KR100911843B1 - Non-volatile dental compositions - Google Patents

Abstract

Disclosed is a dental composite formulation containing an initiator and a polyacrylate compound. The formulation lacks methyl methacrylate, a volatile, irritating and potentially harmful substance commonly found in dental preparations. The polyacrylate compound has at least three acrylate functional groups per molecule. The formulation cures to form a surface lacking an oxygen inhibiting layer. The formulations can be used as dental sealants, as dental coatings, and in thornton / claw recovery applications.

Initiator, polyacrylate compound, dental complex preparation, oxygen inhibiting layer

Description

Non-Volatile Dental Compositions {NON-VOLATILE DENTAL COMPOSITIONS}

The present invention relates to dental composite materials, and more particularly to composite materials containing multifunctional acrylate compounds but lacking volatile compounds such as methyl methacrylate.

Dental sealants and adhesives are widely used in clinical settings. Preferred properties include safety, efficiency, durability and preferred cosmetic properties. Dental compositions are preferably storage stable, are easily formulated, and are not set too quickly because they are difficult to apply to a patient upon rapid setting.

Dental compositions often include monomers that are polymerized by a dentist or technician (eg, light, self-curing, or dual-curing). However, many dental compositions form problematic "oxygen inhibiting layers (OIL)" or "uncured layers" on the surface. Polymerization of this layer is inhibited due to the presence of molecular oxygen radicals in the atmosphere. As a result, incomplete polymerization occurs. These layers often make the surface sticky or sticky, making it difficult to mold or mold a dental composition. This incomplete polymerization lowers the hardness of the surface and / or prevents curing from occurring when thin surfaces are present.

Extoral is a visible-light curing dental resin formulation sold by AFR Imaging Corp. (Portland, Oregon). Extoral may be used for surface treatment or as denture resin. Extoral cures rapidly under ordinary dental light irradiation to form a shiny, hard surface. It is noteworthy that the ectoral does not have an "oxygen inhibiting layer" even when cured with low intensity light. One problem with the use of ectoral is its volatility, which results in a very strong odor. These odors are offensive to both the patient and the dentist / technician, making them difficult to use in the laboratory and rarely used in clinical settings. Another problem is that the surface produced by the ectoral is very brittle, and its use may be limited in certain dental applications such as compressive surfaces.

The odor of ectoral is presumed to be the presence of methyl methacrylate. Methyl methacrylate is a volatile compound used in many dental products. In addition to unpleasant odors, exposure to methyl methacrylate has been associated with various health concerns. Numbness, numbness, decreased lung function, and decreased respiratory function have been observed in dental technicians who have been clinically exposed to methyl methacrylate (Sadoh, DR et al., British Dental J. 186 (8): 380-381, 1999; Nishiwaki, Y. et al. , J. Occup. Health 43: 375-378, 2001). The US Environmental Protection Agency describes methyl methacrylate as an irritant for the nose and bronchus and points out that short-term exposure can cause headaches and fatigue (EPA 749-F-95-014 Fact Sheet, November 1994). .

Thus, it would be very valuable to develop dental compositions that do not contain a methyl acrylate or other volatile compounds that are irritating and potentially harmful to dentists, dental technicians and patients without having an "oxygen inhibiting layer".

Summary of the invention

One embodiment of the present invention relates to a dental acrylic composition containing a polyacrylate compound and an initiator. Curing of the composition results in a surface lacking an oxygen inhibiting layer (“OIL”). This formulation does not contain methyl methacrylate, an irritating and potentially harmful substance found in many dental formulations. The polyacrylate compound contains at least three acrylate units per molecule. This formulation may additionally include other acrylate compounds, solvents, fillers, nanofillers, diluents, or other materials useful in dental formulations. This formulation is useful for applications such as dental coatings, dental sealants, and fingernail / toenail recovery.

Detailed description of the invention

One embodiment of the invention relates to a dental acrylic material composition that cures to form a surface that lacks an oxygen inhibiting layer (“OIL”). This composition preferably does not contain methyl methacrylate. The composition preferably cures rapidly to form a stable, hard and shiny surface.

One embodiment of the invention is a dental composition comprising a polyacrylate compound and an initiator. Multiacrylate compounds are chemical compounds comprising at least three acrylate functional groups per molecule. This composition preferably does not contain methyl methacrylate. The composition preferably does not form an oxygen inhibiting layer upon curing.

Preferred initiators present are phosphine oxide photoinitiators and camphorquinones. Examples of such initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), TPO-L, Irgacure 819, Darocure 4265, and camphorquinone. It is anticipated that other initiators capable of photocleavage with or without the aid of an amine co-initiator will also have utility in accordance with the present invention. The initiator may generally be present at any concentration in the composition. The initiator is preferably present at a concentration such that it does not noticeably discolor the cured composition. Examples of concentration ranges for the initiator include, by the saturation level of the initiator in the composition, at least about 1% by weight or less of the composition, at least about 1% by weight of the composition, at least about 2% by weight of the composition, at least about 3% by weight of the composition, At least about 4% by weight of the composition, at least about 5% by weight of the composition, at least about 6% by weight of the composition, or at least about 7% by weight of the composition. Examples of initiator concentrations include about 3% by weight of the composition, about 6% by weight of the composition, and about 7% by weight of the composition up to the saturation level of the initiator in the composition. It is also expected to be provided at lower concentrations in the presence of volatile dental solvents, such as acetone, which provide a certain higher effective initiator concentration in the composition upon evaporation.

The polyacrylate compound can be any polyacrylate compound having at least three acrylate functional groups per molecule, relatively close to each other in space. Examples of such multiacrylate compounds include hexafunctional aromatic urethane acrylate oligomers, caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, di-trimethylolpropane tetraacrylate, trimethylolpropane tri Acrylates, and ethoxylated trimethylolpropane triacrylate. Other polyacrylate compounds containing three acrylate functional groups per molecule, relatively close to each other in space, compounds containing four acrylate functional groups per molecule, compounds containing five acrylate functional groups per molecule, 6 per molecule Compounds containing 7 acrylate functional groups per molecule, compounds containing 8 acrylate functional groups per molecule, compounds containing 9 acrylate functional groups per molecule, 10 acrylics per molecule It is expected that compounds comprising late functional groups will also have utility in accordance with the present invention. Larger numbers of oligoacrylates or polyacrylates may also be added to the composition.

The polyacrylate compound may generally be present in any concentration for the composition. Examples of concentration ranges include at least about 20% by weight of the composition and at least about 30% by weight of the composition. Specific concentration examples include about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, and about 95% by weight of the composition. % Is included.

The composition may further comprise a co-monomer. Co-monomers are preferably polymerized with polyacrylate compounds. The co-monomers can generally be any type of co-monomers, with nonvolatile acrylates having surface tensions that are comparable to or greater than the surface tensions of the selected multifunctional acrylate compound (s) present in the composition. Preferred co-monomers present include monoacrylate compounds, diacrylate compounds, triacrylate compounds, or tetraacrylate compounds. An example of a monoacrylate is caprolactone acrylate. Examples of diacrylate compounds are tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol diacrylate, epoxy diacrylate, urethane dimethacrylate, and urethane diacrylate. An example of a triacrylate compound is trimethylolpropane triacrylate. An example of tetraacrylate is ditrimethylolpropane tetraacrylate. Ethoxylated forms of these acrylates may be desirable due to their relatively high surface tension.

The composition may further comprise a volatile, nonreactive solvent. Examples of such solvents include acetone, ethanol, a mixture of acetone and water, a mixture of ethanol and water, and / or a mixture of acetone, ethanol and water.

The composition may 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 (which is Ferro, a fluoride release agent).

Additional embodiments of the invention relate to methods of using the aforementioned compositions. The sealing method of the surface comprises the steps of obtaining a surface; Applying a composition comprising a polyacrylate compound and an initiator to the surface; And curing the composition to obtain a sealed surface. The sealed surface preferably does not contain an oxygen inhibiting layer.

The surface may generally be any surface to be sealed, with dental surfaces, teeth, dental implants, artificial teeth, bones, nails or toenails being preferred. In addition, the surface may be the surface of an already applied dental composition, such as a dental composite.

Curing may generally be carried out by any means sufficient to rapidly cure the composition to form a non-oxygen inhibiting layer (NOIL). The curing step preferably includes photocuring. Photocuring may be performed at low or high light intensity. The brightness is preferably suitable for use in a dental laboratory or dental clinic. Examples of light intensity ranges include about 50 mW / cm ² or less, about 100 mW / cm ² or less, 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 ² or less, and higher brightness may be used. It should be understood. Specific examples of luminosity include about 50 mW / cm ² , about 100 mW / cm ² , 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 ² , and about 2000 mW / cm ² . Higher brightness may also be used. For example, the blue wavelength VIP ^TM Dentistry optical path for a light source used in the Visco Chemistry System (Bisco's VIP ^TM Dental Curing Light system) may be used by a dentist. Dental experiments, such as the Dentsply, Inc. generic-Pentron Cure-Lite Plus light box system or Triad light box system Practical photocuring systems can also be used in dental applications. NTL ^TM system of Visco using a light source without a nitrogen atmosphere (Bisco's NTL ^TM System) may also be used. The photocuring time may generally be any time. Preferred time ranges present include about 2 minutes or less, about 1 minute or less, about 30 seconds or less, about 20 seconds or less, about 15 seconds or less, about 10 seconds or less, and about 5 seconds or less. Specific examples of photocuring times include about 1 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 photocuring times are generally desirable for shortening the time to withstand the procedure and for the convenience of dental practitioners.

The following examples are included to describe preferred embodiments of the present invention. It should be understood by those skilled in the art that the techniques disclosed in the following description of techniques disclosed by the inventors may be deemed to function well in carrying out the invention and thus constitute a desirable manner in carrying out. However, one of ordinary skill in the art appreciates that various modifications may be made to the specific embodiments disclosed in light of the present disclosure, and similar results may be obtained without departing from the spirit and scope of the present invention.

Example 1 Abbreviations Used in Examples

The table below lists the chemical compounds and abbreviations used in the Examples section.

Abbreviation / Product Chemical name Where to buy BZ Benzophenone Startomer, Exton, Pennsylvania CQ Camphorquinone Aldrich Chemical CTXO 2-chlorothioxanthene-9-one Aldrich Chemical EDMAB Ethyl (4-dimethylamino) benzoate Esschem Company MEHQ Methylhydroquinone, polymerization inhibitor Aldrich Chemical MMA Methyl methacrylate Aldrich Chemical OX-50 Fumed silicon dioxide filler Degussa TMPTMA Trimethyllopropane Trimethacrylate Esschem Company TPO Lucirin TPO photoinitiator; 2,4,6-trimethylbenzoyldiphenylphosphine oxide BASF, Mount Olive, NJ UDMA Urethane Dimethacrylate Esschem CD 9052 Trifunctional Acid Ester Startomer, Exton, Pennsylvania CN 120 Epoxy diacrylate Startomer, Exton, Pennsylvania CN 383 Monofunctional acrylated amine initiator Startomer, Exton, Pennsylvania CN 975 Hexafunctional aromatic urethane acrylate oligomer Startomer, Exton, Pennsylvania CN 983 Urethane diacrylate Startomer, Exton, Pennsylvania Kayarad DPCA20 (DP20) Caprolactone Modified Dipentaerythritol Hexaacrylate Startomer, Exton, Pennsylvania Kayarad DPCA60 (DP60) Caprolactone Modified Dipentaerythritol Hexaacrylate Startomer, Exton, Pennsylvania SR 259 Polyethylene Glycol (200) Diacrylate Startomer, Exton, Pennsylvania SR 306 Tripropylene Glycol Diacrylate Startomer, Exton, Pennsylvania SR 344 Polyethylene Glycol 400 Diacrylate Startomer, Exton, Pennsylvania SR 349 Ethoxylated Bisphenol A Diacrylate Startomer, Exton, Pennsylvania SR 350 Trimethylolpropane trimethacrylate Startomer, Exton, Pennsylvania SR 351 Trimethylolpropane triacrylate Startomer, Exton, Pennsylvania SR 355 Ditrimethylolpropane tetraacrylate Startomer, Exton, Pennsylvania SR 399 Dipentaerythritol pentaacrylate Startomer, Exton, Pennsylvania SR 459 Caprolactone acrylate Startomer, Exton, Pennsylvania SR 495 Caprolactone acrylate Startomer, Exton, Pennsylvania SR 502 Ethoxylated Trimethylolpropane Triacrylate Startomer, Exton, Pennsylvania, USA SR 610 Polyethylene Glycol (600) Diacrylate Startomer, Exton, Pennsylvania

Example 2: Analysis of Extoral Compositions

Extoral is a commercial product and its composition and components are unknown. A strong unpleasant odor suggested that the ectoral contained methyl methacrylate. The following assays were performed as an attempt to measure the chemical composition of the ectoral.

The evaporation of the volatile component of the ectoral produced a viscous resin. About 40% by weight of the composition was evaporated. It is presumed to be mainly methyl methacrylate.

FTIR analysis of ectoral before and after evaporation shows several transitions. The peak at 1620 cm ⁻¹ becomes larger upon evaporation of methyl methacrylate. This peak is present in butyl acrylate but not in butyl methacrylate. Were combined peak during evaporation of aliphatic 2 moves from 1635.0 cm ^-1 to 1633.8 cm ^-1, which methacrylate- suggest that similar properties to the transition - more acrylate in similar properties. The FTIR spectrum of the ectoral does not suggest the presence of amines.

The UV / Visible spectrum comparing the ectoral and TPO standards confirms the TPO in the ectoral and makes it possible to estimate that the amount is about 4%.

Example 3: Addition of Hexafunctional Acrylate

Compositions were prepared using CN-975, hexafunctional aromatic urethane acrylate, MMA and other compounds. The numbers in the table indicate the amount by weight of each compound in the composition.

Compositions AC-10 and AC-11 have a tacky surface upon curing at 500 mW / cm ² for 5 seconds. FTIR shows that the surface conversion is 47.3% for AC-10 and 47.5% for AC-11, which is about 16% lower than ectoral (63.2%). High TPO concentrations of AC-10A and AC-11A increased the curability. Surface conversion was 65.7% for AC-10A and 58.7% for AC-11A.

The surface of the cured AC-11A is similar to the cured ectoral in terms of non-tackiness, smoothness, rigidity and gloss.

Example 4: Preparation of "No Oxygen Inhibitory Layer" (NOIL) Composition

The NOIL composition contains at least two components of a multifunctional acrylate and a photoinitiator (eg, phosphine oxide). Diluents (eg, ethoxylated di- or tri-acrylates) may also be added to increase the handleability of the polyacrylate and / or the solubility of the initiator. The composition may contain solvents, polymerizable co-monomers, initiators, surfactants, glass fillers, fluorescent or phosphorescent compounds, dyes, colorants, fluoride compounds and other materials used in the dental and orthodontic arts.

Example 5: Preparation of Unfilled Resin Composition

A mixture of multifunctional-acrylate, diluent, TPO or other initiator, and optionally MEHQ, is mixed together. The mixture can be heated at 60 ° C. to 62 ° C. for 4 hours with stirring or shaking to obtain a clear or opaque solution. If it is opaque it will disappear over several days.

Example 6: Preparation of Filled Resin Compositions

Unfilled resin and filler such as OX 50 are combined as a slurry. The slurry is ground for 30 minutes. The grinding process often generates bubbles in the mixture. The bubbles can be removed by centrifugation at> 1000 x g for 30 minutes to obtain an essentially clear solution.

Example 7: Monomers for Use in "No Oxygen Inhibitory Layer" (NOIL) Compositions

It has been found that multifunctional acrylates and acrylated diluent co-monomers are effective components of the NOIL composition. The table below lists exemplary compounds found to be useful.

Trade name Chemical description Property Multifunctional acrylate CN 975 Hexafunctional aromatic urethane acrylate Fast curing, high hardness Kayarad DPCA20 (DP20) Acrylate of caprolactone modified dipentaerythritol Fast curing, low viscosity Kayarad DPCA60 (DP60) Acrylate of caprolactone modified dipentaerythritol Fast curing, flexible Acrylated co-monomer SR 344 Polyethylene Glycol 400 Diacrylate Hydrophobicity, hardness SR 349 Ethoxylated Bisphenol A Diacrylate Ester Hydrophobicity, hardness SR 610 Polyethylene Glycol (600) Diacrylate Low viscosity, flexible SR 459 Caprolactone acrylate Flexible, hydrophobic CN 383 Monofunctional acrylated amines Very low viscosity, polymerization rate accelerator CD 9052 Trifunctional Acid Ester Adhesion promoter

Example 8: Preparation of Volatile MMA Compositions (AC-23 and -33) Containing Tetrafunctional Acrylate

A composition was prepared containing 3 g SR355 (ditrimethylolpropane tetraacrylate), 2 g MMA volatile co-monomer, 0.25 g TPO and 3.5 mg MEHQ ("AC-23"). The composition had a strong odor characteristic of the composition containing methyl methacrylate (MMA). The composition was coated on white paper and exposed to a set of 600 mW / cm ² VIP light sources for a 30 second exposure time. The oxygen inhibiting layer was detected by the touch of the hand, which revealed a smooth surface only after exposure to the light source and waiting 30 minutes. These results suggest that tetrafunctional acrylates are insufficient to prevent the formation of oxygen inhibiting layers in the presence of volatile co-monomer MMA.

Additional compositions were prepared containing 1 g CN975, 4 g SR355 (ditrimethylolpropane tetraacrylate), 0.35 g TPO and 2.5 mg MEHQ (“AC-33”). The composition had a strong odor characteristic of the composition containing methyl methacrylate (MMA). The composition could not be cured without a tack upon exposure to a set of 600 mW / cm ² VIP light guns for less than 60 seconds and was easily scratched after exposure at this brightness for 60 seconds.

Example 9 Preparation of Volatile MMA Composition (AC-24) Containing Pentafunctional Acrylate

A composition containing 3 g SR399 (dipentaerythritol pentaacrylate ester), 2 g MMA volatile co-monomer, 0.25 g TPO and 3.5 mg MEHQ was prepared. The composition had a strong odor characteristic of the composition containing methyl methacrylate (MMA). The composition was coated onto Pyramid composite, shade 3.5 (Bisco, Inc.) and exposed to VIP light gun power for 10 seconds at 300 mW / cm ² . No oxygen inhibiting layer was detected by the touch of the hand, suggesting that the pentafunctional acrylate is sufficient to prevent the formation of an oxygen inhibiting layer in the presence of volatile co-monomer MMA.

Example 10 Preparation of Non-Volatile NOIL Compositions AC-15C and Filled and Colored AC-15C

A composition was prepared containing 2.7 g CN975, 3.3 g SR344, 0.333 g TPO and 3 mg MEHQ ("AC-15C"). A filled mixture of 75 wt% AC-15C and 25 wt% OX50 filler was also prepared. The AC-15C composition contains hexafunctional diacrylate (CN 975) and no MMA. No MMA odor or other detectable odor was detected. AC-15C had twice the double bond conversion of exetoral and showed better photocuring sensitivity than estoral. AC-15 was curable without scratches and scratches after 20 minutes of exposure to a 500 mW / cm ² light source using VIP or 40 seconds to 200 mW / cm ² using the same curing light source. The addition of 10% methyl blue colorant in ethanol did not adversely affect curing. The conversion rates of AC-15C in air and nitrogen environments were the same, suggesting no OIL layer. The Barcol hardness of the AC-15C was 77 after curing at 200 mW / cm ² for 40 seconds using the Cure-Lite Plus light box system.

Example 11: Preparation of Nonvolatile NOIL Composition AC-35

A composition was prepared containing 3.22 g CN975, 1.38 g CN383, 0.4 g TPO and 2.5 mg MEHQ. After curing for 10 seconds at 300 mW / cm ² on a Pyramid shade 3.5 composite using a VIP system, the AC-35 formed a scratch-free surface when touched with human nails and a tacky surface when touched. AC-36, prepared with the same amount of TPO and MEHQ, 2.76 g CN975 and 1.84 g CN383, was scratched with nails after 20 seconds exposure at 300 mW / cm ² using the same composite substrate and photocuring system. It was free of scratches and hard to touch when touched.

Example 12 Preparation of Nonvolatile NOIL Compositions AC-40 and AC-40A

A composition was prepared containing 8.9 g CN975, 10.3 g SR349, 7.8 g SR610, 0.9 g CD9052, 2.1 g TPO and 15 mg MEHQ. The composition was cured to a scratch-free surface after 20 seconds exposure on the Pyramid Shade 3.5 composite using a set of 500 mW / cm ² VIP curing systems. The AC-40 composition was also stored in water at 60 ° C. after 30 and 47 days, and then showed good stability even after curing for 20 seconds at 300 mW / cm ² on a pyramid composite shade 3.5. The result after 47 days was 472 at 20 ° C. Comparable with storage for days. 5% of CN 383 was added to the composition (AC-40A), even after curing with exposure of 300 to 20 seconds at 300 mW / cm ² or 10 seconds at 500 mW / cm ² using a VIP cured light system. A scratch free surface was formed. Due to the relatively high viscosity (about 1200 cps at 22 ° C.), the composition may be attractive as a filler for serious cavities in addition to sealed products.

AC-40 also exhibits good compressive strength of about 282 MPa +/- 27 MPa. Compressive strength was measured by making a sample of 6 mm in height with a stainless steel split mold of 4 mm in diameter. 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 Nalgene bottle filled with deionized water and heated at 37 ° C. for 23 hours. Remove the disc, dry the bottle and allow to cool to room temperature for 1 hour. An Instron Universal Testing Instrument (Model 4465) is used to determine the load reading (kg) when the sample breaks. Calculate the compressive strength as [Load Reading (kg) × 0.0624) / Sample Diameter (cm)].

AC-40 was passed cytotoxicity assays performed using mouse fibroblasts on solid agarose surfaces. Toxicity or deficiency was determined by incubating for 24 hours in 37% C5 in carbon dioxide and then measuring the dissolution zone around the test sample (if present).

Example 13: Preparation of Nonvolatile NOIL Composition DP20-5

5.2 g DP20, 1.5 g CN383, 2.1 g SR610. A composition containing 0.5 g of CD9052, 0.7 g of TPO and 4.4 mg of MEHQ was prepared. The composition after 60 seconds exposure from VIP curing light using a system 3-6 seconds at 500 mW / cm ² on a blank, 300 mW / cm in ^25-10 seconds and 50~100 mW / cm ^2, a scratch-free surface Cured very quickly while forming. The DP-20-5 compound also had a good compressive strength (51 +/- 9 MPa as measured using the Instron test system described in the examples above). It also shows a relatively lower viscosity (410 cps at 22 ° C.) than AC-40. The composition is attractive as a protective coating on the underside and around the enameled orthodontic product, or as an edge sealer which considers rapid cure and flowability as important.

Example 14 Preparation of DP20-5 Filled with a Nonvolatile NOIL Composition

Appropriate weight fillers are mixed with the DP20-5 composition described in Example 13 above to provide 10% filler, 20% filler, 30% filler and 40% filler, and 90%, 80%, 70% and 60% DP-20. A composition of -5 was prepared. The filler used was OX-50 or silanized OX-50. Samples containing DP20-5 filled with 20% OX-50 were scratch-free after irradiation for 5 seconds at 300 mW / cm ² or for 2 seconds at 500 mW / cm ² . Pencil hardness was> 5H. These results are similar to those obtained with fillers without pure resin. The filler had no noticeable effect on the curability of the resin.

Example 15 Preparation of Nonvolatile NOIL Composition DP60-5

A composition containing 15 g DP60, 4.5 g SR349, 4.5 g SR459, 3 g CN383, 0.9 g CD9052, 2.1 g TPO and 15 mg MEHQ was prepared. After coating the composition on the Pyramid Shade 3.5 composite, the composition was cured to a scratch-free surface for 15 seconds at 500 mW / cm ² and 20 seconds at 300 mW / cm ² using a VIP light gun. This composition can also be used for flexible coating or dentition of dental prosthetic devices. The composition can also be used as a narrow gap filler where flexibility is required.

Example 16: Preparation of Nonvolatile NOIL Composition AC-25 Containing Pentaacrylate and AC-26

1 pentaacrylate and 2 diacrylate compositions were prepared containing 3 g SR399, 3 g SR349, 3 g SR610, 0.3 g CD9052, 0.79 g TPO and 5 mg MEHQ (AC-25). . Similar compositions containing 1 hexaacrylate and 2 diacrylate were prepared by combining 3 g CN975, 3 g SR349, 3 g SR610, 0.3 g CD9052, 0.7 g TPO and 5 mg MEHQ ( AC-26). Both compositions AC-25 and AC-26 were scratch-free after irradiation for 20 seconds at 300 mW / cm ² or for 10 seconds at 500 mW / cm ² . The pencil strength of both materials was 1H.

Example 17 Evaluation of Di-, Tri- and Tetra-acrylates in NOIL Surface Preparation

Five resins were selected to compare the NOIL surface manufacturability of diacrylates, triacrylates and tetraacrylates. The monomer resin was dissolved in acetone in a 1: 1 weight ratio. TPO initiator was added and acetone was evaporated in air for about 60 seconds or longer. After 20 seconds of evaporation, acetone had no weight loss detected. The composition was irradiated with blue light of 500 mW / cm ² or bright white light of 200 mW / cm ² . The resulting surface was evaluated as described in the table below.

Monomer (# acrylate / molecule) TPO weight% Survey time and intensity Coated surface SR-355 (4) 5.6 120 seconds, 500 mW / cm ² 120 seconds, 200 mW / cm ² Scratches Almost no scratch SR-355 (4) 7 120 sec, 500 mW / cm ² 60 sec, 200 mW / cm ² No scratches No scratches SR-351 (3) 6 100 sec, 500 mW / cm ² 40 sec, 200 mW / cm ² No scratch no scratch SR-502 (3) 6 120 sec, 500 mW / cm ² 60 sec, 200 mW / cm ² No scratch no scratch SR-350 (3) 8 120 seconds, 500 mW / cm ² 120 seconds, 200 mW / cm ² Thick OIL Thick OIL SR-259 (2) 10 120 sec, 500 mW / cm ² Slightly sticky, thin oil

As used in this table, "no scratching" also means no scratches and tacks on the surface; "No scratch" also means no tack on the surface but scratches. Due to evaporation of the acetone solvent, the actual concentration of TPO is twice that shown in the table. Resins made of tri-acrylate or tetra-acrylate can be polymerized to produce a surface free of oxygen inhibiting layers. Triacrylates and diacrylates tested under these conditions could not produce acceptable surfaces.

Example 18 Scratch Resistance Analysis of Nonvolatile NOIL Sealants

The suitability of the NOIL sealant as orthodontic sealant was evaluated using a scratch resistance analysis. In an attempt to scratch the surface, the surface was rubbed with a pencil containing graphite of different hardness. The surface was evaluated according to how much hardness of graphite was required to produce a detectable scratch.

This analysis is based on ASTM D 3383-00. The sealant was cured by rubbing the composite disc. The pencil was manufactured by Kimberly Graphite Drawing Kit, and had a hardness according to the following table.

This analysis further distinguishes between gouges and scratches. Scratching means the hardness required to indent the surface. Gauge means the hardness required to scrape off the adhesive from the surface. Oxygen inhibiting layers are often easier to scratch than the rest of the cured adhesive, so scratch / gauze analysis is useful for detecting the presence of air inhibiting layers on the surface.

The following adhesive compositions were evaluated: DP20-5, DP-20-5 with fluorescent agent (DP-20-5F), DP-20 with fluorescent agent and 20% glass ionomer (DP-20-5-FG) -5, Visco 1st stage adhesion system, filled L / C sealant, and L / C sealant. The adhesive composition was rubbed onto a composite disk made of Bisco Renew Shade A2 Translucent and cured for 2, 5, 10, 20, 30 and 40 seconds using a VIP cured light system prior to evaluation. The first value in the table below is for gouges and the second value is for scratches.

Since the softest pencil 8B used could scratch the surface, conventional adhesives have a high oxygen inhibition on the surface. Since even the hardest pencils (5H) used were difficult to scratch the surface, the NOIL DP-20-5 composition did not have an oxygen inhibiting layer. The addition of fluorescent and free ionomer fillers did not adversely affect the hardness of the DP-20-5 composition. As evidenced by consistent analytical results over the tested period range, these NOIL compositions photocured very quickly.

Example 19 Evaluation of Photoinitiators for NOIL Surface Preparation

Six photoinitiators were prepared with 50 g of CN-795 (hexafunctional acrylate), 50 g of acetone (volatile solvent), 0.1 g of Flourad FC-431 (surfactant for leveling) and 0.02 g of MEHQ ( Each to a conventional resin containing a storage initiator). The table below lists the initiators.

Initiator Chemical name Absorbance × 10 ^-3 Lucirin TPO (TPO) 2,4,6-trimethylbenzoyl-diphenylphosphinate 6 Lucirin TPO-L (TPOL) Ethyl-2,4,6-trimethylbenzoyl-phenylphosphinate 4 Irgacure 819 (819) Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide 23 Camphorquinone (CQ) Camphorquinone 11 H-Nu 470 (HNu) 5,7-dido-3-butoxy-6-fluoron 2960 PAQ Phenanthrenequinone 466

Absorption is the absorbance in the range of 400-500 mm in acetonitrile, normalized by mass. The higher the value, the higher the absorption in the visible range. The first three initiators undergo monomolecular bond removal upon irradiation. The other three initiators require a public initiator such as an amine, which undergoes a bimolecular reaction. An initiator (and EDMAB amine if necessary) was added to the resin. Samples were coated on white mixing pads and evaporated for at least 60 seconds and then irradiated at 500 mW / cm ² 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. “Airless” cure was performed between two Mylar slips each 0.25 mm thick. Due to the evaporation of acetone, the actual concentration of initiator in the resin was twice that shown in the table. The percent conversion of the surface was evaluated as shown in the table below.

In order to confirm the observation that the DC value is lowered due to the presence of air, three resin samples containing 3% TPO were examined in the absence and presence of air. Mean DC values and standard deviations were measured as shown in the table below.

Survey time air DC (standard deviation) 10 sec existence 46.9% (3.0%) 30 seconds existence 51.6% (4.3%) 10 sec absence 57.4% (1.3%)

The resin was prepared and coated onto the composite disc. After evaporating acetone for 60 seconds or longer, the coating was irradiated for 30 seconds in bright light of 300 mW / cm ² . Pencil hardness was measured as shown in the table below. All surfaces were found to be free of tack and finger scratches.

These results suggest that initiators other than phosphine oxide (eg camphorquinone) can be successfully used for the preparation of NOIL surfaces.

Example 20 Ortho Shear Bond Strength Analysis

The shear strength of the DP-20-5 NOIL composition and L / C bound resin was evaluated. NOIL DP20-5 was prepared with and without 0.75 Lumilux Blue (fluorescent additive) and 20% glass ionomer (X1B44RWG). Bond strength was compared to unfilled and filled L / C binder resin.

Human tooth enamel was etched with 37% semi-gel phosphate for 15 seconds. The etchant was washed by spraying with water and dried completely by air flow. One coat of the above composition was applied as a sealant to the etched area by rubbing onto the etched enamel surface and photocured for 10 seconds at a 500 mW / cm ² intensity using a Bisco VIP light curing system. The orthodontic bracket was bonded and cured to the sealed area using bracket adhesive (Lightbond or Phase II). The bound sample was placed in a deionized water bath at 37 ° C. for 2 hours before testing. The shear test results are shown in the table below.

Bracket adhesive L / C sealant Filled L / C Sealant Uncharged DP-20-5 DP-20-5 Charged with Flouescer Lightbond 22.85 ± 2.0 MPa 23.04 ± 6.4 MPa 23.08 ± 1.7 MPa 20.96 ± 1.3 MPa Phase ii 23.23 ± 5.7 MPa 25.02 ± 5.9 MPa 20.27 ± 2.8 MPa 21.12 ± 1.8 MPa

The bond strengths of the samples tested were very similar. These results suggest that the unfilled and filled NOIL compositions exhibit suitable shear bond strength values for use as orthodontic products.

Example 21 Fluoride Release Assay

The fluoride release of the NOIL composition was compared to the L / C sealant. The NOIL sample was DP20-5 containing 20% glass ionomer for fluoride emission and 0.75% Lumilux blue for phosphorescence.

Shade discs of DP-20-5 and LC sealant were prepared as follows. A round stainless steel mold placed between the polyethylene sheet and the glass slab was used to make a disc of fixed size. The disc was cured using two sets of light guns at 500 ± 50 mW / cm ² . One light gun was placed in the center of the disk and the disk was irradiated for 20 seconds. Next, two light guns were placed at opposite ends across the diameter of the circle, and the disk was irradiated for 10 seconds. The two light guns were moved around the circle to irradiate the disc for 20 seconds from the center and then irradiated four times for 10 seconds (the positions of the two guns around the circular disc: 0 and 180 °, then 90 and 270 °, then 135). And 315 °, and finally 45 and 225 °). The upper glass plate was removed and the curing process repeated. Samples were heated at 37 ± 3 ° C. for 15 ± 1 minutes. Diamond burrs were used to drill holes near the edge of the disc. The disc was sonicated in acetone to remove any air inhibiting layer that may be present. The diameter and height of the disc were measured with calipers and the mass of the disc was measured using an analytical balance. Twist / turn the wires through the holes so that the disk can be held upward in the vial. An aqueous sodium chloride solution (0.2 M, 10 ml) was added to each vial, and the vial was capped and left at 37 ° C. for 1 hour. Fluoride release was measured using a fluoride sensitive electrode immersed in a 50/50 TISAB / sample mixture. Three tests were run on each sample. The results are shown in the table below.

Sample Fluoride Release (㎍ / cm ² ) L / C Sealant Test # 1 0.178 L / C Seal Test # 2 0.172 L / C Seal Test # 3 0.153 DP-20-5 Test # 1 0.286 DP-20-5 Test # 2 0.262 DP-20-5 Test # 3 0.280

These results suggest that NOIL sealants such as DP-20-5 with fluoride glass can release much more fluoride than conventional L / C sealants. Thus, NOIL sealants can be used in products that require or require fluoride release.

Example 22 Use of NOIL as Top Surface on Composites

During restoration of the tooth, the composite can be properly added according to the manufacturer's instructions. The last layer of the composite is positioned, vortexed to the edge, shaped and contoured to the desired final shape. A thin coating of a NOIL composition, such as AC-40 or DP-20-5, is applied slowly around the surface of the composite and around the enamel using a soft brush. The NOIL-coated surface is then photocured using an appropriate light source and irradiation time (eg, visible blue light coming from the VIP light gun at 600 mW / sec ² to 20-40 seconds or less). The prepared surface can have a smooth and glossy surface. In addition, such surfaces can be obtained without the need to mold the composite with burs or abrasives as required by conventional composite products, thereby potentially damaging the surrounding dental tissue cells while further minimizing the treatment time of the patient in the treatment room. Can be prevented.

Example 23: Use of NOIL in Low Viscosity Composites

Low viscosity or flowable composites can be added as appropriate during tooth restoration. The last layer of the composite is positioned, vortexed to the edge, shaped and contoured to the desired final shape. The composite is light cured, for example for a short time of 5 seconds to remove the flow of the composite material. Apply a thin coating of NOIL (such as DP-20-5) slowly on the surface of the composite and around the enamel using a soft brush. The surface is then photocured using an appropriate light source and irradiation time (eg, visible blue light at 600 mW / sec ² ). The prepared surface can have a smooth and glossy surface.

Example 24 Use of NOIL as Root Surface Coating

The root surface requiring loss of sensitivity can be separated, which is then rubbed with a pumice and cavities cleaner slurry using cotton pellets, bubble pellets or microsol. The root surface can be etched with additional phosphoric acid for 15 seconds as needed. Apply NOIL foil-coated or slump-proof fill samples (such as DP-20-5) slowly to the root surface using a soft brush. The NOIL surface is tapered with a relaxed air stream and then photocured using an appropriate light source and irradiation time (eg, visible blue light for ² to 10 seconds at 600 mW / sec using a VIP cured light system).

Example 25 Use of NOIL in Dental Instruments

The shear bond strength (SBS) of the NOIL formulations AC-40 and DP20-5 was tested and compared with the shear bond strength of Fortify Plus. The following substrates were tested: enamel, dentin, composite, uncured composite, Rex III, porcelain, amalgam, acrylic and itself. The following technique was used.

Enamel-The enamel was wiped with pumice, washed and dried. The enamel was etched for 15 seconds with 37% phosphate half-gel before washing and drying. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 20 seconds, 20 seconds and 5 seconds, respectively. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Dentin-The dentin was polished for 30 seconds on a wet 600 grit standard, washed and dried. The dentin was etched for 15 seconds using 32% phosphate half-gel. The dentin was washed and left wet. Five to seven cots of an All Bond 2 Primer A & B mixture were applied to the wet dentin. The primed surface was lightly air-dried. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 20 seconds. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Amalgam and Rex III-Amalgam and Rex III were ground, moistened and dried on a wet 600 grit standard for 30 seconds. The surface was microetched using Accucuprep to homogenize the surface. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 20 seconds, 20 seconds and 5 seconds, respectively. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Composites and Acrylics--Composites and acrylics were ground, washed and dried on a wet 600 grit standard for 30 seconds. The surface was microetched using AccuPrep to homogenize the surface. Prior to cleaning and drying, the surface was etched with 32% phosphate half-gel for 15 seconds. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 20 seconds, 20 seconds and 5 seconds, respectively. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Magnetism-Magnetism was polished for 30 seconds on a wet 600 grit standard, washed and dried. The surface was microetched using AccuPrep to homogenize the surface. The surface was etched with 4% hydrofluoric acid half-gel for 4 minutes, washed and dried. A large amount of magnetic primer was applied to the surface and air-dried. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 20 seconds, 20 seconds and 5 seconds, respectively. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Uncured Composites--Prepare in acrylic using high speed handpieces and burs. The preparation was etched using Accuprep and 32% phosphate half-gel. The etched surface was treated in one step according to the manufacturer's instructions. Renew A2 Translucent was charged to the preparation. One coat of FortiPi Plus, AC-40 or DP20-5 was applied and photocured at 500 mW / cm ² for 40 seconds. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

Self-cured substrates of Fortypy Plus, AC-40 and DP20-5 were placed in acrylic. The composites and acrylics were ground for 30 seconds on a wet 600 grit standard, washed and dried. The surface was microetched using AccuPrep to homogenize the surface. Prior to cleaning and drying, the surface was etched for 15 seconds using 32% phosphate half-gel. One coat of FortiPi Plus, AC-40 or DP20-5 was applied to each substrate and photocured at 500 mW / cm ² for 20 seconds, 20 seconds and 5 seconds, respectively. After storage at 37 ° C. for 2 hours, the posts were bound and sheared.

The results of the shear bond strength (SBS) are shown in the table below, the numerical value being MPa. A # 5 gel cap (bond area 0.1684 cm ² ) was used for each of these tests with an Instron (Model 4466) shear bonder set at a crosshead speed of 5 mm / min, and the shear bond strength (SBS) coupled to the peak load. Calculated in MPa by dividing into areas. Mean and standard deviation were calculated by five iterations (N = 5) for each test.

In general, DP20-5 and AC-40 were performed with experimental error as much as or more than Fortify +.

The failure location was particularly focused on comparing the performance of dental products. The sample set consisted of five specimens. Most failures occurred in the substrate (SUB) or at the interface of the substrate and the sealant (S / S). In some cases, a failure occurred in the sealant layer SEAL. There was a case where a failure occurred at the interface between the sealant and the post (S / P). These observations are summarized in the table below.

Example 26 Use of NOIL in Nail or Toenail Treatment Products

DP-20-5 was tested as a nail treatment composition as follows. A thin layer of DP20-5 was coated on human nails by rubbing until the surface was smooth. The composition was exposed to 500 mW / cm ² light intensity for about 5 seconds using a VIP cured light system. The composition cured to a smooth and shiny surface that was hard to touch.

All compositions and / or methods disclosed and claimed herein can be prepared and practiced without undue experimentation in light of the present disclosure. Although the compositions and methods of the present invention have been described in terms of preferred embodiments, modifications may be made in the compositions and / or methods disclosed herein and in the order of steps of the invention without departing from the spirit, scope, and scope of the invention. Is apparent to those skilled in the art. More specifically, any agent that is chemically and physiologically related can replace the agent disclosed herein, provided that the same or similar results can be achieved. All such similar substitutes and modifications apparent to those skilled in the art are considered to be within the spirit, scope and concept of the present invention.

Claims (45)

A photocurable dental composition comprising a polyacrylate compound and a photoinitiator, The polyacrylate compound includes 5 to 10 acrylate functional groups per molecule, The composition does not contain methyl methacrylate and is cured upon exposure to visible light to form a surface lacking an oxygen inhibiting layer, Wherein the photoinitiator is present at a concentration of 1% to 10% by weight of the composition. delete delete The photocurable dental composition of claim 1, wherein the photoinitiator is a phosphine oxide compound. The photocurable dental composition of claim 1, wherein the photoinitiator is trimethylbenzoyldiphenylphosphine oxide (TPO). delete delete delete delete delete delete The photocurable dental composition of claim 1, wherein the polyacrylate compound comprises five acrylate functional groups per molecule. The photocurable dental composition of claim 1, wherein the polyacrylate compound comprises six acrylate functional groups per molecule. The photocurable dental composition of claim 1, wherein the polyacrylate compound is a six-functional aromatic urethane acrylate oligomer, caprolactone modified dipentaerythritol hexaacrylate, or dipentaerythritol pentaacrylate. The photocurable dental composition of claim 1, wherein the polyacrylate compound is present at a concentration of 20% to 95% by weight of the composition. The photocurable dental composition of claim 1, wherein the polyacrylate compound is present at a concentration of 30% to 95% by weight of the composition. The photocurable dental composition of claim 1, further comprising a co-monomer. 18. The photocurable dental composition of claim 17, wherein the co-monomer is selected from the group consisting of monoacrylate compounds, diacrylate compounds, triacrylate compounds, and tetraacrylate compounds. 19. The photocurable dental composition of claim 18, wherein the co-monomer is a monoacrylate compound and the monoacrylate compound is caprolactone acrylate. The method of claim 18, wherein the co-monomer is a diacrylate compound and the diacrylate compound is selected from the group consisting of tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, and polyethylene glycol diacrylate. Photocuring dental composition. 19. The photocurable dental composition of claim 18, wherein the co-monomer is a triacrylate compound and the triacrylate compound is trimethylolpropane triacrylate. The photocuring dental composition of claim 18, wherein the co-monomer is a tetraacrylate compound and the tetraacrylate compound is ditrimethylolpropane tetraacrylate. The photocurable dental composition of claim 1, further comprising a filler. The photocurable dental composition of claim 1, further comprising a nanofiller. The photocurable dental composition of claim 1, further comprising glass particles. The photocurable dental composition of claim 1, further comprising an acrylated amine compound. The photocurable dental composition of claim 1, further comprising a diluent. The photocurable dental 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, or a mixture of ethanol and water and acetone. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete