COMPOSITION, AND, METHOD TO PRODUCE A THREE-DIMENSIONAL DENTAL PROSTHESIS

专利摘要:
composition, and, method to produce a three-dimensional dental prosthesis. this invention relates to polymerizable material systems for printing to produce dental products such as artificial teeth, dentures, splints, varnishes, fillings, partial crowns, covers, frame patterns, crowns and bridges and the like. a dlp or stereolithographic printer is used to cure the polymerizable material in a layer-by-layer manner to form the object. the resulting three-dimensional object has good dimensional stability.
公开号:BR112015010983B1
申请号:R112015010983-7
申请日:2013-11-14
公开日:2020-12-15
发明作者:Benjamin Jiemin Sun；Christopher R. Kennedy；Veeraraghavan Sundar；Andrew M. Lichkus
申请人:Dentsply International Inc.；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[001] This patent application claims the benefit and priority for U.S. provisional patent application serial number 61 / 726,317, filed on November 14, 2012, which is hereby incorporated by reference for all purposes. TECHNICAL FIELD
[002] The present invention relates in general to rapid phototyping systems for producing dental devices such as, for example, artificial teeth, dentures, splints, varnishes, fillings, partial crowns, capes, frame patterns, crowns and bridges, molds, appliances and the like. More particularly, using light beam irradiation, such as stereolithography (SLA) or DLP (Digital Light Processor, such as EnvisionTec's Perfactory system) to constitute dental devices as three-dimensional objects from novel liquid resins of this invention. SLA using laser beam traces the shape of each layer and hardens the photosensitive resin in a vat. The Perfactory system builds three-dimensional objects using the Digital Light Processor (DLP) projector to project sequential voxel planes onto the liquid resin, which then cause the liquid resin to cure. BACKGROUND OF THE INVENTION
[003] In general, rapid phototyping refers to a conventional manufacturing process used to produce parts, in which the part is built on a layer-by-layer basis using layers of hardening material. For this technology, the part to be manufactured is considered a series of discrete cross-sectional regions that, when combined together, constitute a three-dimensional structure. The constitution of a part layer by layer is very different from conventional machining technologies, where metal or plastic parts are cut and drilled in a desired shape. In rapid phototyping technology, the parts are produced directly from computer aided design (CAD) or other digital images. Software is used to slice the digital image into thin cross-sectional layers. The part is then constructed by placing layers of plastic or other hardening material on top of each other. There are many different techniques that can be used to combine the layers of structural material. A curing step may be required to completely cure the layers of material.
[004] Inkjet printing technology is a method of rapid phototyping that can be used to manufacture the three-dimensional object. In a well-known inkjet printing method that was developed at the Massachusetts Institute of Technology, described in Sachs ET AL., US patent 5,204,055, printheads are used to discharge a binder material onto a layer of particulate sprayed on a bed of dust. The sprayed layer corresponds to a digitally overlapping section of the object that will be produced. The binder causes the dust particles to fuse together in selected areas. This causes a fused cross-sectional segment of the object to form on the platform. The steps are repeated for each new layer until the desired object is achieved, in a final step, a laser beam scans the object causing the pulverized layers to sinter and fuse together. In another inkjet printing process, described in Sanders, US patents 5,506,607 and 5,740,051, a low melting thermoplastic material is dispensed through an inkjet print head to form a three-dimensional object . A second inkjet print head dispenses with wax material to form supports for the three-dimensional object. After the object has been produced, the wax supports are removed, and the object is finished as needed.
[005] Leyden ET AL., US patents 6,660,209 and 6,270,335 disclose a method of inkjet printing using commercial print heads with multiple orifices (nozzles) to selectively fire droplets of material curable by hot molten radiation over a substrate. Each orifice can be equipped with a piezoelectric element that causes a pressure wave to propagate through the material when electrical current is applied. The print head moves along a scanning path, selectively depositing the fluid material on the substrate. In a subsequent step, light radiation is used to cure the material.
[006] Yamane ET AL., US patent 5,059,266 discloses a method of sandblasting, whereby a photocure or thermosetting resin is sandblasted along a rapid passage of the material to a stage to thereby laminate the material in the stage, changing at least one of the blasting direction of the material along the rapid passage and a blasting amount of the material, thereby controlling a blasting operation of the material, and exposing the laminated material to light to cure the material , hereby forming the article.
[007] Bredt ET AL., U.S. patent 5,902,441, describe another inkjet printing method, which involves applying a layer of powder particles containing an activatable adhesive on a flat surface that can be indexed downwards. The inkjet printer introduces an activation fluid over the particle layer in a predetermined pattern. The fluid activates the adhesive in the mixture, causing the particles to stick together in an essentially solid layer. After the first cross-sectional portion of the article is formed, the movable surface can be indexed downwards. Successive layers of the particle mixture are applied in the same way to form the desired article.
[008] Oriakhi ET AL., Publication of patent application No. US 2005/0082710, reveal an inkjet printing method, in which a blend of reactive glass ionomer particulate particles, cross-linkable polyacid particles including acid polyvinyl pyrrolidone co-polyacrylic, and nanocomposites is spread in a manufacturing compartment. An inkjet printer applies an aqueous phase binder over a predetermined area of the particulate blend to form hydrated cement. A glass-ionomer chemical reaction causes the hydrated cement to harden.
[009] Kapserchik ET AL., Publication of patent application No. US 2004/0094058 discloses an inkjet printing system using acid-base cements. Layers of pulverized particulate matter are deposited on a flat surface. The powders include a base such as a metal oxide or an aluminosilicate glass, a polymeric acid or other acid. The inkjet printer does not require an aqueous binder. The basic powder interacts with the acid in the presence of water, causing the formation of an ionically cross-linked hydrogel salt. The formation of the crosslinked hydrogel causes consolidation of the mixture.
[0010] More particularly, inkjet printing methods for producing three-dimensional dental products have been developed and are described in the patent literature. For example, Moszner ET AL., U.S. patent 6,939,489, disclose a process for manufacturing three-dimensional dental-shaped parts for dental restoration and parts replacement using three-dimensional graphic technology. The object is produced in a layered way by cutting microdroplets or microcords discharged by the nozzles in the three-dimensional graphic plotter. The discharged material can be hardened by a variety of mechanisms depending on the type of material used. This includes cooling the molten material, polycondensation, polyaddition, or thermal curing and light radiation. In the '489 patent, three-dimensional plotting technology is described as different from conventional rapid phototyping (selective laser sintering, 3D printing and stereolithography).
[0011] Rheinberger ET AL., US patent 7,189,344, disclose a process for producing three-dimensional dental restorative parts, such as partial or full dental prostheses, using inkjet printers that are used in the developed inkjet printing methods by MIT previously described. The process involves sandblasting a polymerizable material on a base support in a layer-by-layer manner. Each layer of material is polymerized by a light source before the next layer is applied. The polymerizable material is described as wax-like with up to 70% by weight of at least one of a polymerizable oligomer and monomer; from 0.01 to 10% by weight of a polymerization initiator; and at least 20% by weight of a mixture with one selected from a wax and fluid type monomer and a color pigment.
[0012] Feenstra, U.S. patents 6,921,500 and 6,955,776 disclose an inkjet printing process for manufacturing dental elements such as crowns using a liquid binder and powder bed. The element is produced by applying successive layers of powder and discharging the liquid binder over the layers using an inkjet printer. The binder preferably includes solid nanomeric inorganic particles with polymerizable and / or polycondensible organic groups on their surfaces. After the binder has been applied to the last layer of powder, any excess unbound powder is removed. Then, the pulverized layers are sintered by heating to a temperature in the range of about 400 to 800 ° C. The sintering step is performed in such a way that only bottlenecks between the dust particles are formed. The resulting sintered dental element is infiltrated by a second phase material, such as glass-ceramic or polymer, which melts at a lower temperature than the material of the dental element. This reduces the porosity of the dental element.
[0013] Bordkin ET AL., U.S. patent 6,322,728, discloses an inkjet printing process for fabricating dental restorations by printing a binder in layers of powder. The process involves depositing a layer of ceramic or composite powder material on a powder bed. The design of the restoration is based on a CAD representation. A bonding material is applied over the ceramic or composite layer. This application of powder / binder material is repeated several times to produce the desired shape of the restoration. After the layering process is completed, the structure is cured to further promote particle bonding.
[0014] The present invention provides unprecedented liquid resin systems for manufacturing three-dimensional dental devices using Digital Light Processor (DLP) projectors or other light beam irradiation, such as stereolithography. Although the DLP method or stereolithography and materials are described here basically being used to produce a base of dentures and teeth, it should be understood that these are for illustration purposes only. The DLP method or stereolithography and materials can be used to produce any dental device such as, for example, artificial teeth, dentures, splints, varnishes, fillings, partial crowns, covers, orthodontic appliances, aligners, frame patterns, crowns and bridges and similar. We provide an overview of this method and material systems below. (A more detailed description of the methods and materials used to produce the dental devices is given below).
[0015] In this method, a polymerizable liquid resin material or heated resin material like a liquid is loaded into a resin bath of a 3D printer based on a DLP or stereolithography method. In the case of using the DLP method, he builds 3D objects by projecting sequential voxel planes onto the liquid resin (or heated resin), which then polymerizes it into the solid. Successive layers of polymerized material are added in this way until the device is completely manufactured. Then, the device, for example, a denture, is washed, finished and fully cured at the end in the necessary manner. The fully cured and polished denture is now ready for use by the patient. SUMMARY OF THE INVENTION
[0016] In the present invention, several material systems are used to manufacture the dental device. The materials of this invention are suitable for dental application and cured to a high mechanical strength and have excellent physical properties. In addition, these materials have good biocompatibility, making them ideal for dental applications. These polymerizable materials can be prepared using the following components. Polymerizable Materials for Printing
[0017] A polymerizable material for printing is used to manufacture dental products according to the methods of this invention. The term "for printing", as used herein, means a material that is flowable (fluid) at a temperature below room temperature, at room temperature and above room temperature.
[0018] Fluid material has a fluidity temperature in the range of - 30 ° C to 140 ° C. The following components can be used to prepare the polymerizable material for printing according to this invention. Polymerizable Acrylic Compounds
[0019] Polymerizable acrylic compounds that can be used in the compositions of this invention include, but are not limited to, mono-, di- or poly-acrylates and methacrylates such as methyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate, methacrylate ethyl, isopropyl methacrylate, (meth) tert-butyl acrylate, (meth) cyclohexyl acrylate, (meth) 4-tert-butylcyclohexyl acrylate, (t) tetrahydrofurfuryl acrylate, n-hexyl acrylate , (meth) 2-phenoxyethyl acrylate, stearyl acrylate, allyl acrylate, (meth) isobornyl acrylate, (meth) stearyl acrylate, (meth) benzyl phenoxy acrylate, (meth) phenylphenyl ethyl acrylate, diacrylate tris (2-hydroxy ethyl) isocyanurate, the product of the reaction of octadecyl isocyanate and caprolactone of ethyl 2- (methacryloyloxy) ester, the product of the reaction of octadecyl isocyanate and ethyl 2-hydroxyacrylate; the reaction product of octadecyl isocyanate and hydroxypropyl (meth) acrylate; the reaction product of octadecyl isocyanate and 2-hydroxypropyl 2- (methacryloyloxy) -ethyl phthalate; the reaction product of octadecyl isocyanate and 2-hydroxy-3-phenoxypropyl acrylate; the reaction product of octadecyl isocyanate and glycerol dimethacrylate; the reaction product of octadecyl isocyanate and pentaerythritol triacrylate; the reaction product of cyclohexyl isocyanate and 2-hydroxyethyl (meth) acrylate; the reaction product of benzyl isocyanate and 2-hydroxyethyl (meth) acrylate; 1,14- tetradecanedimethacrylate, tricyclodecane dimethylol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate; 1,3-propanediol, trimethylpropane tri (meth) acrylate, 1,2,4-butanethiol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,4-cyclohexanediol dimethacrylate, di (meth) acrylate 6-hexanediol, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexacrylate, 2,2-bis [4- {2-hydroxy-3-acryloyloxypropoxy) phenyl] propane; 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl] propane (Bis-GMA); the product of the Bis-GMA reaction and octadecyl isocyanate; the reaction product of Bis-GMA and cyclohexyl isocyanate; 2,2-bis [4- (acryloyloxy-ethoxy) phenyl] propane; 2,2-bis [4- (methacryloyloxy-ethoxy) phenyl] propane (or ethoxylated bisphenol A dimethacrylate) (EBPADMA); urethane di (meth) acrylate (UDMA), diurethane dimethacrylate (DUDMA), 4, 3-dioxo-3,14 dioxa-5,12-diazaexadecane-1, 16-diol diacrylate; 4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6,1-diol dimethacrylate; 4,19-dioxo-3,20 diacrylate dioxa-5,18-diazaexadecane-1,22-diol; 4.19-dioxo-3,20 dimethacrylate dioxa-5,18-diazaexadecane-1,22-diol; the reaction product of trimethyl 1,6-diisocyanate-hexane and bisphenol A propoxylate and 2-hydroxyethyl methacrylate (TBDMA); the reaction product of 1,6 diisocyanate-hexane and 2-hydroxyethyl methacrylate with water modified (HDIDMA); the reaction product of 1,6-diisocyanate-hexane and water-modified ethyl 2-hydroxyacrylate (HDIDA); the reaction product of 1,6-diisocyanate-hexane, 1,2-decanediol, 1, 10-decanediol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanate-hexane, 3-hydroxy 2,2-dimethylpropyl 3-hydroxy-2,2-dimethyl, 1, 10-decanediol and 2-hydroxyethyl (meth) acrylate reaction; the reaction product of 1,6-diisocyanate-hexane, 1,0-decanediol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanate-hexane, 1,2-decanediol, 1, 10-decanediol, 3-hydroxy 2,2-dimethylpropyl 3-hydroxy-2,2-dimethyl and (met) reaction 2-hydroxyethyl acrylate; the reaction product of 1,6-diisocyanate-hexane, trimethyl 1,6-diisocyanate-hexane, 1, 10-decanediol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanate-hexane, trimethyl 1,6-diisocyanate-hexane, 3-hydroxy 2,2-dimethylpropyl 3-hydroxy-2,2-dimethyl, 1, 10- decanediol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanatohexane, 2,5-dimethyl-2,5-hexanediol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanate-hexane, 4,4'-isopropylidenodicyclohexanol and 2-hydroxyethyl (meth) acrylate; the reaction product of 1,6-diisocyanate-hexane, 1,2-decanediol, 1, 10-decanediol, 3-hydroxy 2,2-dimethylpropyl 3-hydroxy-2,2-dimethyl and (met) reaction 2-hydroxyethyl acrylate; the reaction products of ethyl 2-isocyanatomethacrylate and diols; polyurethane dimethacrylate (PUDMA); alkoxylated pentaerythritol tetra-acrylate; polycarbonate dimethacrylate (PCDMA); bis-acrylates and bis-methacrylates of polyethylene glycols; modified (meth) acrylate silicones; light curable epoxides; epoxy methacrylate (or acrylate), methacrylate (or acrylate) compounds or combinations thereof; various epoxides in combination with various diols [such as 1,3-bis (3-glycidyloxypropyl) tetramethyladisoxane, bisphenol A diglycidyl proxylate, bis (3,4-epoxy-6-methylacyclohexylamethyl) adipate, 1, 10 decanediol, 1,6-hexanediol, branched diol, aromatic diol, bisphenol A, proxylated bisphenol A, etc. Epoxy compounds polymerize by ring opening polymerization contract less because of the increase in extruded free volume associated with the ring opening process in addition to the volume expansion of the phase conversion]; and copolymerizable mixtures of acrylated monomers and acrylated oligomers, and the like.
[0020] The polymerizable acrylic compound can be present in an amount of at least about 10% by weight and preferably at least about 35% by weight of the general polymerizable composition. In addition, the polymerizable acrylic compound can be present in an amount of less than about 99.9% by weight, and preferably less than about 95% by weight of the general polymerizable composition. For example, the polymerizable acrylic compound can range from about 10% to about 99.9% by weight, and preferably from about 35 to about 95% by weight of the general polymerizable composition. Polymerization System
[0021] Polymerizable dental materials for printing and compositions of this invention may include one or more initiation systems to cause them to harden readily. Dental light-curable compositions or composites preferably include a light sensitizer, for example, camphorquinone, 2,4,6-trimethylabenzyldiphenylphosphine oxide, or methyl benzoin which causes polymerization to be initiated upon exposure to light activation wavelengths; and / or a reducing compound, for example, tertiary amine.
[0022] In one embodiment, a photoactive agent, such as, for example, benzophenone, benzoin and its derivatives, or alpha-diketones and their derivatives is added to the composition in order to make it curable with light. A preferred polymerization photoinitiator is camphorquinone (CQ). Cationic polymerization initiator, 4-octyloxy-phenyl-phenyl iodonium hexafluorantimonate (OPPI), can also be used, which initiates ring-opening polymerization as well as volume expansion of the phase change to reduce polymerization shrinkage. Light curing can be initiated by irradiating the composition with visible blue light, preferably with a wavelength in the range of about 400 to about 500 nm. A standard dental blue light curing unit can be used to irradiate the composition. Camphorquinone (QC) compounds have a maximum light absorbance between about 400 to about 500 nm and generate free radicals for polymerization when irradiated with light with a wavelength in this range. Selected photoinitiators from the acylphosphine oxide class can also be used. Such compounds include, for example, monoacyl phosphine oxide, bisacyl phosphine oxide derivatives, and triacyl phosphine oxide derivatives. For example, 2,4,6-trimethylabenzoyl-diphenyl-phosphine oxide (TPO) can be used as the polymerization photoinitiator.
[0023] In addition to the photoactive agents, the material of this invention can include a polymerization inhibitor such as, for example, butylated hydroxytoluene (BHT); hydroquinone; monomethyl hydroquinone ether; benzoquinone; chloranil; phenol; butyl hydroxyanaline (BHA); tertiary butyl hydroquinone (TBHQ); tocopherol (Vitamin E); and the like. Preferably, butylated hydroxytoluene (BHT) is used as the polymerization inhibitor. Polymerization inhibitors act as removers to trap free radicals in the composition and prolong the shelf life of the material.
[0024] In one embodiment, a material referred to as "ALF" comprising camphorquinone (CQ); butylated hydroxytoluene (BHT); N, N-dimethylaminonopentyl acrylate, gamma-methacryloxypropyl trimethoxy silane and methacrylic acid can be used in the composition.
[0025] The initiator component can be present in an amount of at least 0.05% by weight, and preferably at least about 0.3% by weight of the general polymerizable composition. The general polymerizable composition can include less than about 20% and more preferably less than about 5% by weight of the initiator component. For example, the initiator component can be present in a range of from about 0.05% to about 10%, and preferably from about 0.3% to about 5% by weight of the general polymerizable composition. Loads
[0026] Conventional filler materials such as inorganic fillers, which can be naturally occurring or synthetic, can be added to the material and polymerizable dental composition for printing. Such materials include, but are not limited to, silica, titanium dioxide, iron oxides, silicon nitrides, glasses such as calcium-based glasses, lead, lithium, cerium, tin, zirconium, strontium, barium and aluminum, borosilicate glasses , strontium borosilicate, barium silicate, lithium silicate, aluminum lithium silicate, kaolin, quartz and talc. Preferably, the silica is in the form of silanized fumed silica. Preferred glass fillers are barium aluminosilicate and silanized boron and barium fluoride aluminosilicate and silanized boron. Preferably, these inorganic fillers can be suspended in polymerizable resin for printing. Organic particles such as poly (methyl methacrylate) (PMMA), highly cross-linked PMMA microspheres, poly (methyl / ethyl methacrylate), poly (methyl / butyl methacrylate), rubber-modified PMMAs, rubber impact modifiers, polyacrylates crosslinked, thermoplastic and crosslinked polyurethanes, ground polymerized compounds of this invention, polyethylene, polypropylene, polycarbonates and polyepoxides, and the like can also be used as fillers. These organic fillers can be added to the polymerizable resin for printing described above. Preferably, these organic fillers can dissolve or suspend in polymerizable resin for printing.
[0027] Inorganic filler particles can be treated on the surface with a silane compound or other coupling agent to improve the bond between the particles and the resin matrix. Suitable silane compounds include, but are not limited to, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, and combinations thereof.
[0028] Loading is optional. The filler component can be present in an amount of at least 0% by weight, and more preferably at least about 2% by weight of the general polymerizable composition. In addition, the filler component may be present in an amount less than about 75% by weight and more preferably less than about 65% by weight of the general polymerizable composition. For example, the filler component can be present in a range of about 0 to about 75, and preferably about 2 to about 65% by weight of the general polymerizable composition. Pigments
[0029] Examples of inorganic pigment include, but are not limited to, black iron oxide, yellow iron oxide, ultramarine blue, brown iron oxide, titanium oxide, zinc flower, zinc oxide, iron oxide, aluminum oxide , silicon dioxide, talc, barium sulphate, calcium sulphate, red oxide, chromium cobalt green, Armenian blue, carbon black, mica, cobalt violet, molybdenum red, titanium cobalt green, molybdate orange, etc. Examples of organic pigments include Cromophtal Red-BRN 2-naphthalenecarboxamide, azo pigments, polyazzo pigments, azomethine pigments, isoindoline pigments, anthraquinone pigments, phthalocyanine pigments, benzimidazolone pigments, etc.
[0030] Pigmented materials based on polymerizable resins for printing of this invention contain one or more pigments as coloring or shading agents. Pigments include inorganic pigments and organic pigments. Pigments can be modified to increase dispersibility. For example, pigments modified with a silane group, a polymerizable silane group, a dialkylaminomethyl group or a dialkylaminoethysphonic acid group are preferred. In a further example, inorganic pigments can be treated on the surface with a silane compound or other coupling agent to improve the bond between the particles and the resin matrix and dispersion in materials. Suitable silane compounds include, but are not limited to, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, and combinations thereof.
[0031] The term "pigment" refers to visible materials that are not soluble, but are suspended or dispersed as fine particles in the object materials. The preferred solid pigments are those with fine particle pigments, such as black iron oxide 7053, yellow iron oxide 7055, titanium dioxide, Cromophtal Red-BRN 2-naphthalenecarboxamide, N, N'-2-chlorine-1,4- phenylene) bis {4 - {(2,5-dichlorophenyl) azo} -3-hydroxy-}, ultramarine blue and brown iron oxide 420. In addition, a fluorescent agent can be included, such as Lumilux Blue LZ fluorescent agent (dihydroxy acid terephthalate ester). The pigment surface can be organically modified to improve its compatibility with the resin matrix. Pigments can also be prepolymerized in a resin matrix as small microspheres or in bulk and then ground into powder, in order to improve their suspension in low viscosity liquid resins. Polymerizable materials for printing are applied directly to form dental devices and solidify immediately by irradiation / light projection, material migration is prevented and dimensional accuracy is achieved.
[0032] Pigmented materials are desirable because they have superior hue stability and can even withstand UV light irradiation. This invention overcomes the potential pigment separation of dental resins by better dispersing the particles in the solution to prevent settling and grinding into smaller particles. This invention further overcomes the potential pigment separation of dental resins using nanodispersed and fine inorganic and organic pigments.
[0033] The pigment is optional. Clear formulations do not need any pigment. The pigment component can be present in an amount of at least 0% by weight, and more preferably at least about 0.001% by weight of the general polymerizable composition. The general polymerizable composition can also include less than about 5% by weight and more preferably less than about 1% by weight of the pigment component. For example, the pigment component can be present in a range of from about 0 to about 5%, and preferably from about 0.001 to about 1% by weight of the general polymerizable composition.
[0034] Compositions of polymerizable dental materials for printing of the invention can include various inorganic and organic fillers, pigments, initiators, catalysts, stabilizers, plasticizers, fibers or combinations thereof. Preferred stabilizers are butylated hydroxytoluene (BHT) and hydroquinone methyl ether (EHQ). They can also include compounds to introduce radiopacity into the material.
[0035] Polymerizable dental materials for printing of the invention are able to solidify quickly upon irradiation of light. Rapid solidification provides a combination of fluidity and dimensional stability, depending on its temperature before polymerization. Rubber Impact Modifier
[0036] This invention provides an unprecedented rubber impact modifier approach by using the special selected rubber impact modifier (eg S2006, a silicone rubber based on Mitsubishi Raioon Co.) in a resin / liquid system, where the core-shell rubber impact modifier (core is silicone, shell is acrylic PMMA) does not dissolve, but swells and forms a colloid at room temperature or elevated temperature. Surprisingly, this unprecedented approach provides significantly improved impact strength and fracture toughness of the resin / liquid system. In accordance with a preferred form of the present invention, novel rubber modified resin / liquid impact dental compositions are provided, which are polymerized by known techniques, such as light irradiations, in prosthetic devices that have chemical and physical properties that are significantly improved over those of dental devices made of non-rubber modified impact resin / liquid composition or even conventional acrylic materials of the prior art. Notably, dental devices, such as, for example, various prosthetic devices, such as denture bases, produced from an unprecedented modified rubber resin / liquid impact dental composition prepared according to the invention are characterized by better fracture toughness.
[0037] In addition, denture devices, such as denture bases, produced from novel rubber-modified resin / liquid impact compositions of the invention have excellent stain, chemical and solvent resistance. They also have excellent bonding strength on plastic acrylic teeth or other dental devices on the market. In comparison with light curable denture bases, even conventional acrylic denture bases, the denture bases produced in accordance with this invention are characterized by exceptional fracture toughness.
[0038] The novel rubber modified impact resin / liquid compositions are formed according to the invention by combining at least one monomer, crosslinking agents for said monomer, at least one rubber impact modifier, which disperses evenly and maintains a homogeneous appearance in this resin / liquid.
[0039] In general, it is preferable that the general polymerizable composition includes at least one impact modifier. In the form used herein, as with any other ingredient of the present invention, the term "impact modifier" can include an impact modifier or several impact modifiers. Various impact modifiers can be employed in the practice of the present invention and often include one or more elastomers. It is generally preferred that the impact modifier is at least 0.5%, more typically at least 1%, even more typically at least 2%, still more typically at least 3% and even more typically at least 5% by weight of general polymerizable composition and it is also preferable that the impact modifier is less than 40%, more typically less than 25%, even more typically less than 15% by weight of the general polymerizable composition, although greater or lesser amounts may be used in particular embodiments. For example, the impact modifier can be present in an amount ranging from about 2% to about 40%, typically from about 3% to about 25%, and preferably from about 5% to about 15% in weight of the general polymerizable composition.
[0040] Rubber impact modifiers are in the form of small particles with average diameters ranging from about 0.01 micron to about 100 microns. Preferably, particles have diameters ranging from 0.02 microns to about 20 microns. More preferably, particles have diameters ranging from 0.05 microns to about 10 microns. The particles of the rubber impact modifiers are completely dispersed in the monomer, crosslinking agents and the rest of the molten liquid / resin. Its hard shells are fully swollen and penetrated by the monomer / oligomer used. The soft cores remain relatively intact in order to maintain different hard and soft phases and provide adequate suspension in the rest of the components in the composition and make a part of the network of crosslinked and interpenetrating polymer. It has been found that the composition of this rubber impact modifier and the relative proportion of this modifier dramatically affects the impact strength and toughness on fracture of the final cured composition, as well as the handling properties in the uncured stage. This invention provides components for a desired composition in terms of obtaining the desired properties in the final hardened or cured product produced from them, notably impact resistance and fracture toughness.
[0041] The present invention can provide modified rubber impact compositions, which are particularly useful in the production of light-curable dental materials, for example, denture bases, with properties, especially fracture toughness, superior to those of curable denture bases with light or even conventional acrylic systems currently used in the art. Advantageously, the modified impact compositions of the present invention allow the introduction of homogeneous rubber modified impact liquids / resins, unique rubber impact modifiers, which improve the impact resistance and toughness in the fracture of the cured product surprisingly.
[0042] In the form used herein, the term core / shell impact modifier may denote an impact modifier in which a substantial portion (for example, greater than 30%, 50%, 70% or more by weight) of it is comprised of a first polymeric material (i.e., the first material or core material) which is substantially all encapsulated by a second polymeric material (i.e., the second material or shell material). The first and second polymeric materials, in the form used herein, can be comprised of one, two, three or more polymers which are combined and / or reacted with each other (for example, sequentially polymerized) or can be part of separate core / shell systems or the same.
[0043] The first and second polymeric materials of the core / shell impact modifier may include elastomers, polymers, thermoplastics, copolymers, other components, combinations thereof or the like. In preferred embodiments, the first polymeric material, the second polymeric material or both of the core / shell impact modifier include or are substantially entirely compounds (for example, at least 70%, 80%, 90% or more by weight) of one or more thermoplastics. Exemplary thermoplastics include, without limitation, polycarbonate, polyester, polyolefin, polystyrene polypropylene, poly (ethylene terephthalate), poly (vinyl chloride), polyamide, polyethylene, poly (butylene terephthalate), acrylonitrile-butadiene-styrene resin, polymethacrylate methyl, or the like, and / or any combination thereof. Desirably, silicone-acrylic rubber and / or butadiene-based rubber (for example, MMA-butadiene-styrene or acrylonitrile-butadiene-styrene) core / shell impact modifiers can be included to achieve both superior high resistance to impact and / or excellent resistance to weathering.
[0044] Examples of useful core-shell graft copolymers are those where hard compounds, such as styrene, acrylonitrile or methyl methacrylate, are grafted onto the core made of polymers of compounds with soft or elastomeric material such as butadiene or butyl acrylate. The core polymer can also include other compounds containing copolymerizable material, such as styrene, vinyl acetate, methyl methacrylate, butadiene, isoprene or the like. The polymer material of the core may also include a crosslinking monomer with two or more unconjugated double bonds of approximately equal reactivities such as ethylene glycol diacrylate, butylene glycol dimethacrylate, and the like. The polymer material of the core may also include a graft bonding monomer with two or more unconjugated double bonds of different reactivities.
[0045] A characteristic of the modified rubber impact liquid / resin is that the rubber impact modifier will be insoluble, but will absorb or soak, in the liquid or molten polymerizable monomer component used in the preparation of the modified rubber impact liquid / resin and it will form a colloid at room temperature or elevated temperature, a homogeneous mixture at room temperature or elevated temperature. A desirable rubber impact modifier may include a multilayer polymer that is made up of the core layer (s) containing a composite rubber containing an acrylic component and a silicone component and the layer (s) of the bark. Preferably, the multilayer polymer does not contain unreacted epoxy groups and / or unreacted allyl groups as constituent components, although not required. Rubber impact modifiers that can be used in the composition of this invention include, but are not limited to, Metablen S2006, S2001, S2030, SRK200, C223 (all sold by Mitsubishi Raioon Co.), and D440 (sold by Arkema), etc. Methods 3D printing using DLP system and 3D printing using stereolithography
[0046] In general, these two approaches (DLP printer or stereolithographic printer) can be used to manufacture the three-dimensional object using the materials of this invention.
[0047] Following each of these approaches, the polymerizable material for printing is fluid or heated to form a fluid liquid. The printer builds successive layers of the polymerizable material by projecting or radiating light onto the construction and curing plane to form the denture or other dental device. The resulting denture or other dental device must have excellent mechanical and physical properties, hue and color properties.
[0048] Various polymerizable materials for printing with different hues and colors can be prepared and placed in separate baths. In a case of building a denture, the denture base is constructed from the tinted bath of the denture base layer by layer. This denture base is washed and transferred to a dentin bath to build up part of the dentin of the denture tooth at the base of the denture layer by layer. After being washed it is transferred to an enamel bath, where a layer of enamel is built layer by layer and forms a final denture device with integral teeth at the base of the denture.
[0049] In a case of mass production of denture teeth, multiple teeth can be constructed by first forming multiple neck parts of denture teeth in a neck resin bath, and adding body parts of denture teeth in the resin bath of the body, finally building enamel parts of denture teeth in a resin enamel bath and final curing to form multiple denture teeth. Multiple baths in the ambient atmosphere and high temperature can be used in the desired way to achieve the desirable aesthetics of the formed dental devices.
[0050] Preferably, high strength dental products are produced by the methods of this invention. In a preferred embodiment, the polymerizable material for printing (without reinforcement charges) can be cured from the printer to produce the high strength dental product. "High strength" in the form used here means that the products have a flexural modulus of at least 1,378.9 mPa and a flexural strength of at least 34.47 mPa. More preferably, the product has a flexural modulus of at least 2,068.4 mPa and a flexural strength of at least 55.15 mPa. Above all, the product preferably has a flexural modulus of at least 2,413.1 mPa and a flexural strength of at least 82.73 mPa. "Flexural strength and flexural modulus" as used here refer to properties measured according to the methods of ASTM D790 (1997).
[0051] Also, as described in the following examples, various formulations of polymerizable materials for printing can be prepared for use in a printing device. It is important that the formulations have sufficiently low viscosity so that they can be handled and cured and the device can be easily removed from the liquid resin bath (reservoir). At the same time, formulations must be able to produce dental products with sufficient mechanical strength and integrity. Various polymerizable materials for printing fluids have been prepared with various hues for different applications. Polymerizable materials for fluid printing have been successfully cured locally to form various 3D objects. Several selected examples are shown in the Example Section. The materials of this invention were cured in this way layer by layer and formed into 3D dental objects that can be separated from the rest of the liquid resin in the 3D printer bath. In addition, washing solvents (eg, ethyl acetate, alcohols, acetone, THF, heptane, etc. or combinations thereof) can be used to remove uncured resin from 3D dental objects and final curing or heat treatment can be used to improve its mechanical and physical properties as well as its performance. Air barrier coating or sealer can be used before final curing. Inert atmosphere can be used for final curing of dental devices or mass production of dental devices (for example, denture teeth, denture bases, crowns) in a manufacturing environment.
[0052] Alternatively, the materials of this invention can be made by other means to construct 3D objects. Furthermore, the resin systems developed in this invention can be used in other industries, such as aerospace, animation and entertainment, architecture and art, automotive, consumer goods and packaging, education, electronics, hearing aids, sports products, jewelry , medical, manufacturing, etc. EXAMPLES EXAMPLE 1 Preparation of Oligomer
[0053] A reactor was charged with 1,176 grams of trimethyl-1,6-diisocyanate-hexane (5.59 mol) and 1,064 grams of bisphenol A propoxylate (3.09 mol) under a dry nitrogen flow and heated to about 65 ° C under positive nitrogen pressure. To this reaction mixture, 10 drops of dibutyltin dilaurate catalyst were added. The temperature of the reaction mixture was maintained between 65 ° C and 140 ° C for about 70 minutes and followed by an additional 10 drops of dibutyltin dilaurate catalyst. An intermediate product capped at the viscous paste isocyanate end was formed and stirred for 100 minutes. To this intermediate product, 662 grams (5.09 mol) of 2-hydroxyethyl methacrylate and 7.0 grams of BHT as an inhibitor were added over a period of 70 minutes while the reaction temperature was maintained between 68 ° C and 90 ° C. ° C. After about five hours of stirring at 70 ° C, heating was turned off, and the oligomer was collected from the reactor as a semi-translucent flexible solid and stored in a dry atmosphere. EXAMPLE 2 Monomer Preparation
[0054] A reaction flask was loaded with 700 grams of 1,6-diisocyanate-hexane and heated to about 70 ° C under positive nitrogen pressure. To this reactor, 1,027 grams of 2-hydroxyethyl methacrylate, 0.75 grams of dibutyltin dilaurate catalyst and 4.5 grams of butylated hydroxytoluene (BHT) were added. The addition was slow and under a dry nitrogen flow for a period of two hours. The temperature of the reaction mixture was maintained between 70 ° C and 90 ° C for two more hours and followed by the addition of 8.5 grams of purified water. One hour later, the reaction product was discharged as a clean liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere. EXAMPLE 3 Monomer Preparation
[0055] A reaction flask was loaded with 168 grams of 1,6-diisocyanate-hexane and heated to about 70 ° C at a positive nitrogen pressure. To this reactor were added 228 grams of 2-hydroxyethyl acrylate, 0.12 grams of dibutyltin dilaurate catalyst and 0.86 grams of butylated hydroxytoluene (BHT). The addition was slow and under a dry nitrogen flow for a period of two hours. The temperature of the reaction mixture was maintained between 70 ° C and 85 ° C for another three hours and followed by the addition of 0.9 grams of purified water. One hour later, the reaction product was discharged as a clean liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere. EXAMPLE 4 Monomer Preparation
[0056] A reaction flask was loaded with 200 grams of octadecyl isocyanate and heated to about 78 ° C at a positive nitrogen pressure. To this reactor were added 90.6 grams of 2-hydroxyethyl methacrylate, 0.14 grams of dibutyltin dilaurate catalyst and 0.58 grams of butylated hydroxytoluene (BHT). The addition was slow and under a dry nitrogen flow for a period of two hours. The temperature of the reaction mixture was maintained between 70 ° C and 85 ° C for an additional three hours, and the reaction product was discharged as a clean liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere. EXAMPLE 5 Preparation of Urethane Monomer (UCDPMAA)
[0057] A 500 mL flask was loaded with 38.8 grams (0.200 mol) of 1,3-bis (isocyanatomethyl) cyclohexane under a dry nitrogen flow and heated to about 60 ° C under positive nitrogen pressure. To this reaction mixture, 3 drops of dibutyltin dilaurate catalyst were added. A mixture of 22.7 grams of 2-hydroxy-3-phenoxy acrylate, 26.6 grams (0.204 mol) of 2-hydroxyethyl methacrylate, 11.5 grams (0.099 mol) of 2-hydroxyethyl acrylate and 0 , 10 grams of BHT as an inhibitor were added over a period of 70 minutes while the reaction temperature was maintained between 56 ° C and 78 ° C. After about four hours of stirring, the heating was turned off, and the monomer was collected from the flask as a viscous liquid and stored in a dry atmosphere. EXAMPLE 6 Organic fill material
[0058] A polymerizable dental material was prepared by stirring a liquid mixture of 38.65 grams of oligomer at 85 ° C (for example, about 25 to about 55%, preferably from about 30 to about 45% by weight of the organic filler material) produced following the procedure of Example 1; 46.5 grams of the compound of Example 2 (for example, about 30 to about 60, preferably about 35 to about 55% by weight of the organic filler); 6.5 grams of the compound of Example 3 (for example, about 0.5 to about 15%, preferably from about 1 to about 10% by weight of the organic filler); 8.0 grams of the compound of Example 4 (for example, about 0.5 to about 20%, preferably from about 1 to about 15% by weight of the organic filler); and 0.35 grams of 2,4,6-trimethylabenzoyldiphenylphosphine oxide, (Lucirin TPO produced by BASF) (for example, about 0.005 to about 10%, preferably from about 0.05 to about 5% by weight organic material). This material was light cured and subsequently ground to form particulate powder containing particles with an average particle size in the range of about 1 to about 150 microns, preferably about 2 to about 50 microns. Alternatively, these polymer microspheres can be produced by suspension or emulsion polymerizations. EXAMPLE 7 Composite loading material
[0059] A polymerizable dental composite material was prepared by stirring at 85 ° C a liquid mixture of 4.12 grams of oligomer produced following the procedure of Example 1 (for example, about 0.5 to about 15, preferably about 1 to about 10% by weight of the composite loading material); 4.20 grams of the compound of Example 2 (for example, about 0.5 to about 15, preferably about 1 to about 10% by weight of the composite filler); 1.45 grams of the compound of Example 3 (for example, about 0.05 to about 10, preferably about 0.5 to about 5% by weight of the composite filler); 5.45 grams of 7,7,9-trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1, 16-diol dimethacrylate (for example, about 0.5 to about 15 , preferably from about 1 to about 10% by weight of the composite filler); 6.00 grams of Ethoxylated Bisphenol A Dimethacrylate (SR348 from Sartomer Company, Inc.) (e.g., about 0.5 to about 20, preferably about 1 to about 15% by weight of the composite filler) ; 2.00 grams of silane fumed silica (SiO2) (e.g., about 0.05 to about 15, preferably from about 0.5 to about 10% by weight of the composite filler) with a particle size average of about 0.01 to about 0.04 micrometers; 62 grams of BAFG silane barium aluminofluorsilicate glass particles (for example, about 40 to about 80, preferably about 50 to about 70% by weight of the composite filler) with an average particle size of about from 0.1 to about 1 micrometer; 14 grams of BAFG silane barium aluminofluorsilicate glass particles (for example, about 1 to about 30, preferably about 5 to about 25% by weight of the composite filler) with an average particle size of about from 1 to about 10 micrometers; and 0.28 grams of visible light initiation solution (for example, about 0.005 to about 10, preferably from about 0.05 to about 5% by weight of the composite filler) containing 5-20% ( for example, about 13.3%) of camphorquinone (QC), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) N, N-dimethylaminoethylaneopentyl acrylate, and 5-30% (for example, about 16.3%) y-methacryloxypropyltrimethoxysilane. This material was light cured and subsequently ground to form particulate powder containing particles with an average particle size in the range of about 1 to about 150 microns, preferably about 2 to about 50 microns. Alternatively, these composite microspheres can be produced by suspension or emulsion polymerizations. EXAMPLE 8 Organic fill material
[0060] A polymerizable dental material was prepared by stirring a liquid mixture of 40 grams of oligomer produced at 85 ° C following the procedure of Example 1 (for example, about 20 to about 60, preferably from about 30 to about 50 % by weight of the organic filler); 39.25 grams of the compound of Example 2 (for example, about 20 to about 60, preferably about 30 to about 50% by weight of the organic filler); 20 grams of the compound of Example 3 (for example, about 5 to about 40, preferably about 10 to about 30% by weight of the organic filler); 0.75 gram of visible light initiation solution (for example, about 0.005 to about 10, preferably from about 0.05 to about 5% by weight of the organic filler material) containing 5-20% (for example example, about 13.3%) of camphorquinone (CQ), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1 , 3%) butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) of N, N-dimethylaminoethylanopentyl acrylate, and 5-30% (for example, about 16.3%) of y- methacryloxypropyltrimethoxysilane. This material was subsequently ground to cryogenic temperature to form particulate powder containing particles with an average particle size in the range of about 1 to about 150 micrometers. Alternatively, these polymer microspheres can be produced by suspension or emulsion polymerizations. EXAMPLE 9 Composite loading material
[0061] A polymerizable dental composite material was prepared by mixing a mixture of 51 grams of oligomer produced following the procedure of Example 1 (for example, about 1 to about 25, preferably about 5 to about 20% by weight of the composite loading material); 28 grams of the compound of Example 2 (for example, about 0.5 to about 20, preferably about 1 to about 10% by weight of the composite filler); 18 grams of the compound of Example 3 (for example, about 0.5 to about 15, preferably about 1 to about 10% by weight of the composite filler); 59.93 grams of silane fumed silica (SiO2) (for example, about 1 to about 30, preferably about 5 to about 20% by weight of the composite filler) with an average particle size of about 0.01 to about 0.04 micrometers; 179.8 grams of BAFG silane barium aluminum fluorosilicate glass particles (e.g., about 20 to about 70, preferably about 40 to about 60% by weight of the composite filler material) with a medium particle size from about 0.1 to about 1 micrometer; 59.93 grams of BAFG silane barium aluminum fluorosilicate glass particles (e.g., about 1 to about 30, preferably about 5 to about 20% by weight of the composite filler) with a medium particle size from about 1 to about 10 micrometers, 0.08 grams of # 115 Phosphor (e.g., about 0.005 to about 5, preferably from about 0.009 to about 0.1% by weight of the composite filler) ; 0.0192 grams of Lumilux Blue LZ fluorescent agent (dihydroxy acid ester terephthalate) (for example, about 0.0005 to about 0.1, preferably from about 0.001 to about 0.05 by weight of the material composite load); 0.4 gram of Lucirin-TPO (2,4,6-Trimethylabenzoyldiphenylphosphine oxide) (for example, about 0.01 to about 5, preferably about 0.05 to about 1% by weight of the composite load); and 2.0 grams (0.50%) of visible light initiation solution (for example, about 0.05 to about 5, preferably from about 0.1 to about 1% by weight of the composite filler) containing 5-20% (for example, about 13.3%) of camphorquinone (QC), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) N, N-dimethylaminoethylenepentyl acrylate, and 5-30% (for example, about 16.3%) of Y-methacryloxypropyltrimethoxysilane. This composite material was subsequently ground at cryogenic temperature to form powders with an average particle size ranging from about 1 to about 150 microns, preferably about 2 to about 50 microns. Alternatively, these composite microspheres can be produced by suspension or emulsion polymerizations. Polymerizable compositions for printing
[0062] Polymerizable compositions for printing are used in a 3D printer resin construction bath to manufacture dental objects. These compositions may contain acrylate or methacrylate monomers or oligomers, polymers, fillers, pigments, stabilizers and light curable initiators, etc. Preferably, these resins will form fluid liquids at room temperature or elevated temperatures and will cure quickly at those temperatures required for different resins to form 3D objects layer by layer. This causes stable three-dimensional objects to be formed immediately. EXAMPLE 10 Dental materials
[0063] A polymerizable dental material was prepared by stirring a liquid mixture of 38 grams of oligomer produced at room temperature following the procedure of Example 1 (for example, about 15 to about 50, preferably about 25 to about 40% weight of dental material); 57 grams of methyl methacrylate (MMA) (for example, about 30 to about 80, preferably about 40 to about 70% by weight of dental material); 4 grams of ethylene glycol dimethacrylate (for example, about 0 to about 15, preferably from about 1 to about 10% by weight of the dental material), and 1.0 gram of visible light initiation solution (eg example, about 0.05 to about 10, preferably about 0.1 to about 5% by weight of dental material) containing 5-20% (e.g., about 13.3%) of camphorquinone (QC ), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) butylated hydroxytoluene (BHT), 30- 60% (for example, about 46%) of N, N-dimethylaminoethylanopentyl acrylate, and 5-30% (for example, about 6.3%) of Y-methacryoxypropyltrimethoxysilane. EXAMPLE 10A Dental materials
[0064] A polymerizable dental material was prepared by stirring at 35 ° C a liquid mixture of oligomer produced at room temperature following the procedure of Example 1 (for example, about 15 to about 50, preferably about 20 to about 40% by weight of dental material); 46.0 grams of methyl methacrylate (MMA) (for example, about 30 to about 60, preferably about 40 to about 55% by weight of the dental material); 10 grams of ethyl 2-phenoxyacrylate (for example, about 0 to about 30, preferably about 5 to about 20% by weight of the dental material); 7.5 grams of a silicone-acrylic rubber impact modifier such as S2006 from Mitsubishi Rayon Co. (eg, about 0.5 to about 20, preferably from about 5 to about 10% in weight of dental material); 1.0 gram of 2,4,6-trimethylabenzoyldiphenylphosphine oxide, (Lucirin TPO available from BASF) (for example, about 0.005 to about 8, preferably from about 0.05 to about 5% by weight of the material dental); and 0.5 grams of visible light initiation solution (for example, about 0 to about 8, preferably about 0.05 to about 5% by weight of the dental material) containing 5-20% (for example , about 13.3%) of camphorquinone (CQ), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1, 3%) butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) of N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (for example, about 16.3%) of Y -methacryloxypropyltrimethoxysilane. EXAMPLE 11 Dental materials
[0065] A polymerizable dental material was prepared by stirring a liquid mixture of about 20 to about 30% by weight of the oligomer produced following the procedure of Example 1 at room temperature; about 60 to about 70% by weight of methyl methacrylate (MMA); about 0.5 to about 10% by weight of ethylene glycol dimethacrylate; about 1 to about 10% by weight of a silicone-acrylic rubber impact modifier; about 0.05 to about 5% by weight of visible light initiation solution containing 10-20% (for example, about 13.3%) camphorquinone (CQ), 15-30% (for example, about of 23.0%) methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) of butylated hydroxytoluene (BHT), 35-55% (for example, about 46%) N, N-dimethylaminoethylneopentyl acrylate, and 10-20% (e.g., about 16.3%) y-methacryloxypropyltrimethoxysilane. EXAMPLE 12 Dental materials
[0066] A polymerizable dental material was prepared by stirring a liquid mixture of about 20 to about 30% by weight of the oligomer produced following the procedure of Example 5 at room temperature; about 45 to about 55% by weight of methyl methacrylate (MMA); about 5 to about 15% by weight of the D7-99 polymer (manufactured by Dentsply International); about 3 to about 10% by weight of S2006 rubber impact modifier (from Mitsubishi Rayon Co.); about 5 to about 15% by weight of 1,14-tetradecanedimethacrylate: about 0.05 to about 5% by weight of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, (Lucirin TPO available from BASF); and about 0 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about 23.0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (e.g., about 16.3%) y-methacryloxypropyltrimethoxysilane. EXAMPLE 13 Dental materials
[0067] A polymerizable dental material was prepared by stirring a liquid mixture of about 10 to about 38% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 *, from Sartomer] at room temperature; about 40 to about 55% by weight of methyl methacrylate (MMA); about 0 to about 15% by weight of SR399 * (diparterythritol pentacrylate, from Sartomer); about 0 to about 7% by weight of CN 21 * (Sartomer epoxy acrylate oligomer); about 0 to about 10% by weight of [Poly (methyl methacrylate-co-ethylacrylate) Elvacite 2009, from Sartomer]; about 0 to about 5% by weight of BKY-UV 3530 (polyether modified polydimethyl functional siloxane); about 0.5 to about 7% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) of camphorquinone (QC), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) acrylate of N, N-dimethylaminoethylneopentyl, and 5-30% (e.g., about 16.3%) y-methacryloxypropyltrimethoxysilane. EXAMPLE 14 Dental materials
[0068] A polymerizable dental material was prepared by stirring a liquid mixture of about 10 to about 30% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 *, from Sartomer] at room temperature; about 40 to about 60% by weight of methyl methacrylate (MMA); about 1 to about 10% by weight of SR399 * (diparterythritol pentacrylate, from Sartomer); about 5 to about 15% by weight of polymer D7-99 (manufactured by Dentsply International); about 1 to about 15% by weight of a silicone-acrylic rubber impact modifier; about 0.5 to about 10% by weight 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0.05 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about of 23.0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) of N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (for example, about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 15 Dental materials
[0069] A polymerizable dental material was prepared by stirring a liquid mixture of about 10 to about 30% by weight of monomer CD401 (purchased from Sartomer) at room temperature; about 50 to about 75% by weight of methyl methacrylate (MMA); about 1 to about 10% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 * triacrylate, from Sartomer]; about 0.005 to about 5% by weight 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0.005 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) of butyrated hydroxytoluene (BHT), 30-60% (for example, about 46%) of acrylate of N, N-dimethylaminoethylneopentyl, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 16 Dental materials
[0070] A polymerizable dental material was prepared by stirring a liquid mixture of about 1 to about 10% by weight of CD401 monomer (purchased from Sartomer) at room temperature; about 60 to about 90% by weight of methyl methacrylate (MMA); about 1 to about 10% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 * triacrylate, from Sartomer]; about 5 to about 15% by weight of the D7-99 polymer (manufactured by Dentsply International); about 0.005 to about 5% by weight 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0.005 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) of butyrated hydroxytoluene (BHT), 30-60% (for example, about 46%) of acrylate of N, N-dimethylaminoethylneopentyl, and 530% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 17 Dental materials
[0071] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 5 to about 18% by weight of oligomer produced following the procedure of Example 1; about 25 to about 35% by weight of the compound of Example 2; about 7 to about 18% by weight of the compound of Example 3; about 40 to about 50% by weight of 1,4-tetradecanedimethacrylate, and about 0.005 to about 5% by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF). EXAMPLE 18 Dental materials
[0072] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 35 to about 50% by weight of the oligomer produced following the procedure of Example 1; about 45 to about 60% by weight of 7,7,9-trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6-diol dimethacrylate; and about 1 to about 20% by weight of the compound of Example 4; and about 0.05 to about 5% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) of camphorquinone (QC), 1035% (for example, about 23.0 %) methacrylic acid (MM), 0.05-5% (for example, about 1.3%) butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) N-acrylate , N-dimethylaminoethylneopentyl, and 530% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 19 Dental materials
[0073] A polymerizable dental material was prepared by stirring a liquid mixture of about 35 to about 48% by weight of the oligomer produced at 85 ° C following the procedure of Example 1; about 35 to about 48 wt.% 7,7,9-trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6-diol dimethacrylate; about 1 to about 15% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 * triacrylate, from Sartomer]; about 5 to about 18% by weight of ethylene glycol dimethacrylate; and about 0.05 to about 5% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0 to about 5% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) of camphorquinone (QC), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) acrylate of N, N-dimethylaminoethylneopentyl, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 20 Dental materials
[0074] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 20 to about 38% by weight of the oligomer produced following the procedure of Example 1; about 10 to about 20% by weight of the compound of Example 2; about 1 to about 12% by weight of the compound of Example 3; about 10 to about 28% by weight of 1,14-tetradecanedimethacrylate; about 5 to about 18% by weight of dimethiol tricyclodecane diacrylate; about 5 to about 18 wt.% 7,7,9 trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6-diol dimethacrylate; about 12 to about 28% by weight of Genomer 4256 (aliphatic polyester urethane methacrylate supplied by Rohm America Inc.); and from about 0.005 to about 5% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO supplied by BASF). EXAMPLE 21 Dental materials
[0075] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 15 to about 30% by weight of the oligomer produced following the procedure of Example 1, about 20 to about 35% by weight of the compound Example 2; about 5 to about 20% by weight of the compound of Example 3; about 1 to about 12% by weight of 7,7,9-trimethyl-4,13-dioxo-5,12-diazaexadecane-1, 16-diol dimethacrylate, about 30 to about 45% by weight of 1, 14-tetradecanedimethacrylate, and about 0.005 to about 3% by weight of visible light initiation solution containing 5-20% (e.g., about 13.3%) camphorquinone (CQ), 10-35% (e.g., about 23.0%) methacrylic acid (MAA), 0.05-5% (e.g., about 1.3%) butylated hydroxytoluene (BHT), 30-60% (e.g. about 46%) of N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 22 Dental materials
[0076] A polymerizable dental composite material was prepared by mixing a mixture of about 15 to about 28% by weight of monomer produced following the procedure of Example 5; about 10 to about 22% by weight of triethylene glycol diimethacrylate; about 0.5 to about 10% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 * triacrylate, from Sartomer]; about 0.005 to about 5% by weight of silane fumed silica (SiO2) with an average particle size of about 0.01 to about 0.04 micrometers; about 55 to about 68% by weight of BAFG silane barium aluminum fluorosilicate glass particles with an average particle size of about 0.1 to about 1 micrometer; about 0.005 to about 5% by weight of Lumilux Blue LZ fluorescent agent (dihydroxy acid ester terephthalate) and pigments; about 0.005 to about 3% by weight of Lucirin-TPO (2,4,6-trimethylabenzoyldiphenylphosphine oxide); and about 0.005 to about 3% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) of butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 23 Dental materials
[0077] A polymerizable dental composite material was prepared by mixing a mixture of about 5 to about 18% by weight of monomer produced following the procedure of Example 5; about 5 to about 18% by weight of NCO monomer (produced by Dentsply Caulk); about 10 to about 22% by weight of triethylene glycol diimethacrylate; about 0.5 to about 10% by weight of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 * triacrylate, from Sartomerj; about 0.005 to about 3% by weight of silane fumed silica (SiO2) with an average particle size of about 0.01 to about 0.04 micrometers; about 55 to about 65% by weight of the composite load of Example 9; about 0.005 to about 3% by weight of Lumilux Blue LZ fluorescent agent (dihydroxy acid ester terephthalate) and pigments; about 0.005 to about 3% by weight of Lucirin-TPO (2,4,6-trimethylabenzoyldiphenylphosphine oxide); and about 0.005 to about 3% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) camphorquinone (QC), 10-35% (for example, about 23.0%) of methacrylic acid (MAA), 0.05-5% (for example, about 1.3%) of butylated hydroxytoluene (BHT), 30-60% (for example, about 46%) N, N-dimethylaminoethylneopentyl acrylate, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 24 Dental materials
[0078] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 35 to about 48% by weight of the oligomer produced following the procedure of Example 1; about 35 to about 48 wt.% 7,7,9-trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6-diol dimethacrylate; about 2 to about 18% by weight of methyl methacrylate; about 5 to about 18% by weight of a silicone-acrylic rubber impact modifier; and about 0.05 to about 5% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0.005 to about 3% by weight of visible light initiation solution containing 5-20% (for example, about 13.3%) of camphorquinone (QC), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) acrylate of N, N-dimethylaminoethylneopentyl, and 5-30% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 25 Dental materials
[0079] A polymerizable dental material was prepared by stirring at 85 ° C a liquid mixture of about 15 to about 28% by weight of the oligomer produced following the procedure of Example 5; about 15 to about 28% by weight of 7,7,9-trimethyl-4,13-dioxo-3,14 dioxa-5,12-diazaexadecane-1,6-diol dimethacrylate; about 30 to about 45% by weight of methyl methacrylate; about 5 to about 15% by weight of a silicone-acrylic rubber impact modifier; about 5 to about 18% by weight of the D7-99 polymer (manufactured by Dentsply International); and from about 0.005 to about 3% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide (Lucirin TPO available from BASF); about 0.05 to about 3% by weight of visible light initiation solution containing 520% (for example, about 13.3%) camphorquinone (CQ), 10-35% (for example, about 23 , 0%) methacrylic acid (MAA), 0.05-5% (eg about 1.3%) butylated hydroxytoluene (BHT), 30-60% (eg about 46%) acrylate of N, N-dimethylaminoethylneopentyl, and 530% (e.g., about 16.3%) Y-methacryloxypropyltrimethoxysilane. EXAMPLE 26 Dental materials
[0080] A polymerizable wax-like dental material was prepared by stirring at 75 ° C a liquid mixture of about 65 to about 88% by weight of bisphenol A proxilate diglycidyl ether, about 20 to about 38% by weight of 1, 10 decanediol, 1.0 gram 4-octyloxy-phenyl iodonium hexafluorantimonate (OPPI), about 0.005 to about 3% by weight of 2,4,6-trimethylabenzoyldiphenylphosphine oxide, (Lucirin TPO produced by BASF), about 0.005 to about 3% by weight of pigment concentrates. EXAMPLE 27 Dental materials
[0081] A polymerizable dental material was prepared by stirring around 0 to 50% (for example, 4 to 45%) of the oligomer produced following the procedure of Example 1; 40% to 90% (for example, 50 to 80%) of methyl methacrylate (MMA); 0 to 50% (for example, 4 to 45%) of various mono to multifunctional (meth) acrylates; 0 to 20% (e.g., 2 to 18%) of PMMA polymer; 0 to 20% (for example, 2 to 18%) of rubber impact modifiers; 0 to 60% (for example, 5 to 55%) of inorganic fillers or composites; 0 to 10% (for example, 1 to 9%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 9%) of light initiators. EXAMPLE 28 Dental materials
[0082] A polymerizable dental material was prepared by stirring a liquid mixture of 0 to 50% (for example, 5 to 45%) of oligomer produced following the procedure of Example 5 around room temperature; 40 to 90% (for example, 45 to 85%) of methyl methacrylate (MA); 0 to 20% (e.g., 2 to 18%) of PMMA polymer; 0 to 20% (for example, 2 to 18%) of rubber impact modifiers; 0 to 50% (for example, 5 to 45%) of various mono to multifunctional (meth) acrylates; 0 to 60% (for example, 5 to 55%) of organic, inorganic or composite fillers; 0 to 10% (for example, 1 to 9%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 8%) of light initiators. EXAMPLE 29 Dental materials
[0083] A polymerizable dental material was prepared by stirring a 0 to 50% (eg 5 to 45%) liquid mixture of [Tris (2-Hydroxy Ethyl) isocyanurate SR368 *, from Sartomer] around room temperature. ; 40 to 90% (for example, 50 to 80%) of methyl methacrylate (MMA); 0 to 20% (e.g., 2 to 18%) of PMMA polymer; 0 to 20% (for example, 2 to 18%) of rubber impact modifiers; 0 to 50% (for example, 5 to 45%) of various mono to multifunctional (meth) acrylates; 0 to 60% (for example, 10 to 50%) of organic, inorganic or composite fillers; 0 to 10% (for example, 1 to 9%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 8%) of light initiators. EXAMPLE 30 Dental materials
[0084] A polymerizable dental material was prepared by stirring a liquid mixture of 0 to 99.5% (for example, 10 to 85% at about 70 ° C to about 100 ° C) , preferably 20 to 75%) of oligomer produced following the procedure of Example 1; 0 to 50% (for example, 5 to 45%) of the compound of Example 2; 0 to 50% (for example, 5 to 45%) of the compound of Example 3; 0 to 80% (e.g., 20 to 70%) of various mono to multifunctional (meth) acrylates; 0 to 60% (for example, 10 to 50%) of organic, inorganic or composite fillers; 0 to 10% (for example, 1 to 9%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 8%) of light initiators. EXAMPLE 31 Dental materials
[0085] A polymerizable dental material was prepared by stirring a liquid mixture of 0 to 99.5% (for example, 25 to 75% at about 70 ° C to about 100 ° C) ) of oligomer produced following the procedure of Example 1; 0 to 80% (e.g., 20 to 70%) of various mono to multifunctional (meth) acrylates; 0 to 60% (for example, 10 to 50%) of various inorganic fillers (with an average particle size of about 0.01 to about 3 micrometers or about 0.1 to about 2.5 micrometers); 0 to 60% (for example, 10 to 50%) of various composites or organic fillers (with an average particle size of about 1 to about 100 microns or about 5 to about 75 microns); 0 to 10% (for example, 1 to 9%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 9%) of light initiators. EXAMPLE 32 Dental materials
[0086] A polymerizable dental composite material was prepared by mixing a mixture of 0 to 99.5% (for example, 25 to 75%) of monomer produced following the procedure of Example 5; 0 to 80% (e.g., 20 to 70%) of various mono to multifunctional (meth) acrylates; 0 to 60% (for example, 0 to 45%) of various inorganic fillers (with an average particle size of about 0.01 to about 3 microns or about 0.1 to about 2.5 microns); 0 to 60% (for example, 5 to 45%) of various composites or organic fillers (with an average particle size of about 1 to about 100 micrometers or about 25 to about 75 micrometers); 0 to 10% (for example, 1 to 8%) of pigments and other additives, such as fluorescent agents and inhibitors; and 0.01 to 10% (e.g., 0.1 to 7%) of light initiators. EXAMPLE 33 (PROPHETIC) Dental Product Manufacturing
[0087] The material in Example 10 with the addition of pigments is loaded into the reservoir of an EnvisionTec printer and sequential voxel plans are projected onto the computer-controlled layer-by-layer liquid resin. This process can be used to form a denture in a layer-by-layer manner. This process produces a denture in which teeth can subsequently be added to the formed cavities. Once the denture is made, submitted to final cure, finished and polished, the denture is delivered to the patient. EXAMPLE 33A (PROPHETIC) Dental Product Manufacturing
[0088] The material of Example 10A with the addition of pigments is loaded into the reservoir of a 3D printer based on SLA and the traces of the laser beam (light) on the liquid layer-by-layer resin controlled by a computer. This process can be used to form a denture in a layer-by-layer manner. This process produces a denture in which teeth can subsequently be added to the formed cavities. If additional layers are required for teeth, additional reservoirs can be used according to the aforementioned method. Once the denture is made, submitted to final cure, finished and polished, the denture is delivered to the patient. EXAMPLE 34 (PROPHETIC) Dental Product Manufacturing
[0089] The materials of Example 15 and 16 with the addition of pigments are loaded into two separate reservoirs of an envisiontec printer and sequential voxel plans are projected onto the first liquid resin (Example 16) from layer to layer controlled by a computer to form dentine parts of artificial teeth. Parts of the dentine formed from artificial teeth are removed from this bath. After being washed with solvent and dried, these parts of the dentin are immersed in the second bath and sequential voxel planes are projected onto the second liquid resin (Example 15) layer by layer controlled by a computer to form enamel parts over the parts of the dentin to form artificial teeth. Finally, artificial teeth are removed from the bath, washed and subjected to final curing. After polished and finished, these artificial teeth can be used to produce dentures and other dental devices. This process can be used for mass manufacturing of artificial teeth and other dental devices. EXAMPLE 34A (PROPHETIC) Dental Product Manufacturing
[0090] The materials of Example 15 and 16 with the addition of pigments are loaded into two separate reservoirs of a 3D printer based on SLA and the traces of the laser beam (light) on the first liquid resin (Example 16) layer by layer controlled by a computer to form parts of the dentin of artificial teeth. Parts of the dentine formed from artificial teeth are removed from this bath. After being washed with solvent and dried, these parts of the dentin are dipped in a second bath and sequential voxel planes are projected onto the second liquid resin (Example 15) from computer-controlled layer to layer to form enamel parts over the parts dentin to form artificial teeth. Finally, artificial teeth are removed from the bath, washed and subjected to final curing. After polished and finished, these artificial teeth can be used to produce dentures and other dental devices. If additional layers are required for teeth, additional reservoirs can be used according to the aforementioned method. This process can be used for mass manufacturing of artificial teeth and other dental devices. EXAMPLE 35 (PROPHETIC) Dental Product Manufacturing
[0091] The materials of Example 11, 15 and 16 with the addition of pigments are loaded into three separate reservoirs of an envisiontec printer and sequential voxel plans are projected onto the first liquid resin (Example 1) from layer to layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath and sequential voxel planes are projected onto the second liquid resin (Example 16) from layer to layer controlled by a computer to form parts of the artificial teeth dentine on top denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and sequential voxel layers were projected onto the second liquid resin (Example 15) from layer to layer controlled by a computer to form enamel parts over the dentine parts to forming dentures. If additional layers are required for denture or tooth bases, additional reservoirs can be used according to the aforementioned method. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 35A (PROPHETIC) Dental Product Manufacturing
[0092] The materials of Example 10A, 15 and 16 with the addition of pigments are loaded into three separate reservoirs of a 3D printer based on SLA and the laser beam traces (light) in the first liquid resin (Example 0A) layer layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath and subsequently traces of the laser beam (light) in the second liquid resin (Example 16) from layer to layer controlled by a computer to form parts of the dentin of teeth artificial teeth over the denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and the laser beam traces (light) in the second liquid resin (Example 5) layer by layer controlled by a computer to form enamel parts over the parts dentin to form dentures. Following the same approach, additional layers can be built, if desired. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 36 (PROPHETIC) Dental Product Manufacturing
[0093] The materials of Example 18, and 19 (two tints) with the addition of pigments are loaded into three heated reservoirs separated from an envisiontec printer and sequential voxel plans are projected onto the first liquid resin (Example 18) layer by layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath (tinted dentine from Example 19) and sequential voxel planes are projected onto the second liquid resin (tinted dentine from Example 19) from layer to layer controlled by a computer to form parts of dentin from artificial teeth over the denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and sequential voxel layers are projected onto the second liquid resin (tinted enamel from Example 19) from layer to layer controlled by a computer to form enamel parts on top of the parts dentin to form dentures. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 36A (PROPHETIC) Dental Product Manufacturing
[0094] The materials of Example 18, and 19 (two tints) with the addition of pigments are loaded into three heated reservoirs separated from a 3D printer based on SLA and the laser beam traces (light) on the first liquid resin (Example 18) layer by layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath (tinted dentine from Example 19) and sequential voxel planes and laser beam traces (light) in the second liquid resin (tinted dentine from Example 19) layer-by-layer controlled by a computer to form parts of the dentin of artificial teeth on top of the denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and the traces of laser beam (light) in the second liquid resin (tinted enamel from Example 19) layer by layer controlled by a computer to form enamel parts by over the dentin parts to form dentures. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 37 (PROPHETIC) Dental Product Manufacturing
[0095] The materials of Example 22 (enamel and tinted dentin) are loaded into two separate reservoirs (heated as needed) from an envisiontec printer and sequential voxel plans are projected onto the first liquid resin (tinted dentine) in layer layer controlled by a computer to form crown shapes. Formed crown parts are removed from this bath. After being washed with solvent and dried, these parts of the crown are immersed in the second bath and sequential voxel layers are projected onto the second liquid resin (tinted enamel) from layer to layer controlled by a computer to form enamel parts over the parts of the crown. dentin to form final crowns. Finally, crowns are removed from the bath, washed and subjected to final curing. This process can be used for mass manufacturing crowns, bridges, artificial teeth and other dental devices.
[0096] Optional sealant can be applied to these crowns, and then cured in a luminous curing unit for 1 to 10 minutes. This curing step produces final crown products, which can be coated or cemented onto a tooth prepared in the crown in a patient's mouth. EXAMPLE 37A (PROPHETIC) Dental Product Manufacturing
[0097] The materials of Example 22 (enamel and tinted dentine) are loaded into two separate reservoirs (heated as needed) from a 3D printer based on SLA and the laser beam traces (light) on the first liquid resin ( tinted dentin) from layer to layer controlled by a computer to form crown shapes. Formed crown parts are removed from this bath. After being washed with solvent and dried, these parts of the crown are immersed in the second bath and the traces of laser beam (light) in the second liquid resin (tinted enamel) layer by layer controlled by a computer to form enamel parts on top of the dentin parts to form final crowns. Finally, crowns are removed from the bath, washed and subjected to final curing. This process can be used for mass manufacturing crowns, bridges, artificial teeth and other dental devices.
[0098] Optional sealant can be applied to these crowns, and then cured in a luminous curing unit for 1 to 10 minutes. This curing step produces final crown products, which can be coated or cemented onto a tooth prepared in the crown in a patient's mouth. EXAMPLE 38 (PROPHETIC) Dental Product Manufacturing
[0099] The materials of Example 20 (with the addition of pigments and red fibers), and 23 (two hues) are loaded into three heated reservoirs separated from an envisiontec printer and sequential voxel plans are projected onto the first liquid resin (Example 20 ) layer by layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath (tinted dentine from Example 23) and sequential voxel planes are projected onto the second liquid resin (tinted dentine from Example 23) in a layered manner by a computer to form parts of artificial teeth dentine over the denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and sequential voxel layers are projected onto the second liquid resin (tinted enamel from Example 23) layer by layer controlled by a computer to form enamel parts on top of the parts dentin to form dentures. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 38A (PROPHETIC) Dental Product Manufacturing
[00100] The materials of Example 20 (with the addition of pigments and red fibers), and 23 (two hues) are loaded into three heated reservoirs separated from a 3D printer based on SLA and the laser beam traces (light) on first liquid resin (Example 20) from layer to layer controlled by a computer to form denture bases. Bases of dentures formed are removed from this bath. After being washed with solvent and dried, these denture bases are immersed in the second bath (tinted dentine from Example 23) and the laser beam traces (light) in the second liquid resin (tinted dentine from Example 23) controlled layer by layer by a computer to form parts of the dentin of artificial teeth above the denture bases. Denture bases formed with parts of the dentine are removed from this bath. After being washed with solvent and dried, these parts are immersed in the third bath and the laser beam traces (light) in the second liquid resin (tinted enamel from Example 23) layer by layer controlled by a computer to form enamel parts by over the dentin parts to form dentures. Finally, dentures are removed from the bath, washed and subjected to final healing. Once the dentures are made, final cured, finished and polished, the dentures are delivered to patients. EXAMPLE 39 (PROPHETIC) Manufacture of Dental Models and Braces
[00101] Materials such as light-curing epoxies (irradiation) (such as material in example 26) and silicones can be loaded into separate and optionally heated reservoirs of an envisiontec Printer and sequential voxel plans are projected onto the first layer liquid bath in layer controlled by a computer to form molds, appliances or accessory products in the manufacture of restorations or appliances. Molds formed, appliances are removed from this bath. After optional solvent washing and drying of these models, devices are immersed in subsequent baths for the addition of other layers (for example, of different core) and sequential voxel plans are designed in these layer-by-layer liquid resin baths controlled by a computer to form layered devices. Molds and formed appliances are removed from these subsequent baths. Finally, braces can be post-processed after cleaning, for delivery to a dental professional or patient.
[00102] It should be further realized that functions or structures of a plurality of components or steps can be combined into a single component or step, or the functions or structures of a step or component can be divided between several steps or components. The present invention contemplates all such combinations. Unless otherwise stated, dimensions and geometries of the various structures represented here should not be restrictive of the invention, and other dimensions or geometries are possible. Furthermore, although a feature of the present invention may have been described in the context of just one of the illustrated modalities, that feature can be combined with one or more other features of other modalities, for any given application. It should also be understood from the above that the manufacture of the exclusive structures here and their operation are also methods according to the present invention. The present invention also encompasses end products and intermediates resulting from the practice of the methods here. The use of "comprising" or "including" also includes modalities that "essentially consist" or "consist of the aforementioned resource".
[00103] The explanations and illustrations presented here aim to familiarize those versed in the technique with the invention, its principles and its practical application. Experienced in the art, they can adapt and apply the invention in its numerous forms, which may be better suited to the requirements of a particular use. Accordingly, the specific embodiments of the present invention presented should not be exhaustive or limiting to the invention. The scope of the invention, therefore, must be determined not with reference to the description presented, but, instead, it must be determined with reference to the appended claims, along with the total scope of equivalents to which such claims relate. The disclosures of all articles and references, including patent applications and publications, are incorporated into the reference for all purposes.

权利要求:
Claims (2)
[0001]
1. Method to produce a three-dimensional dental prosthesis by a 3D printer based on a DLP (Digital Light Processor) or stereolithography method, characterized by the fact that it comprises the steps of: a. loading a printable polymerizable liquid resin material or heated resin material like a liquid into a resin bath on a 3D printer; B. applying sequential voxel plans of light to the printable polymerizable liquid resin or heated resin to form a first layer of material, which polymerizes to a solid; ç. applying one or more successive layers of the polymerized material until a predetermined shape is formed; d. washing and / or transferring the formed form to a separate resin bath, which has a different hue or / and different physical properties, to build additional layers of materials on the surface of the form formed layer by layer according to steps a) to c); and. optionally, repeat step d) as needed.
[0002]
Method according to claim 1, characterized in that the printable polymerizable liquid resin material or heated resin material as a liquid includes a composition having: 35 to 48% by weight of at least one oligomer; 35 to 66% by weight of one or more mono or multifunctional (meth) acrylates; 0 to 60% by weight of at least one inorganic filler and / or at least one organic filler; 2 to 18% by weight of a core-shell impact modifier having at least one core that includes a silicone-acrylic rubber component or a butadiene-based rubber component and at least one shell that includes at least a thermoplastic being selected from the group consisting of polycarbonate, polystyrene, polypropylene, poly (ethylene terephthalate), poly (vinyl chloride), polyamide, polyurethane, poly (butylene terephthalate), acrylonitrile-butadiene-styrene resin, poly (methyl methacrylate) and combination thereof; 0 to 10% by weight of pigments, and 0.01 to 10% by weight of light initiators; based on a total of 100% by weight.

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CN104853693B|2018-06-26|

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法律状态:
2018-01-23| B07D| Technical examination (opinion) related to article 229 of industrial property law [chapter 7.4 patent gazette]|

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2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-01-29| B07G| Grant request does not fulfill article 229-c lpi (prior consent of anvisa) [chapter 7.7 patent gazette]|Free format text: NOTIFICACAO DE DEVOLUCAO DO PEDIDO POR NAO SE ENQUADRAR NO ART. 229-C DA LPI. |

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2020-04-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-15| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-04-13| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REF. RPI 2606 DE 15/12/2020 QUANTO AO TITULO. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261726317P| true| 2012-11-14|2012-11-14|

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US61/726317|2012-11-14|

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PCT/US2013/070099|WO2014078537A1|2012-11-14|2013-11-14|Three-dimensional fabricating material systems for producing dental products|

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