WO2004017928A1 - Compositions dentaires non volatiles - Google Patents

Compositions dentaires non volatiles Download PDF

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Publication number
WO2004017928A1
WO2004017928A1 PCT/US2002/026560 US0226560W WO2004017928A1 WO 2004017928 A1 WO2004017928 A1 WO 2004017928A1 US 0226560 W US0226560 W US 0226560W WO 2004017928 A1 WO2004017928 A1 WO 2004017928A1
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Prior art keywords
composition
compound
multiacrylate
initiator
per molecule
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PCT/US2002/026560
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English (en)
Inventor
Byoung In Suh
Li Feng
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Bisco Inc
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Bisco Inc
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Priority to CA002495934A priority Critical patent/CA2495934A1/fr
Priority to PCT/US2002/026560 priority patent/WO2004017928A1/fr
Priority to CNA028296613A priority patent/CN1668269A/zh
Priority to AU2002331653A priority patent/AU2002331653B2/en
Priority to EP02768631A priority patent/EP1534211A1/fr
Priority to JP2004530739A priority patent/JP4401959B2/ja
Publication of WO2004017928A1 publication Critical patent/WO2004017928A1/fr
Anticipated expiration legal-status Critical
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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

Definitions

  • 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.
  • 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.
  • Dental compositions frequently contain monomers which are polymerized by the dentist or technician (e.g. by light, self-cure, or dual-cure).
  • many dental compositions form a problematic "oxygen inhibited layer” (OIL) or "uncured layer” on their surface.
  • OIL oxygen inhibited layer
  • This layer's polymerization is inhibited due to the presence of molecular oxygen radicals in ambient air.
  • 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.
  • 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/teclumbleans, making it difficult to use in a laboratory, and nearly impossible to use in a clinical setting.
  • Extoral' s odor is suggestive of the presence of methyl methacrylate.
  • Methyl methacrylate is a volatile compound used in several dental products.
  • 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.
  • 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.
  • 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.
  • One embodiment of the invention is a dental composition
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 compound(s) 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.
  • the composition can further include a volatile, non-reactive solvent.
  • solvents include acetone, ethanol and mixtures of acetone and water, ethanol and water and/or acetone, ethanol and water.
  • compositions can further comprise fillers, nanofillers, glass particles, or other dental materials.
  • fillers include Ox-50, silane-treated Ox-50, glass ionomer powder IXG 1944 RGW from Ferro, which is also a fluoride release agent.
  • 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.
  • 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.
  • the curing can generally be performed by any means sufficient to rapidly cure the composition to form a non-oxygen inhibited layer (NOIL).
  • 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/cm , less than about 100 mW/cm 2 , about 200 mW/cm 2 or less, about 300 mW/cm 2 or less, about 400 mW/cm 2 or less, about 500 mW/cm 2 or less, about 600 mW/cm 2 or less, about 800 mW/cm 2 or less, and about 2000 mW/cm or less, it being understood that higher light intensities can also be employed.
  • light intensities include about 50 mW/cm , about 100 mW/cm , about 150 mW/cm 2 , about 200 mW/cm 2 , about 250 mW/cm 2 , about 300 mW/cm 2 , about 350 mW/cm 2 , about 400 mW/cm 2 , about 450 mW/cm 2 , about 500 mW/cm 2 , about 600 mW/cm 2 ' about 800 mW/cm , and about 2000 mW/cm . Higher light intensities may also be used.
  • Bisco's NIPTM 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 ⁇ TLTM 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.
  • 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.
  • Example 1 Abbreviations used in the Examples
  • 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.
  • Extoral 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.
  • FTIR assays of pre- and post-evaporation Extoral revealed several transitions. A peak at 1620 cm " 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.
  • compositions were prepared using C ⁇ -975, a hexafunctional aromatic urethane acrylate, MMA, and other compounds. Numbers represent the amount of each compound in the composition by weight percent.
  • compositions AC-10 and AC-11 had sticky surfaces upon curing at 500 mW/cm 2 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-10A and AC- 11A enhanced the curability.
  • the surface conversion was 65.7% for AC-10A and 58.7% for AC-11 A.
  • 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
  • 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.
  • 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.
  • 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” (NOIL) compositions
  • 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.
  • Example 8 Preparation of volatile MMA compositions containing a tetrafunctional acrylate (AC-23 and -33)
  • a composition containing 3g SR355 (ditrimethylolpropane tetraacrylate), 2g MMA volatile co-monomer, 0.25g TPO, and 3.5mg 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/cm 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.
  • a composition containing 3g SR399 (dipentaerythritol pentaacrylate esters), 2g MMA volatile co-monomer, 0.25g TPO, and 3.5mg 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 NIP light gun output for 10 seconds at 300 mW/cm . 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- 15C
  • 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/cm 2 light source using NIP, or 40 seconds at 200 mW/cm using the same curing light source.
  • a composition containing 3.22g CN975, 1.38g CN383, 0.4g TPO, and 2.5mg 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/cm 2 on Pyramid shade 3.5 composite using the VIP system.
  • Example 12 Preparation of non- volatile NOIL compositions AC-40 and AC-40A
  • a composition containing 8.9g CN975, 10.3g SR349, 7.8g SR610, 0.9g CD9052, 2.1g TPO, and 15mg 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/cm 2 .
  • the AC-40 composition also exhibited good stability after storage under water at 60 °C, curing in 20 seconds at 300 mW/cm 2 on Pyramid composite shade 3.5 after 30 days and 47 days, the latter being comparable to storage for 472 days at 20 °C.
  • composition (AC-40 A) caused a scratch-free surface to form after curing at 300 mW/cm for 15-20 seconds, or 10 seconds at 500 mW/cm 2 exposure on Pyramid composite using the NIP curing light system.
  • this composition may also be attractive as a deep cavity filler due to its relatively high viscosity (around 1200 cps at 22 °C).
  • 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 4mm diameter stainless steel split mold. The sample is cured at 500 ⁇ 50 mW/cm 2 for 60 seconds per side. The disc is heated at 37 °C for 15 minutes. The disc is placed in a 30 ml ⁇ algene 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).
  • 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
  • a composition containing 5.2g DP20, 1.5g CN383, 2.1g SR610, 0.5g 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/cm 2 , 5-10 seconds at 300 mW/cm 2 , and 60 seconds at 50-100 mW/cm 2 on white paper using the NIP curing light system
  • the DP-20-5 compound also had good compressive strength (51 -+7-9 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
  • 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 9 at 300 mW/cm or for 2 seconds at 500 mW/cm .
  • the pencil hardness was > 5H.
  • Example 15 Preparation of non- volatile. NOIL composition DP60-5
  • a composition containing 15g DP60, 4.5g SR349, 4.5g SR459, 3g CN383, 0.9g CD9052, 2.1g TPO, and 15mg MEHQ was prepared.
  • the composition cured to a scratch-free surface in 15 seconds at 500 mW/cm 2 and 20 seconds at 300 mW/cm 2 exposure using the NIP 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
  • a pentaacrylate and two diacrylate composition containing 3g SR 399, 3g SR349, 3g SR610, 0.3g CD9052, 0.7g TPO, and 5mg 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 5mg MEHQ (AC-26). Both compositions AC-25 and AC-26 were scratch free after irradiation at 300 mW/cm 2 for 20 seconds, or 500 mW/cm 2 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
  • 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.
  • 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.
  • the following adhesive compositions were evaluated: (DP20-5, DP-20-5 with a fluorescing agent (DP-20-5F), 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 NIP curing light system before evaluating.
  • the first value in the table is for gouging, the second value is for scratching.
  • Example 19 Evaluation of photoinitiators for the preparation of a NOIL surface
  • 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 mW/cm 2 using a Bisco VIP light curing system.
  • 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/cm 2 bright light. The pencil hardness was measured, as shown in the following Table. All surfaces were found to be tack and fingernail scratch free.
  • 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.
  • 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.
  • 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/cm 2 . 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.
  • 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 atop surface over a composite
  • 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 NIP light gun at 600 mW/sec 2 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
  • 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/sec ).
  • the produced surface will have a smooth, glossy surface.
  • Example 24 Use of NOIL as a root surface coating
  • 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/sec using the VIP curing light system)
  • 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.
  • 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.
  • 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/cm 2 . Post was bonded and sheared after being stored in 37 °C water for two hours.
  • 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/cm . Post was bonded and sheared after being stored in 37 °C water for two hours.
  • 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 5s respectively at 500 mW/cm 2 . Post was bonded and sheared after being stored in 37 °C water for two hours.
  • 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/cm . Post was bonded and sheared after being stored in 37 °C water for two hours.
  • 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/cm . Post was bonded and sheared after being stored in 37 °C water for two hours.
  • SBS shear bond strength
  • Example 26 Use of NOIL in fingernail or toenail repair applications
  • 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/cm 2 light intensity using VIP curing light system for about 5 seconds. The composition cured into a smooth shiny surface that was hard to the touch.
  • 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 art 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.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des formulations de composites dentaires contenant un initiateur et un composé de multiacrylate. Les formulations sont exemptes de méthylmétacrylate, une substance volatile, irritante et potentiellement dangereuse que l'on trouve normalement dans les formulations dentaires. Le composé de multiacrylate possède au moins trois fonctionnalités d'acrylate par molécule. Les formulations durcissent de manière à former une surface sans couche d'inhibition d'oxygène. Les formulations peuvent être utilisées comme résines de scellement, revêtements dentaires et applications de réparation des ongles des mains et des pieds.
PCT/US2002/026560 2002-08-21 2002-08-21 Compositions dentaires non volatiles Ceased WO2004017928A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002495934A CA2495934A1 (fr) 2002-08-21 2002-08-21 Compositions dentaires non volatiles
PCT/US2002/026560 WO2004017928A1 (fr) 2002-08-21 2002-08-21 Compositions dentaires non volatiles
CNA028296613A CN1668269A (zh) 2002-08-21 2002-08-21 非挥发性牙科组合物
AU2002331653A AU2002331653B2 (en) 2002-08-21 2002-08-21 Non-volatile dental compositions
EP02768631A EP1534211A1 (fr) 2002-08-21 2002-08-21 Compositions dentaires non volatiles
JP2004530739A JP4401959B2 (ja) 2002-08-21 2002-08-21 不揮発性歯科組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2002/026560 WO2004017928A1 (fr) 2002-08-21 2002-08-21 Compositions dentaires non volatiles

Publications (1)

Publication Number Publication Date
WO2004017928A1 true WO2004017928A1 (fr) 2004-03-04

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JP (1) JP4401959B2 (fr)
CN (1) CN1668269A (fr)
AU (1) AU2002331653B2 (fr)
CA (1) CA2495934A1 (fr)
WO (1) WO2004017928A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006085682A1 (fr) * 2005-02-10 2006-08-17 Sun Medical Co., Ltd. Formule de matériau de réparation dentaire
EP1702605A1 (fr) * 2005-03-18 2006-09-20 Tokuyama Corporation Composition durcissable
WO2007028159A3 (fr) * 2005-09-02 2007-04-19 Dentsply Int Inc Compositions dentaires contenant des particules de l'ordre du nanometre utilisees comme resine de scellement
US8183305B2 (en) 2008-08-13 2012-05-22 Ernst Muhlbauer Gmbh & Co. Kg Radiopaque infiltrant
US8362172B2 (en) 2009-03-06 2013-01-29 Ernst Muhlbauer Gmbh & Co. Kg Infiltrant for dental application
EP2414623A4 (fr) * 2009-03-31 2013-09-04 Schlumberger Technology Bv Revetement d'une colonne de production de puits
ES2671909A1 (es) * 2016-12-09 2018-06-11 Manuel Enrique TORAL BARDINA Uña postiza
WO2022059702A1 (fr) * 2020-09-18 2022-03-24 Mitsui Chemicals, Inc. Composition de revêtement dentaire
US12564543B2 (en) 2019-10-08 2026-03-03 Kuraray Noritake Dental Inc. Dental composition

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Publication number Priority date Publication date Assignee Title
JP4773824B2 (ja) * 2005-03-18 2011-09-14 株式会社トクヤマ 硬化性組成物
CN110251422A (zh) * 2012-06-04 2019-09-20 欧莱雅 用于产生无粘性表面的快速固化化妆品组合物
CN109044879A (zh) * 2018-06-28 2018-12-21 吉林省登泰克牙科材料有限公司 一种美甲组合物及其制备方法
CA3196983A1 (fr) 2020-10-28 2022-05-05 Tatsuya Kajikawa Composition dentaire durcissable ayant une bonne compatibilite de couleur
JP7759897B2 (ja) 2020-12-25 2025-10-24 クラレノリタケデンタル株式会社 歯科用組成物
US20240091107A1 (en) 2020-12-25 2024-03-21 Kuraray Noritake Dental Inc. Dental composition
WO2023191112A1 (fr) 2022-04-01 2023-10-05 クラレノリタケデンタル株式会社 Composition dentaire durcissable présentant une compatibilité de couleur favorable

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EP0173567A2 (fr) * 1984-08-30 1986-03-05 JOHNSON & JOHNSON DENTAL PRODUCTS COMPANY Méthode de traitement de dents avec des compositions photopolymérisables contenant un acylphosphine oxyde comme catalyseur
EP0980682A1 (fr) * 1998-08-20 2000-02-23 Kuraray Co., Ltd. Compositions adhésives à usage dentaire
WO2002005752A1 (fr) * 2000-07-19 2002-01-24 Tokuyama Corporation Materiau photopolymerisable pour protheses dentaires

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JPH0655654B2 (ja) * 1987-07-21 1994-07-27 株式会社クラレ 光硬化性歯冠材料および該歯冠材料を用いる歯冠成形法
JPH09143021A (ja) * 1995-11-17 1997-06-03 Kuraray Co Ltd 歯科用光重合性組成物
JP4198237B2 (ja) * 1998-08-20 2008-12-17 株式会社クラレ 抗菌性歯科用接着剤システム

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EP0173567A2 (fr) * 1984-08-30 1986-03-05 JOHNSON & JOHNSON DENTAL PRODUCTS COMPANY Méthode de traitement de dents avec des compositions photopolymérisables contenant un acylphosphine oxyde comme catalyseur
EP0980682A1 (fr) * 1998-08-20 2000-02-23 Kuraray Co., Ltd. Compositions adhésives à usage dentaire
WO2002005752A1 (fr) * 2000-07-19 2002-01-24 Tokuyama Corporation Materiau photopolymerisable pour protheses dentaires
EP1236459A1 (fr) * 2000-07-19 2002-09-04 Tokuyama Corporation Materiau photopolymerisable pour protheses dentaires

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006085682A1 (fr) * 2005-02-10 2006-08-17 Sun Medical Co., Ltd. Formule de matériau de réparation dentaire
EP1702605A1 (fr) * 2005-03-18 2006-09-20 Tokuyama Corporation Composition durcissable
US7741381B2 (en) 2005-03-18 2010-06-22 Tokuyama Corporation Curable composition
WO2007028159A3 (fr) * 2005-09-02 2007-04-19 Dentsply Int Inc Compositions dentaires contenant des particules de l'ordre du nanometre utilisees comme resine de scellement
US8183305B2 (en) 2008-08-13 2012-05-22 Ernst Muhlbauer Gmbh & Co. Kg Radiopaque infiltrant
US8362172B2 (en) 2009-03-06 2013-01-29 Ernst Muhlbauer Gmbh & Co. Kg Infiltrant for dental application
US9211236B2 (en) 2009-03-06 2015-12-15 Muhlbauer Gmbh & Co. Kg Infiltrant for dental application
EP2414623A4 (fr) * 2009-03-31 2013-09-04 Schlumberger Technology Bv Revetement d'une colonne de production de puits
ES2671909A1 (es) * 2016-12-09 2018-06-11 Manuel Enrique TORAL BARDINA Uña postiza
WO2018104574A1 (fr) * 2016-12-09 2018-06-14 Toral Bardina Manuel Enrique Faux ongle et procédé pour le conformer sur un ongle naturel
US12564543B2 (en) 2019-10-08 2026-03-03 Kuraray Noritake Dental Inc. Dental composition
WO2022059702A1 (fr) * 2020-09-18 2022-03-24 Mitsui Chemicals, Inc. Composition de revêtement dentaire

Also Published As

Publication number Publication date
CA2495934A1 (fr) 2004-03-04
AU2002331653B2 (en) 2010-03-11
JP2006510583A (ja) 2006-03-30
CN1668269A (zh) 2005-09-14
JP4401959B2 (ja) 2010-01-20
AU2002331653A1 (en) 2004-03-11
EP1534211A1 (fr) 2005-06-01

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