Source: http://www.google.com/patents/US7816423?dq=5,893,120
Timestamp: 2017-09-25 00:14:54
Document Index: 159030790

Matched Legal Cases: ['Application No. 173567', 'Application No. 2002331604', 'Application No. 2', 'Application No. 2', 'Application No. 02815839', 'Application No. 02815839', 'Application No. 02', 'Application No. 2003']

Patent US7816423 - Hardenable self-supporting structures and methods - Google Patents
Compositions, particularly for forming dental products, having a hardenable self-supporting structure with sufficient malleability to be subsequently customized into a second shape and then hardened, and methods....http://www.google.com/patents/US7816423?utm_source=gb-gplus-sharePatent US7816423 - Hardenable self-supporting structures and methods
Publication number US7816423 B2
Application number US 12/250,309
Also published as CA2454617A1, CN1541084A, CN100415198C, EP1416902A1, EP1416902B1, EP2272485A2, EP2272485A3, EP2275077A2, EP2275077A3, US7674850, US20030114553, US20090032989, US20110003266, WO2003015720A1
Publication number 12250309, 250309, US 7816423 B2, US 7816423B2, US-B2-7816423, US7816423 B2, US7816423B2
Inventors Naimul Karim, Todd D. Jones, Kevin M. Lewandowski, Duane D. Fansler, James M. Nelson, Marcelino Salviejo-Rivas, Babu N. Gaddam, Ahmed S. Abuelyaman, Sumita B. Mitra
Patent Citations (182), Non-Patent Citations (39), Referenced by (12), Classifications (27), Legal Events (2)
US 7816423 B2
providing a preformed dental product comprising a hardenable self-supporting structure comprising a composition that includes a resin system, a filler system, and an initiator system, wherein the composition is in the form of a hardenable, self-supporting, malleable structure having a first semi-finished shape, which is sufficiently malleable to be formed into a second shape at a temperature of about 15° C. to 38° C.;
forming the self-supporting, malleable structure having a first semi-finished shape into a second shape custom fit to a patient shape at a temperature of about 15° C. to 38° C.; and
wherein the term “self-supporting” means that the composition is dimensionally stable and will maintain its shape without significant deformation at room temperature for at least about two weeks when free-standing and in the absence of conditions that activate the initiator system and in the absence of an external force other than gravity;
customizing the shape of the dental product at a temperature of about 15° C. to 38° C. in the mouth of a subject; and
wherein the term “self-supporting” means that the composition is dimensionally stable and will maintain its shape without significant deformation at room temperature for at least about two weeks when free-standing and in the absence of conditions that activate the initiator system and in the absence of an external force other than gravity.
providing a preformed dental impression tray comprising a hardenable self-supporting structure comprising a composition that includes a resin system, a filler system, and an initiator system, wherein the composition is in the form of a hardenable, self-supporting, malleable structure having a first semi-finished shape, which is sufficiently malleable to be formed into a second shape at a temperature of about 15° C. to 38° C.;
forming the self-supporting, malleable structure having a first semi-finished shape into a second shape custom fit to a patient at a temperature of about 15° C. to 38° C.; and
It would be desirable to eliminate the initial mixing of the liquid resin and the polymeric powder and thereby create such prosthetic devices more efficiently. It would also be desirable to eliminate the impression-taking step. Dental waxes, commonly used for taking impressions in the mouth, exhibit many desirable properties for creating devices that are customized to a patient's mouth. These properties include malleability, low memory, sufficient strength to be self-supporting, and the thermal and rheological properties shown in FIG. 1. These wax (e.g., paraffin) materials typically have melting points near 55° C., with softening transitions near 40° C. Elastic and viscous moduli G′ and G″ are approximately 106 Pascals (Pa) at 25° C., sufficiently low to be easily deformed without being tacky. Although these materials exhibit desirable properties for creating devices customized to fit a patient's mouth, they are not hardenable (e.g., through polymerization), nor do they possess desirable properties such as compressive strength and wear resistance. As a result, these materials are not suitable for dental prosthetic applications.
U.S. Pat. No. 6,057,383 (Völkel et al.) discloses a dental material based on polymerizable waxes, wherein the materials are malleable and curable; however, they are based on little or no filler, typically 0-60% by weight, and high amounts of waxes, typically more than 20% by weight. As such, these materials have generally poor mechanical properties, such as flexural strength and wear resistance. Other thermoplastic molding compounds have been prepared, but these are typically highly viscous above their melting point (Tm), and somewhat elastic below Tm due to the high molecular weight of the included polymer. Moreover, these compositions must typically be warmed significantly above room temperature before becoming malleable.
Herein, the “resin system” can include one or more resins, each of which can include one or more monomers, oligomers, and/or polymerizable polymers.
The term “self-supporting” means that the composition is dimensionally stable and will maintain its shape (e.g., preformed shape of a crown) without significant deformation at room temperature (i.e., about 20° C. to about 25° C.) for at least about two weeks when freestanding (i.e., without the support of packaging or a container). Preferably, the compositions of the present invention are dimensionally stable at room temperature for at least about one month, and more preferably, for at least about six months. Preferably, the compositions of the present invention are dimensionally stable at temperatures above room temperature, more preferably up to about 40° C., even more preferably up to about 50° C., and even more preferably up to about 60° C. This definition applies in the absence of conditions that activate the initiator system and in the absence of an external force other than gravity.
The term “sufficient malleability” means that the self-supporting structure is capable of being custom shaped and fitted, for example, to a patient's mouth, under a moderate force (i.e., a force that ranges from light finger pressure to that applied with manual operation of a small hand tool, such as a dental composite instrument).
A preferred embodiment of the invention is a composition that includes a resin system including a crystalline component, greater than 60 percent by weight (wt-%) of a filler system (preferably, greater than 70 wt-% of a filler system), and an initiator system, wherein the composition is in the form of a hardenable self-supporting structure having a first shape. The self-supporting structure has sufficient malleability to be formed into a second shape, preferably at a temperature of about 15° C. to 38° C. (more preferably, about 20° C. to 38° C., which encompasses typical room temperatures and body temperatures, and most preferably, at room temperature). Advantageously, the compositions of the present invention do not need to be heated above body temperature (or preferably, even about room temperature) to become malleable.
wherein R is hydrogen or a (C1-C4)alkyl group, X is —CH2—, —C(O)O—, —O—C(O)—, —C(O)—NH—, —HN—C(O)—, —O—, —NH—, —O—C(O)—NH—, —HN—C(O)—O—, —HN—C(O)—NH—, or —Si(CH3)2—, in is the number of repeating units in the polymer (preferably, 2 or sore), and n is great enough to provide sufficient side chain length and conformation to form polymers containing crystalline domains or regions.
Thus, another embodiment of the invention includes a composition that includes a resin system, a filler system at least a portion of which is an inorganic material having nanoscopic particles with an average primary particle size of no greater than about 50 nanometers (nm), a surfactant system, and an initiator system. The composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape, preferably at a temperature of about 15° C. to 38° C. In such preferred embodiments with a surfactant system and nanoscopic particles, the resin system preferably includes at least one ethylenically unsaturated component, and the filler system is present in an amount of greater than 50 wt-%.
wherein R is hydrogen or a (C1-C4)alkyl group, X is —CH2—, —C(O)O—, —O—C(O)—, —C(O)—NH—, —HN—C(O)—, —O—, —NH—, or —O—C(O)—NH—, —HN—C(O)—O—, —HN—C(O)—NH—, or —Si(CH3)2—, m is the number of repeating units in the polymer (preferably, 2 or more), and n is great enough to provide sufficient side chain length and conformation to form polymers containing crystalline domains or regions, and combinations thereof. The composition further includes greater than about 60 wt-% of a filler system and an initiator system, wherein the composition is in the form of a hardenable self-supporting structure having a first shape. The self-supporting structure has sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C. Preferably, if the filler system includes fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.
The present invention also provides a dental impression tray. A preferred tray includes a resin system, a filler system, and an initiator system in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C. Preferably, the dental impression tray includes at least one structured surface. Preferably, the structured surface is formed by a porous substrate. Alternatively, the structured surface is a microreplicated surface.
The present invention also provides a method of preparing a dental product. The method includes: providing a composition comprising a resin system, a filler system, and an initiator system, wherein the composition is in the form of a hardenable, self-supporting, malleable structure having a first semi-finished shape (e.g., that of a preformed crown or preformed bridge); forming the self-supporting, malleable structure into a second shape; and hardening the self-supporting structure having the second shape to form a dental product. Preferably, forming the self-supporting, malleable structure into a second shape occurs at a temperature of about 15° C. to 38° C. Herein, forming the self-supporting, malleable structure into a second shape occurs under a force that ranges from light finger pressure to that applied with manual operation of a small hand tool, such as a dental composite instrument.
The present invention also provides a method of preparing a dental tray. The method includes: providing a composition comprising a resin system, a filler system, and an initiator system, wherein the composition is in the form of a hardenable, self-supporting, malleable structure having a first semi-finished shape of a preformed dental tray; forming the self-supporting, malleable structure into a second shape custom fit to the patient; and hardening the self-supporting structure having the second shape to form a dental tray. Preferably, forming the self-supporting, malleable structure into a second shape occurs a temperature of about 15° C. to 38° C.
The present invention provides a composition that includes a resin system, a filler system, and an initiator system in the form of a hardenable self-supporting (i.e., free-standing) structure having a first shape, preferably the shape of a dental crown. The resin system (one or more resins), filler system (one or more fillers), and initiator system (one or more initiators) are chosen such that: the composition can be relatively easily molded to form the initial self-supporting structure; the self-supporting structure maintains its first shape at room temperature for at least about two weeks (in the absence of conditions that activate the initiator system and in the absence of an external force other than gravity), and the self-supporting structure has sufficient malleability to be reformed into a second shape (preferably at a temperature of about 15° C. to 38° C., more preferably, at a temperature of about 20° C. to 38° C., and most preferably, at room temperature).
As used herein, a resin includes one or more monomers, oligomers, and/or polymerizable polymers, including combinations thereof. Although, in this context oligomers and polymers are both used, the terms “polymer” and “polymeric” are used herein to refer to any materials having 2 or more repeat units, thereby encompassing oligomers. Thus, unless otherwise specified, polymers include oligomers. Furthermore, the term polymer is used herein to encompass both homopolymers and copolymers, and the term copolymer is used herein to encompass materials with two or more different repeat units (e.g., copolymers, terpolymers, tetrapolymers).
By “crystalline” it is meant that the material displays a crystalline melting point at 20° C. or above when measured in the composition by differential scanning calorimetry (DSC). The peak temperature of the observed endotherm is taken as the crystalline melting point. The crystalline phase includes multiple lattices in which the material assumes a conformation in which there is a highly ordered registry in adjacent chemical moieties of which the material is constructed. The packing arrangement (short order orientation) within the lattice is highly regular in both its chemical and geometric aspects.
A crystalline component may be in a “semicrystalline state” in that long segments of polymer chains appear in both amorphous and crystalline states or phases at 20° C. or above. The amorphous phase is considered to be a randomly tangled mass of polymer chains. The X-ray diffraction pattern of an amorphous polymer is a diffuse halo indicative of no ordering of the polymer structure. Amorphous polymers show softening behavior at the glass transition temperature, but no true melt or first order transition. A material in a semicrystalline state shows characteristic melting points, above which the crystalline lattices become disordered and rapidly lose their identity. The X-ray diffraction pattern of such “semicrystalline” materials generally is distinguished by either concentric rings or a symmetrical array of spots, which are indicative of the nature of the crystalline order. Thus, herein a “crystalline” component encompasses semicrystalline materials.
The crystalline component includes at least one material that crystallizes, preferably above room temperature (i.e., 20° C. to 25° C.). Such crystallinity, that may be provided by the aggregation of crystallizable moieties present in the component (e.g., when the component is a polymer, in the backbone (i.e., main chain) or pendant substituents (i.e., side chains) of the component), can be determined by well known crystallographic, calorimetric, or dynamic/mechanical methods. For the purposes of the present invention, this component imparts to the resin system at least one melting temperature (Tm) as measured experimentally (for example by DSC) of greater than about 20° C. Preferably, this component imparts a Tm to the resin system of about 30° C.-100° C. If more than one crystalline material is used in the crystalline component, more than one distinct melting point may be seen.
wherein R is hydrogen or a (C1-C4)alkyl group, X is —CH2—, —C(O)O—, —O—C(O)—, —C(O)—NH—, —HN—C(O)—, —O—, —NH—, —O—C(O)—NH—, —HN—C(O)—O—, —HN—C(O)—NH—, or —Si(CH3)2—, in is the number of repeating units in the polymer, and n is great enough to provide sufficient side chain length and conformation to form polymers containing crystalline domains or regions. Preferably, m is at least 2, and more preferably, 2 to 100, and preferably, n is at least 10. The crystalline polymeric materials may be prepared by the polymerization of monomers containing the pendant (side chain) crystallizable moieties or by the introduction of pendant crystallizable moieties by chemical modification of a polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyvinyl ester, or poly-α-olefin polymers or copolymers. The preparation and morphology/conformational properties that determine the crystalline character of such side chain crystallizable or “comb-like” polymers are reviewed by Plate and Shibaev, “Comb-Like Polymers. Structure and Properties,” Journal of Polymer Science, Macromolecular Reviews, 8, 117-253 (1974).
Examples of suitable crystalline materials are acrylate or methacrylate polymers derived from acrylate or methacrylate esters of nontertiary higher alkyl alcohols. As used herein, the term “(meth)acrylate” means methacrylate or acrylate. The alkyl groups of these alcohols contain at least about 12, preferably about 16-26, carbon atoms. Examples of crystalline monomers that can be used to make crystalline polymeric materials include dodecyl (meth)acrylate, isotridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-octadecyl (meth)acrylate, behenyl (meth)acrylate, eicosanyl (methyl)acrylate, and mixtures thereof. Hexadecyl (methacrylates) and octadecyl (meth)acrylates are commercially available from Monomer-Polymer & Dajac laboratories, Inc., Feasterville, Pa., and Polysciences, Inc., Warrington, Pa. (Meth)acrylate esters of non-tertiary alcohols, the alkyl portions of which comprise from about 30 to about 50 carbon atoms, are commercially available under the trade designation UNILIN from Petrolite Corp., Tulsa, Okla. As long as the crystalline oligomer or polymer has a melting point, it can include noncrystallizable monomers. Acrylate or methacrylate or other vinyl monomers that are free-radically reactive may optionally be utilized in conjunction with one or more of (tie side chain crystallizable acrylate and methacrylate monomers provided that the resultant polymer has a melting or softening temperature above room temperature. Examples of such free-radically reactive monomers include, but are not limited to, tert-butyl acrylate, isobornyl acrylate, butyl methacrylate, vinyl acetate, acrylonitrile, styrene, isooctyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like. Various combinations of these monomers can be used.
Micron-size particles are very effective for improving post-cure wear properties. In contrast, nanoscopic fillers are commonly used as viscosity and thixotropy modifiers. Due to their small size, high surface area, and associated hydrogen bonding, these materials are known to assemble into aggregated networks. Materials of this type (“nanoscopic” materials) have average primary particle sizes (i.e., the largest dimension, e.g., diameter, of unaggregated material) of less than 200 nanometers (nm). Preferably, the nanoscopic particulate material has an average primary particle size of at least about 2 nanometers (nm), and preferably at least about 7 nm. Preferably, the nanoscopic particulate material has an average primary particle size of no greater than about 50 nm, and more preferably no greater than about 20 nm in size. The average surface area of such a filler is preferably at least about 20 square meters per gram (m2/g), more preferably, at least about 50 m2/g, and most preferably, at least about 100 m2/g.
Yet another type of photoinitiator includes acylphosphine oxides, such as those described in European Pat. Application No. 173567 (Ying). Suitable acylphosphine oxides are preferably of the general formula (R4)2—P(═O)—C(═O)—R5, wherein each R4 is individually a hydrocarbon group, preferably an alkyl group, alicyclic group, aryl group, and aralkyl group, any of which can be substituted with a halo-, alkyl- or alkoxy-group, or the two R4 groups can be joined to form a ring along with the phosphorous atom, and wherein R5 is a hydrocarbon group, preferably, a S—, O—, or N-containing five- or six-membered heterocyclic group, or a —Z—C(═O)—P(═O)—(R4)2 group, wherein Z represents a divalent hydrocarbon group such as alkylene or phenylene having from 2 to 6 carbon atoms. Examples of suitable acylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide, for example. Optionally, tertiary amine reducing agents may be used in combination with an acylphosphine oxide. Illustrative tertiary amines useful in the invention include those described above as well as ethyl 4-(N,N-dimethylamino)benzoate and N,N-dimethylaminoethyl methacrylate.
Generally, a preformed article of appropriate size and shape (the first shape) is selected and custom shaped at a temperature of about 15° C. to 38° C. (preferably, about 20° C. to 38° C., which encompasses typical room temperatures and body temperatures, and more preferably, at room temperature). This shaping can be done by a variety of methods including applying pressure with fingers or an instrument of choice (e.g., hand operation of dental composite instrument), trimming, Cutting, sculpting, grinding, etc. Once the desired custom shape has been achieved, the article is hardened (e.g., cured) by exposing it to heat/radiation to cause activation of the initiator system. This can be done either in a single step, or in multiple steps with successive steps of custom shaping being clone in-between. One or more of these steps can be carried out in an oxygen-free inert atmosphere or in vacuum. After the final shaping and hardening steps, the hardened article can be further modified in shape by grinding, trimming, etc., if desired. Once the final custom shape of the article has been obtained, it can be polished, painted, or otherwise surface treated, if required for the intended application. Preferably, the final custom shaped articles prepared from the compositions of the present invention do not need an additional veneering material (e.g., a second material that provides a desired appearance or property). The intended application may require mounting, bonding, or otherwise attaching the custom shaped cured article to a second object adhesively, mechanically, or by combination of both.
This invention also includes a customizable dental impression tray, formed from a self supporting composition as described herein. Dental trays are commonly used to obtain accurate impressions of a patient's teeth. Commonly, the tray is supplied as a preformed non-customizable item, albeit in a range of sizes. This tray is filled with an impression material (e.g., one or more flowable elastomeric materials, such as polyvinylsiloxane, polyether, or polysulfide) and pressed around the teeth of the upper or lower jaw. The impression material contained within the tray is then cured in place. More accurate impressions can be obtained with increased patient comfort through the use of a customized tray, which can be shaped to fit the patient's mouth more accurately than a generic “one size fits all” tray. Thus, the compositions of the present invention can be used to make a customizable dental impression tray.
Elastic Moduli (G′) and Viscous Moduli (G″) as an indication of composition rheology were measured according to the following test procedure. A composition sample was heated to 70° C. in an oven and pressed between two Teflon-lined glass plates into a sheet having a thickness of approximately 2 millimeters (mm). After cooling to room temperature and aging for 48 hours, an 8-mm diameter disk was cut from the resulting sheet. Rheological measurements were carried out on a Rheometrics RDA II dynamic mechanical analyzer (Rheometric Scientific, Piscataway, N.J.) using 8-mm parallel plate fixtures. Elastic and Viscous Moduli were measured at 25° C. as a function of frequency (Hz) for the disk of pre-cured composite and results reported in kilopascals (kPa).
The objective of this test is to determine if a composition could be made into a self-supporting crown and then determine qualitatively if that crown is malleable, shapeable, and trimable at room temperature. A composite sample was manually formed into a 2-mm thick “cup” approximately the size of a molar and was pressed at 85° C. between a positive mold of a slightly reduced maxillary central incisor and a negative mold of 3M ESPE polycarbonate crown #10. The positive and negative molds were prepared from 3M ESPE IMPRINT II Monophase and 3M ESPE EXPRESS STD Putty Material (3M Co., St. Paul, Minn.), respectively. In order for a composition sample to “pass” this Test Method, the pressed crown should easily be removed from the mold after cooling to room temperature without any markable deformation.
The crown sample was further evaluated based on its ability to be custom fitted on a more heavily reduced maxillary central incisor on a TYPODONT arch (Columbia Dentoform, Long Island City, N.Y.). The crown sample was examined for (1) how well it retained its form while being handled, (2) how easily it could be trimmed with scissors, and (3) how well it could be custom-fitted on the central incisor by adapting the crown shape with a composite instrument while positioned on the reduced tooth, without either breaking or demonstrating any elastic deformation. In order for a composition to “pass” this Test Method, the formed crown sample was required to successfully meet each of these three quality parameters.
The packability of a composite material was qualitatively determined according to the following procedure. The first molar tooth on a lower arch model (SM-PVR-860 from Columbia Dentaform Corporation, long Island City, N.Y.) was prepared with a mesio occluso cavity preparation. A metal matrix band (dead soft HO Band-Young, type universal #1 from Henry Schein catalog) was fitted around the molar with the help of a Tofflemire matrix retainer (type universal, from Henry Schein catalog). This model was then placed in a small heating chamber, which was kept at a constant temperature of 38° C. Once the model had reached a temperature of 38° C. it was taken out of the heated chamber and a pellet of the composite to be tested was placed in the prepared tooth cavity. Packability of the composite was evaluated by compacting the pellet in the cavity with a double-ended amalgam plugger (½ Black. DE from Henry Schein catalog). The ability of the composite material to be condensed, rather than flowing around the plugging instrument, was determined. Evaluation also included the ability of the composite material to transfer some of the compacting force to the metal matrix band, and thereby to deform the band. A composite material that both could be condensed in the cavity and that deformed the band was judged to be packable.
The crystallinity and melting point of samples was determined by differential scanning calorimetry using a DSC 2920 instrument from TA Instruments (New Castle, Del.). A sample weighing 5-10 mg that had been aged for at least 72 hours was placed in a standard aluminum pan and heated at 5° C./min from −40° C. to 120° C. The resulting thermogram was examined for evidence of a melting point range and endothermic peaks that would be associated with the melting of crystalline species. The absence of endothermic peaks would be indicative of no crystalline component in the sample.
Flexural Strength and Flexural Modulus were measured according to the following test procedure. A composition sample was pressed at 65° C. in a preheated mold to form a 2-mm×2-mm×25-mm test bar. The bar was aged at room temperature for 24 hours and light cured for 90 seconds by exposure to two oppositely disposed VISILUX Model 2500 blue light guns (3M Co.). The bar was then post-cured for 180 seconds in a Dentacolor XS unit (Kulzer, Inc., Germany) light box, and sanded lightly with 600-grit sandpaper to remove flash from the molding process. After storing in distilled water at 37° C. for 24 hours, the Flexural Strength and Flexural Modulus of the bar were measured on an Instron tester (Instron 4505, Instron Corp., Canton, Mass.) according to ANSI/ADA (American National Standard/American Dental Association) specification No. 27 (1993) at a crosshead speed of 0.75 mm/minute. Six bars of cured composite were prepared and measured with results reported in megapascals (MPa) as the average of the six measurements.
Compressive Strength was measured according to ANSI/ADA Specification No. 27 (1993). Specifically, a composition sample was heated to 85° C., packed into a 4-mm (inside diameter) glass tube, and the tube capped with silicone rubber plugs and compressed axially at approximately 0.28 MPa for 5 minutes. The sample was light cured for 90 seconds by exposure to two oppositely disposed VISILUX Model 2500 blue light guns (3M Co.) and then irradiated for 180 seconds in a Dentacolor XS light box (Kulzer, Inc.). The cured sample was then cut on a diamond saw to form cylindrical plugs 8-mm long for measurement of CS. The plugs were stored in distilled water at 37° C. for 24 hours prior to testing. Measurements were carried out on an Instron tester (Instron 4505, Instron Corp.) with a 10-kilonewton (kN) load cell. Five plugs of cured composite were prepared and measured with results reported in MPa as the average of the five measurements.
BHT 2,6-Di-tert-butyl-4-methylphenol (Sigma-Aldrich Fine
EDMA Ethyl 4-(N,N-dimethylamino)benzoate (Sigma-Aldrich)
M5 Hydrophilic fumed (pyrogenic) silica (Cab-O-Sil M5,
R711 Methacryl silane-treated fumed (pyrogenic) silica
R972 Hydrophobic fumed (pyrogenic) silica (AEROSIL R-972,
ARQ Cationic surfactant ARQUAD 2HT-75 (Akzo Nobel
TPEG Nonionic surfactant Carbowax TPEG 990 (Dow,
STZ Silane-Treated ZrO2/SiO2 prepared as described in U.S.
TONE 0230 Hydroxy-terminated polycaprolactone (Dow)
TONE 0230- Reaction product between TONE 0230 Diol and IEM;
IEM prepared as described in U.S. patent application Ser. No.
MAA Methacrylic anhydride (Sigma-Aldrich)
PE-Diol Polyethylene diol (MW approximately 2500, Sigma-
Polyol PP50 Pentaerythritol ethoxylate (Perstorp Speciality Chemicals,
DBU 1,8-Diazabicycol[5.4.0]undec-7-ene (Sigma-Aldrich)
OligoVDM Vinyl dimethylazlactone oligomer, prepared as described
TEGDMA Triethyleneglycol dimethacrylate (Sartomer Co.)
Benzotriazole 2-(2-Hydroxy-5-methacrylyoxyethylphenyl)-2H-
LEX110 Lexorez-1150-110 polyester polyol (Inolex Chemical
LEX160 Lexorez-1150-160 polyester polyol (Inolex Chemical
LEX110-IEM Reaction product between Lexorez-1150-110 and IEM;
LEX160-IEM Reaction product between Lexorez-1150-160 and IEM;
THEIC-TMA Tris(2-hydroxyethyl) isocyanurate triacrylate (SR 368,
THEIC-TA Tris(2-hydroxyethyl) isocyanurate triacrylate (SR 290,
CHDM-DMA Cyclohexane dimethanol dimethacrylate (CD 401,
THEI(5)-IEM Reaction product (1:15:3 molar ratio) of 1,3,5-tris(2-
THEI(10)- Reaction product (1:30:3 molar ratio) of 1,3,5-tris(2-
IEM hydroxyethyl)cyanuric acid with ε-caprolactone and IEM
BisGMA(5)- Reaction product (1:10:2 molar ratio) of BisGMA with ε-
IEM caprolactone and IEM prepared as described herein
GGDA(5)- Reaction product (1:15:3 molar ratio) of Glycerol 1,3-
IEM diglycerolate diacrylate with ε-caprolactone and IEM
Polyethylene diol (PE-Diol, 25 grams (g)) and methacrylic anhydride (4.0 ml, Sigma-Aldrich) were added to a round-bottom flask along with BHT (0.02 g) to scavenge free radicals. The flask was purged with nitrogen for 10 minutes, and then heated with stirring overnight at 100° C. The resulting material was poured into methanol, recovered by filtration, dissolved in hot toluene, reprecipitated with methanol, again recovered by filtration, and dried overnight on a vacuum line. The dried solid was designated Resin A. Analysis by 1NMR indicated complete conversion of the diol to methacrylate functionality.
A 58% by weight solution of octadecyl acrylate (Sigma-Aldrich) in ethyl acetate (82 g of solution), HEMA (2.5 g) and toluene (50 g) were charged into at 3-neck reaction vessel equipped with magnetic stirring, a water-cooled condenser, a thermocouple and a nitrogen inlet. The solution was heated under nitrogen to 115° C. and, with stirring, tert-butylperoxybenzoate (0.1 g, Sigma-Aldrich) dissolved in toluene (3 g) was charged into the vessel. A small exotherm (temperature increase of approximately 3-5° C.) was observed. After 30 minutes, 3.34 g of IEM in the presence of a catalytic amount of dibutyltin dilaurate (0.68 g, Sigma-Aldrich) was added in order to functionalize the pendant hydroxyl units of the resin. The resulting mixture was agitated overnight in a 60° C. shaker bath. The resulting methacrylate functional resin was isolated by precipitation with methanol and subsequent filtration. The dried solid was designated Resin B. The methacrylate functionalization was confirmed by crosslinking a mixture of the HEMA-IEM adduct and isooctyl acrylate in the presence of a photoinitiator, DAROCUR 1173 (Ciba-Geigy, Hawthorn, N.Y.), and exposure to UV light.
A polycaprolactone 4-arm star resin was prepared according to the following procedure. Polyol PP50 (35.6 g, 0.1 mole (mol)) and ε-caprolactone (320.0 g, 2.8 mol, Sigma-Aldrich) were added to a glass vessel and heating under nitrogen to 110° C. FASTCAT 4224 (0.21 g, 0.5 millimole (mmol), Atofina Chemicals, Inc., Philadelphia, Pa.) was added and the mixture was heated at 170° C. for five hours. After cooling, a tan, solid (melting point 48-52° C.) was formed, collected by filtration, and dried. The solid had an OH equivalent weight of 709. A portion of the solid (50.0 g, 18 mmol) was mixed with methacrylic anhydride (11.09 g, 72 mmol, Sigma-Aldrich) and BHT (0.35 g, 1.6 mmol). After heating at 100° C. for 17 hours and cooling to room temperature, a tan solid was obtained. The dried solid was designated Resin C.
To a stirred solution of OligoVDM (25 g, 1.7×10−1 mol) and THF (250 ml) under nitrogen were added octadecyl alcohol (29.7 g, 1.1×10−1 mol), HEMA (1.5 g, 1.2×10−2 mol), and DBU (0.2 g, 1.3×10−3 mol). The resultant suspension was heated to 40° C. and maintained at this temperature with stirring overnight for approximately 12 hours. The resulting yellow-orange viscous liquid was isolated by pouring into methanol and evaporation of the methanol/THF solvent at 80° C. for 12 hours under a vacuum. The dried material was designated Resin D.
In a 250-ml 3-neck flask equipped with a mechanical stirrer under nitrogen atmosphere, 1,3,5-tris(2-hydroxyethyl)cyanuric acid (4.30 g, 0.016 mol) was suspended in ε-caprolactone (54.70 g, 0.48 mol) with a continuous stirring. A few drops of tin(II) ethyl hexanoate were added and the mixture was heated at 130-150° C. overnight. A clear yellow liquid was obtained. The reaction temperature was lowered to 50° C. (and then BHT (50 mg) was added followed by 5 drops of dibutyltin dilaurate. IEM (7.66 g, 0.049 mol) was then charged at 50° C. over 45 minutes. After 20 minutes of stirring, the heat was turned off. The liquid solidified into a material that was characterized by IR, NMR and GPC. (Mw=6.46E+03, Mn=5.69E+03, P=1.14)
A mixture of 20.0 g (20 mmol) LEXOREZ-1150-110, 6.24 g (40 mmol) 2-isocyanatoethyl methacrylate, 70 g acetone, and 0.03 g (0.05 mmol) dibutyltin dilaurate was heated to 50° C. for 5 hours. The solvent was then removed under reduced pressure to provide the product as a white solid.
A mixture of 20.0 g (28 mmol) LEXOREZ-1150-160, 8.57 g (55 mmol) 2-isocyanatoethyl methacrylate, 70 g acetone, and 0.03 g (0.05 mmol) dibutyltin dilaurate was heated to 50° C. for 5 hours. The solvent was then removed under reduced pressure to provide the product as a white solid.
Examples 1-14 and Comparative Example 1 (CE-1) Self-Supporting Light-Curable Composites
Self-supporting, light-curable composites (Examples 1-14 and Comparative Example 1) were prepared according to the following procedure. The photoinitiator components were initially dissolved in bisGMA, UDMA, or bisGMA/UDMA/bis-EMS6/TEGDMA blend in a water bath. Then the ingredients (names and quantities for each example shown in Table 1) were weighed into a MAX 20 plastic mixing cup having a screw cap (Flakteck, Landrum, S.C.) and the closed cup heated in an oven at 85° C. for 30 minutes. The cup was placed in a DAC 150 FV speed mixer (Flakteck) and spin mixing carried out for 1 minute at 3000 rpm. The cup was then reheated for 30 minutes at 85° C. followed by another minute of mixing at 3000 rpm to afford the final blended composite. A similar blended composite was made without the photoinitiators (CPQ and EDMA) for ease of pre-cure physical property testing.
Bis (Semi-Crystalline) Surfactant-(g) STZ CPQ EDMA
Ex. GMA (g) (g) Fumed Silica-(g) (g) (phr*) (phr)
CE-1 4.0 — — 16.0 0.25 1.0
1 3.8 — ARQ-0.2 15.8 0.25 1.0
2 2.0 TONE0230-IEM - 2.0 — 16.0 0.25 1.0
3 2.0 TONE0230-IEM - 2.0 ARQ-0.12 15.80 0.25 1.0
4 2.99 TONE0230-IEM - 1.0 TPEG-0.12 15.72 0.25 1.0
5 1.0 TONE0230-IEM - 2.99 TPEG-0.12 15.72 0.25 1.0
6 2.8 Resin A - 1.2 — 16.0 0.175 0.7
7 3.0 Resin B - 1.0 — 16.0 0.188 0.75
8 2.0 Resin C - 2.0 — 16.0 0.125 0.5
9 1.99 Resin C - 1.99 TPEG-0.12 15.72 0.125 0.5
10  3.0 Resin D - 1.0 — 16.0 0.188 0.75
11  3.8 — ARQ-0.2 16.0 0.25 1.0
12  1.9 TONE0230-IEM - 1.9 TPEG-0.2 16.0 0.25 1.0
13  2.0 TONE0230-IEM - 2.0 M5-0.2 15.8 0.25 1.0
14  — TONE0230-IEM - 4.0 — 16.0 0.25 1.0
15  2.4** TONE0230-IEM - 5.6 TPE-0.24 11.5 0.25 1.0
Example 15 Dental Impression Tray Preparation and Simulated Use
The bulk composite was pressed in a Carver press between two siliconized paper liners (TPK 7120, 3M Co.) to a thickness of approximately 2 mm and heated to 40° C. The two paper liners were discarded and the sheet was laminated manually under hand pressure at 40° C. between two layers of a nonwoven fabric (SONTARA 8010, DuPont, Old Hickory, Tenn.). While still warm, a 10-cm×10-cm sheet of the resulting laminate was placed over a stone model of a lower jaw, shaped to fit the contour loosely, and allowed to cool down to room temperature overnight. The contoured form was carefully removed from the model and cut into the shape of an impression tray including a handle to provide a self-supporting, malleable and curable custom tray.
Examples 16-32 Self-Supporting Light-Curable Composites
Bis Resin Additive
GMA (Semi-Crystalline) Surfactant-(g) STZ Photo-
Ex. (g) (g) Fumed Silica-(g) (g) initiator
16 1.95 LEX160-IEM - 1.95 TPEG-0.12 15.13 PI#1**
17 2.93 LEX110-IEM - 0.98 TPEG-0.12 15.13 PI#1
18 2.7* TONE0230-IEM - 0.9 ARQ-0.11 14.80 PI#2***
19 2.52 TONE0230-IEM - 1.18 TPEG-0.11 14.36 PI#2
20 2.93 THEI(10)-IEM - 0.98 TPEG-0.12 15.21 PI#1
21 1.95 THEI(5)-IEM - 1.95 TPEG-0.12 15.13 PI#1
22 1.99 BisGMA(5)-IEM - 1.99 TPEG-0.12 15.72 PI#1
23 1.99 GGDA(5)-IEM - 1.99 TPEG-0.12 15.72 PI#1
24 2.93 THEIC-TMA - 0.98 TPEG-0.12 15.13 PI#1
25 1.95 THEIC-TA - 1.95 TPEG-0.12 15.13 PI#1
26 2.93 THEIC-TA - 0.98 TPEG-0.12 15.13 PI#1
27 2.52* CHDM-DMA - 1.08 TPEG-0.11 14.90 PI#2
28 3.50* None TPEG-0.11 14.47 PI#2
29 3.50* None TPEG-0.11 14.39 PI#2
30 3.24* TONE0230-IEM - 0.36 TPEG-0.11 15.16 PI#2
31 3.24* TONE0230-IEM - 0.36 TPEG-0.11 14.89 PI#2
32 3.24* THEI(10)-IEM - 0.36 TPEG-0.11 14.89 PI#2
G′ G″ Diametral
kPa Flexural Compressive Tensile Strength, Flexural
Ex. (at 0.005 Hz) Strength, MPa Strength, Mpa MPa Modulus, MPa
CE-1 1.4 2.3 133 (21) 277 (26) 44 (6) 7933 (805)
1 127 108 134 (15) 323 (13) 42 (6) 8487 (678)
2 95 80 115 (12) 340 (19) 52 (11) 5275 (630)
3 577 350 121 (12) 319 (21) 44 (6) 5169 (726)
4 138 120 168 (13) 328 (38) 42.5 (7)  8928 (194)
5 3080 2410 122 (10) 284 (16) 26 (8) 4551 (449)
6 624 303 109 (7)  171 (25) 28 (2) 5146 (356)
7 1890 947 107 (18) 263 (13) 24 (3) 7359 (777)
8 213 156 79 (15) 298 (12) 42 (4) 3410 (354)
9 557 357 87 (8) 272 (31) 46 (13) 3121 (224)
10  268 203 85 (25) 233 (12) 33 (8) 5688 (1069)
11  88 73 120 (4)  299 (12) 39 (7) 6429 (608)
12  232 146 86 (12) 356 (6)  54 (7) 3943 (204)
13  520 224 137 (8)  318 (22) 45 (10) 5430 (742)
14  2120 1610 76 (10) 296 (16) 45 (16) 1960 (363)
kPa Flexural Strength, Compressive Tensile Strength, Flexural
Ex. (at 0.01 Hz) MPa Strength, MPa MPa Modulus, MPa
16 732 358 125 (14) 356 (6)  72 (11) 4380 (199)
17 707 363 130 (15) 358 (11) 74 (5) 6649 (325)
18 547 264 141 (11) 348 (7)  65 (5) 6125 (473)
19 525 257 142 (8)  368 (11) 66 (6) 7929 (380)
20 712 349 135 (14) 363 (10) 66 (13) 5533 (343)
21 1377 652 109 (10) 329 (21) 85 (4) 3348 (355)
22 416 210 114 (10) 348 (11) 68 (3) 5098 (299)
23 1136 507 105 (12) 350 (11) 64 (11) 5289 (251)
24 291 156 131 (13) 317 (14) 82 (3) 9864 (454)
25 433 225 155 (14) 407 (23) 82 (12) 12497 (421)
26 325 179 136 (14) 374 (12) 62 (3) 11920 (574)
27 1353 630 153 (18) 375 (13) 70 (7) 9088 (365)
28 132 81 173 (15) 378 (14) 83 (8.2) 10299 (786)
29 291 138 172 (7)  385 (13) 93 (7) 10079 (477)
30 98.5 49 157 (16) 381 (25) 92 (5) 7604 (491)
31 180 94.4 147 (13) 388 (19) 82 (9) 6896 (392)
32 146 73.6 151 (7)  352 (16) 80 (10) 7547 (403)
In addition to the testing results provided in Tables 3 and 4; Examples 2, 3, 13, 14, 24, 25, and 26; and the commercial material REVOTEK LC Resin (GC Dental Products Corp., Japan) were confirmed to contain a crystalline component having a melting point above 20° C. when evaluated according to the Pre-Cure DSC Test Method described herein. A sample of the commercial material SUREFIL High Density Posterior Restorative (Dentsply) showed the presence of a crystalline component having a melting point below 20° C. That is, there is no crystalline component as defined herein. In contrast, DSC evaluations of Example 1 and the commercial materials PRODIGY Condensable Composite Restorative System (Kerr, Orange, Calif.) and TRIAD Visible Light Cure Provisional Material (Dentsply Caulk, Milford, Del.) suggested the absence of any crystalline component. The results of these DSC measurements are provided in Table 5. The Elastic Moduli (G′) and Viscous Modulit (G″) of the four commercial materials (according to the Test Method provided herein, except that samples were pressed without heating) are also provided in Table 5.
G′ G″ Crystalline
KPA (at Melting Point Range (° C.) Component
Example 0.01 Hz) (Peak Exotherm (° C.)) (at 22° C.)
1 NM* NM No Melting Point No
2 NM NM 27-43 (36.9) Yes
3 NM NM 29-43 (36.9) Yes
13 NM NM 27-43 (37.4) Yes
14 NM NM 29-43 (36.9) Yes
24 NM NM Broadly from 0-35 (no Yes
25 NM NM Broadly from 0-35 (no Yes
26 NM NM Broadly from 0-35 (no Yes
TRIAD 79.5 48.8 No Melting Point No
PRODIGY 83.3 41.7 No Melting Point No
SUREFIL 594 257 7-16 (11) No
REVOTEK** 883 437 32-75 (65.0) Yes
*NM—Not Measured
US622068 Nov 14, 1898 Mar 28, 1899 Charlotte E payne
US1468428 Jul 18, 1921 Sep 18, 1923 Amos S Wells Dental molding apparatus
US1864365 Sep 6, 1929 Jun 21, 1932 Ac Spark Plug Co Process and apparatus for forming ceramic bodies
US1896123 Jun 13, 1928 Feb 7, 1933 Schweitzer Heinrich Wax dental form and method of making same
US2271454 Jun 25, 1938 Jan 27, 1942 Dental Res Corp Method of forming a reproducting of an article
US2310448 Mar 11, 1940 Feb 9, 1943 Leib Henry H Dental apparatus
US2332537 Feb 20, 1941 Oct 26, 1943 Abraham Slatis Method of compression molding
US2474676 Feb 27, 1946 Jun 28, 1949 Myerson Tooth Corp Method of forming artificial teeth
US2480048 Jul 10, 1944 Aug 23, 1949 William S Rice Casting process
US2551812 Jul 14, 1947 May 8, 1951 Nelson Alex A Process of preparing an artificial denture
US3390458 May 10, 1965 Jul 2, 1968 Joseph M. Lytton Method of preparing for dental impressions
US3565387 Sep 17, 1968 Feb 23, 1971 Dental Innovations Inc Prefabricated dental pattern having adjusting slot means
US3585723 Jun 20, 1969 Jun 22, 1971 Ion Co The Dental crown and method of installation thereof
US3949476 Mar 25, 1974 Apr 13, 1976 Henry Kahn Device useful in dental crown procedures and method of using the same
US3997637 Apr 23, 1975 Dec 14, 1976 Olbert William Rogers Method of making tooth reconstructions such as inlays and crowns
US4080412 Apr 20, 1977 Mar 21, 1978 Polythetics, Inc. Dentures and process for making the same
US4113499 Mar 18, 1976 Sep 12, 1978 Valentin Nikolaevich Ivanov Suspension for making molds in disposable pattern casting
US4115488 Apr 20, 1977 Sep 19, 1978 Polythetics, Inc. Dentures and process for making the same
US4129946 Feb 17, 1977 Dec 19, 1978 Unitek Corporation Dental crown form
US4347888 Mar 20, 1980 Sep 7, 1982 Butler Melvyn P Method of making forms for investment casting and products produced therefrom
US4449936 Sep 8, 1982 May 22, 1984 Peter Bayer Process for the preparation of dentures
US4514174 Nov 19, 1982 Apr 30, 1985 Dentsply Research & Development Corp. Methods for posterior dental restoration employing light curable packable compositions
US4718849 Mar 6, 1986 Jan 12, 1988 Weissenfluh Hans Von Sheet-like dental die
US4776795 Mar 3, 1987 Oct 11, 1988 Wolfgang Hornig Process for making metal artificial tooth parts
US4957441 Dec 20, 1988 Sep 18, 1990 Minnesota Mining And Manufacturing Company Method of enhancing the curing of a photocurable dental restorative material
US5024790 Jul 9, 1990 Jun 18, 1991 Corning Incorporated Glazing dental constructs
US5102332 Feb 25, 1991 Apr 7, 1992 Ticore Dental Systems Braided fiber dental retainer and container therefor
US5135545 Mar 22, 1991 Aug 4, 1992 The Dow Chemical Company Method for making machinable abrasive greenware
US5332390 Oct 5, 1992 Jul 26, 1994 Rosellini Davey G Shell tooth form
US5487663 Dec 15, 1994 Jan 30, 1996 Wilson; George M. Oral appliances and method
US5707236 Aug 28, 1995 Jan 13, 1998 Minnesota Mining And Manufacturing Company Selectively sorbent article and method for use in dental applications
US5775913 May 27, 1997 Jul 7, 1998 Updyke; John R. Process for minimal time tooth capping
US5785178 Nov 4, 1996 Jul 28, 1998 Minnesota Mining And Manufacturing Co. Packaged photocurable composition
US5827063 Apr 7, 1997 Oct 27, 1998 Greenstein; Jean Method of making dental restoration employing preforms
US5876209 Feb 27, 1998 Mar 2, 1999 Letcher; William F. Method of manufacturing a dental crown
US5914185 Sep 13, 1996 Jun 22, 1999 Shoher; Itzhak Moldable dental material composition
US5919870 Jun 5, 1996 Jul 6, 1999 Fmc Corporation Functional telechelic star polymers
US5951294 Sep 9, 1998 Sep 14, 1999 Pierson; Kenneth W. Method of creating an interim crown
US5996796 Jul 27, 1998 Dec 7, 1999 3M Innovative Properties Company Packaged photocurable composition
US6114409 Jan 4, 1995 Sep 5, 2000 Krebber; Burghardt Dental material and tool for its application
US6244870 Apr 6, 1998 Jun 12, 2001 Injex Corporation Abutment tooth model and method of manufacturing a prosthetic restoration to be formed on the abutment tooth model
US6382980 Mar 21, 2000 May 7, 2002 Itzhak Shoher Compact dental multi-layered material for crown and bridge prosthodontics and method
US20020102519 Jan 26, 2001 Aug 1, 2002 Lloyd Baum Dental prostheses fabrication method using pre-contoured impressionable pattern
US20020117393 Mar 26, 2002 Aug 29, 2002 Sun Benjamin J. Licht curing system and method
US20040224283 Nov 26, 2003 Nov 11, 2004 Sun Benjamin J. Method of forming a dental product
US20050040551 Aug 19, 2003 Feb 24, 2005 Biegler Robert M. Hardenable dental article and method of manufacturing the same
US20050042576 Aug 19, 2003 Feb 24, 2005 Oxman Joel D. Dental article forms and methods
US20050042577 Aug 19, 2003 Feb 24, 2005 Kvitrud James R. Dental crown forms and methods
US20050100868 Aug 19, 2004 May 12, 2005 Naimul Karim Hardenable dental article and method of manufacturing the same
US20050147944 Dec 31, 2003 Jul 7, 2005 Naimul Karim Curable dental mill blanks and related methods
US20060052470 Jul 15, 2004 Mar 9, 2006 Eric Grech Photopolymerizable composition based on an epoxyvinylester resin and on a urethane acrylate resin and use thereof for making dental prosthesis preforms and or models
US20070018346 Mar 31, 2006 Jan 25, 2007 Sun Benjamin J Light curing system and method
US20090032989 Oct 13, 2008 Feb 5, 2009 3M Innovative Properties Company Hardenable self-supporting structures and methods
USD403768 May 9, 1997 Jan 5, 1999 Minnesota Mining And Manufacturing Company Fiber tip applicator
CA1117685A1 Title not available
DE2751057A1 Nov 15, 1977 May 24, 1978 Sybron Corp Photopolymerisierbare dental-wiederherstellungsmasse
DE19924116A1 May 26, 1999 Jan 25, 2001 Rainer Kuppi Plastic filled ceramic cap, for use as tooth crown, manufacture comprises a plastic secondary part, introduced into the interior of a primary part, placed over a tooth stump, before curing the plastic and fixing both parts in position
DE29921182U1 Dec 3, 1999 Apr 13, 2000 Dental Forschung Schleicher Gm Formelement zum Herstellen von Gießkanälen in Formen für die Fertigung von Dental-Werkstücken
EP0284991A2 Mar 23, 1988 Oct 5, 1988 Mitsubishi Rayon Co., Ltd. Photopolymerizable dental composition
EP0284991A3 Mar 23, 1988 Jan 10, 1990 Mitsubishi Rayon Co., Ltd. Photopolymerizable dental composition
EP0284991B1 Mar 23, 1988 Aug 26, 1992 Mitsubishi Rayon Co., Ltd. Photopolymerizable dental composition
EP0970680A2 May 28, 1999 Jan 12, 2000 Kerr Corporation Dental restorative composite
EP0970680A3 May 28, 1999 Jan 29, 2003 Kerr Corporation Dental restorative composite
EP1138272A1 Mar 30, 2000 Oct 4, 2001 Helmut Purner Method for manufacturing a dental prosthesis
EP1644441A2 Jul 15, 2004 Apr 12, 2006 Commissariat A L'energie Atomique Photopolymerizable composition based on an epoxyvinylester resin and a urethane acrylate resin and use thereof for making dental prosthesis preforms and/or models
FR2454795A1 Title not available
FR2598076A1 Title not available
FR2857668A1 Title not available
GB647261A Title not available
GB1591741A Title not available
WO1995035071A1 Jun 1, 1995 Dec 28, 1995 Minnesota Mining And Manufacturing Company Dental crown liner compostion and methods of preparing provisional restorations
WO1998035630A2 Feb 13, 1998 Aug 20, 1998 Bisco, Inc. System for fabrication of indirect dental restoratives
WO1998035630A3 Feb 13, 1998 Jan 28, 1999 Bisco Inc System for fabrication of indirect dental restoratives
WO1998036729A1 Feb 18, 1998 Aug 27, 1998 Dentsply International Inc. Low shrinking polymerizable dental material
WO1999045890A1 Feb 15, 1999 Sep 16, 1999 Stick Tech Oy A novel prepreg
WO2001012679A1 Jul 28, 2000 Feb 22, 2001 Deltamed Medizinprodukte Gmbh Composition that hardens with visible light and use thereof
WO2001074301A1 Aug 9, 2000 Oct 11, 2001 3M Innovative Properties Company Dental materials with extendable work time, kits, and methods
WO2002026197A2 Sep 25, 2001 Apr 4, 2002 Dentsply International Inc. Wax-like polymerizable dental material, method and shaped product
WO2002026197A3 Sep 25, 2001 Aug 14, 2003 Dentsply Int Inc Wax-like polymerizable dental material, method and shaped product
WO2002036039A1 Oct 31, 2001 May 10, 2002 Mattias Molin Prosthetic construct and methods for its manufacture and use
WO2002085313A1 Jan 24, 2002 Oct 31, 2002 3M Innovative Properties Company Dental composition
WO2003015720A1 Aug 15, 2002 Feb 27, 2003 3M Innovative Properties Company Hardenable self-supporting structures and methods
WO2003082142A1 Jan 13, 2003 Oct 9, 2003 Dentsply International Inc. Light curing system and method
WO2005007743A2 Jul 15, 2004 Jan 27, 2005 Commissariat A L'energie Atomique Photopolymerizable composition based on an epoxyvinylester resin and a urethane acrylate resin and use thereof for making dental prosthesis preforms and/or models
WO2005007743A3 Jul 15, 2004 Mar 17, 2005 Olivier Besnard Photopolymerizable composition based on an epoxyvinylester resin and a urethane acrylate resin and use thereof for making dental prosthesis preforms and/or models
WO2005018476A3 Jul 30, 2004 Jul 7, 2005 3M Innovative Properties Co Dental crown forms and methods
WO2005018479A1 Aug 17, 2004 Mar 3, 2005 3M Innovative Properties Company Dental article forms and methods
WO2005018484A2 Aug 19, 2004 Mar 3, 2005 3M Innovative Properties Company Hardenable dental article and method of manufacturing the same
WO2005018484A3 Aug 19, 2004 Jun 9, 2005 3M Innovative Properties Co Hardenable dental article and method of manufacturing the same
WO2005065572A1 Dec 16, 2004 Jul 21, 2005 3M Innovative Properties Company Method for making a dental appliance from an uncured, self supporting, hardena ble organic composition
WO2006119003A1 Apr 27, 2006 Nov 9, 2006 3M Innovative Properties Company Malleable symmetric dental crowns
WO2008033758A3 Sep 10, 2007 May 8, 2008 3M Innovative Properties Co Preformed malleable solid crown
WO2008033911A3 Sep 12, 2007 Mar 19, 2009 3M Innovative Properties Co Dental compositions including organogelators, products, and methods
1 "radica(TM) provisional & diagnostic resin" datasheet [online]. Dentsply Ceramico, Burlington, NJ, [retrieved on Aug. 17, 2007]. Retrieved from the Internet; 2 pgs.
2 "radica™ provisional & diagnostic resin" datasheet [online]. Dentsply Ceramico, Burlington, NJ, [retrieved on Aug. 17, 2007]. Retrieved from the Internet<URL:http://www.ceramco.com/prod—radica.shtml>; 2 pgs.
3 "REVOTEK(TM) LC Light-cured Composite Resin for Temporary Resorations" datasheet [online]. GC America Inc., Alsip, IL, [retrieved on Aug. 28, 2007]. Retrieved from the Internet; 2 pgs.
4 "REVOTEK™ LC Light-cured Composite Resin for Temporary Resorations" datasheet [online]. GC America Inc., Alsip, IL, [retrieved on Aug. 28, 2007]. Retrieved from the Internet<URL:http://www.gcamerica.com>; 2 pgs.
5 ANSI/ADA, American National Standard/American Dental Association, Specification No. 27; "Resin-Based Filling Material," Council on Dental Materials, Instruments and Equipment, American Dental Association; Chicago, IL; Jul. 16, 1993; 36 pgs. total.
6 Australian Office Action dated Aug. 18, 2006 for Australian Patent Application No. 2002331604 (2 pgs).
7 Canadian Office Action dated Feb. 15, 2010 for Canadian Patent Application No. 2,454,617 (4 pgs).
8 Canadian Office Action dated Mar. 26, 2009 for Canadian Patent Application No. 2,454,617 (6 pgs).
9 Chinese Office Action dated Aug. 26, 2005 for Chinese Patent Application No. 02815839.3 (11 pgs).
10 Chinese Office Action dated May 12, 2006 for Chinese Patent Application No. 02815839.3 (12 pgs).
11 European Patent European Office Action dated Nov. 21, 2008 for European Patent Application No. 02 76 8577.5- 2108 (4 pgs).
12 Fedors, "A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids," Polymer Sci. and Eng., Feb. 1974; 14(2):147-154.
13 International Preliminary Examination Report for PCT/US02/261234; 4 pgs.
14 ISO 4049 International Standard; "Dentistry-Polymer-based filling, restorative and luting materials," International Organization for Standardization, Geneva, Switzerland; Title Page, Publication Page, Table of Contents, and pp. 1-27 (33 pgs total) (Jul. 15, 2000).
15 ISO 4049 International Standard; "Dentistry—Polymer-based filling, restorative and luting materials," International Organization for Standardization, Geneva, Switzerland; Title Page, Publication Page, Table of Contents, and pp. 1-27 (33 pgs total) (Jul. 15, 2000).
16 Japanese Office Action dated Sep. 11, 2008 for Japanese Patent Application No. 2003-520681 (7 pgs).
17 Klee et al., "Synthesis for low shrinking composites, 2a Synthesis of branched methacrylates and their application in dental composites," Macromol. Chem. Phys., 1999; 200:517-523.
18 Lichkus, J., "Comparative DSC Study of Novel Composite Radica(TM), Cristobal®+ and Esthet-X®," The IDAR/AADR/CADR 85th General Session and Exhibition [online]. New Orleans, LA, Mar. 21-24, 2007 available online [retrieved on Aug. 24, 2007]. Retrieved from the Internet; 1 pg.
19 Lichkus, J., "Comparative DSC Study of Novel Composite Radica™, Cristobal®+ and Esthet-X®," The IDAR/AADR/CADR 85th General Session and Exhibition [online]. New Orleans, LA, Mar. 21-24, 2007 available online [retrieved on Aug. 24, 2007]. Retrieved from the Internet<URL:http://iadr.confex.com/iadr/2007orleans/techprogram/abstract—90 574.htm>; 1 pg.
20 Office Action dated Dec. 5, 2006 for U.S. Appl. No. 10/643,748; 8 pgs.
21 Office Action dated Feb. 23, 2006 for U.S. Appl. No. 10/643,748; 12 pgs.
22 Office Action dated Jun. 27, 2006 for U.S. Appl. No. 10/643,748; 10 pgs.
23 Office Action dated May 11, 2007 for U.S. Appl. No. 10/643,748; 10 pgs.
24 Plate et al., "Comb-Like Polymers, Structure and Properties," Journal of Polymer Science, Macromolecular Reviews, 1974; vol. 8; Title Page, Publication and Table of Contents page, and pp. 117-253.
25 Product Directions for Use and Material Safety Data Sheet, "Triad® Visible-Light Cure Provisional Material Directions for Use," Dentsply Trubyte, York, PA, Jun. 1997; 6 pgs.
26 Product Directions for Use, "Revotek LC Light-Cured Resin for Temporary Crown & Bridge," GG Dental Products Corp., Alslo, IL, Nov. 2000; 5 pgs.
27 Product Directions for Use, "SureFil(TM) High Density Posterior Restorative," Dentsply Caulk, Dentsply International, Inc., Milford, DE, Oct. 1998; 5 pgs.
28 Product Directions for Use, "SureFil™ High Density Posterior Restorative," Dentsply Caulk, Dentsply International, Inc., Milford, DE, Oct. 1998; 5 pgs.
29 Product Instructions for Use, "Kerr Prodigy Condensable," Kerr U.S.A., Orange, CA, 1 pg. (Available at least as early as Aug. 15, 2001).
30 Revised American National Standard / American Dental Association (ADA); Specification No. 9 for Dental Silicate Cement; ADA, Chicago, IL, Jun. 30, 1980; 17 pgs.
31 U.S. Appl. No. 09/541,417, filed Apr. 3, 2000, Karim.
32 U.S. Appl. No. 60/312,355, filed Aug. 15, 2001, Karim et al.
33 U.S. Appl. No. 60/913,037, filed Apr. 20, 2007, Karim.
34 U.S. Appl. No. 60/990,665, filed Nov. 28, 2007, Karim et al.
35 U.S. Appl. No. 60/990,672, filed Nov. 28, 2007, Karim et al.
36 U.S. Appl. No. 60/990,675, filed Nov. 28, 2007, Karim et al.
37 U.S. Appl. No. 60/990,678, filed Nov. 28, 2007, Karim et al.
38 Wan et al., "Methacrylol Derivitized Hyperbranched Polyester.2.Photo-Polymerization and Properties for Dental Resin Systems," J.M.S.-Pure Appl. Chem., 2000; A37(11):1317-1331.
39 Wan et al., "Methacrylol Derivitized Hyperbranched Polyester.2.Photo-Polymerization and Properties for Dental Resin Systems," J.M.S.—Pure Appl. Chem., 2000; A37(11):1317-1331.
U.S. Classification 523/109, 264/16, 524/401, 524/590, 264/19, 524/612, 524/81, 524/599
International Classification C08L101/00, C08K3/00, C08K5/00, C08G18/02, C08G73/06, A61K6/083, C08G63/60, A61K6/08, A61K6/10, A61K6/09, C09D5/16
Cooperative Classification A61K6/083, A61K6/0073, A61K6/087, A61K6/10
European Classification A61K6/083, A61K6/00F1, A61K6/087, A61K6/10