230381066A1 (en) | 2020-10-28 | 2023-11-30 | Kuraray Noritake Dental Inc. | Dental curable composition having good color compatibility |
| US20240074946A1 (en) | 2020-12-25 | 2024-03-07 | Kuraray Noritake Dental Inc. | Dental composition |
| WO2022138973A1 (en) | 2020-12-25 | 2022-06-30 | クラレノリタケデンタル株式会社 | Dental composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR852068B (en) * | 1984-08-30 | 1985-12-24 | Johnson & Johnson Dental Prod | |
| JPH0655654B2 (en) * | 1987-07-21 | 1994-07-27 | 株式会社クラレ | Photocurable crown material and crown forming method using the same |
| JPH09143021A (en) * | 1995-11-17 | 1997-06-03 | Kuraray Co Ltd | Photopolymerizable composition for dental purpose |
| JP4198237B2 (en) * | 1998-08-20 | 2008-12-17 | 株式会社クラレ | Antibacterial dental adhesive system |
| AU763355B2 (en) * | 1998-08-20 | 2003-07-17 | Kuraray Co., Ltd. | Bonding compositions for dental use |
| US6849670B2 (en) * | 2000-07-19 | 2005-02-01 | Tokuyama Corporation | Photo-curable reparative material for dental use |
-
2002
- 2002-08-21 CN CNA028296613A patent/CN1668269A/en active Pending
- 2002-08-21 WO PCT/US2002/026560 patent/WO2004017928A1/en active Application Filing
- 2002-08-21 CA CA002495934A patent/CA2495934A1/en not_active Abandoned
- 2002-08-21 JP JP2004530739A patent/JP4401959B2/en not_active Expired - Fee Related
- 2002-08-21 EP EP02768631A patent/EP1534211A1/en not_active Withdrawn
- 2002-08-21 AU AU2002331653A patent/AU2002331653B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002331653B2 (en) | 2010-03-11 |
| JP2006510583A (en) | 2006-03-30 |
| AU2002331653A1 (en) | 2004-03-11 |
| WO2004017928A1 (en) | 2004-03-04 |
| CN1668269A (en) | 2005-09-14 |
| EP1534211A1 (en) | 2005-06-01 |
| JP4401959B2 (en) | 2010-01-20 |
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