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WO2025264579A1 - Compositions pour la fabrication additive au moyen de charges activables - Google Patents

Compositions pour la fabrication additive au moyen de charges activables

Info

Publication number
WO2025264579A1
WO2025264579A1 PCT/US2025/033816 US2025033816W WO2025264579A1 WO 2025264579 A1 WO2025264579 A1 WO 2025264579A1 US 2025033816 W US2025033816 W US 2025033816W WO 2025264579 A1 WO2025264579 A1 WO 2025264579A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
energy
filler
polymeric material
activatable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/033816
Other languages
English (en)
Inventor
Christian Gorsche
Christian Frank
Michael Leitner
Markus KURY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Align Technology Inc
Original Assignee
Align Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Align Technology Inc filed Critical Align Technology Inc
Publication of WO2025264579A1 publication Critical patent/WO2025264579A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
    • A61C7/08—Mouthpiece-type retainers or positioners, e.g. for both the lower and upper arch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/35—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • the present technology generally relates to manufacturing, and in particular, to composition for additive manufacturing with activatable fillers.
  • Hybrid polymer-metal devices such as mechatronic integrated devices (MIDs) are useful in a wide variety of applications, including consumer electronics, telecommunications, automotive systems, and medical devices.
  • hybrid dental appliances including both polymeric and metallic materials can provide improved mechanical properties and increased functionality compared to polymer only or metal only appliances.
  • Conventional materials and methods for manufacturing hybrid polymer-metal devices generally use traditional polymer processing technologies, such as injection molding, to form the polymeric component. However, these approaches may not be suited for large scale production of objects with customized geometries, such as patient-specific dental appliances.
  • FIG. 1 is a flow diagram illustrating a method for fabricating a hybrid object, in accordance with embodiments of the present technology.
  • FIG. 2 is a partially schematic diagram providing a general overview of an additive manufacturing process, in accordance with embodiments of the present technology.
  • FIG. 3 A illustrates a representative example of a tooth repositioning appliance configured in accordance with embodiments of the present technology.
  • FIG. 3B illustrates a tooth repositioning system including a plurality of appliances, in accordance with embodiments of the present technology.
  • FIG. 3C illustrates a method of orthodontic treatment using a plurality of appliances, in accordance with embodiments of the present technology.
  • FIG. 4 illustrates a method for designing an orthodontic appliance, in accordance with embodiments of the present technology.
  • FIG. 5 illustrates a method for digitally planning an orthodontic treatment and/or design or fabrication of an appliance, in accordance with embodiments of the present technology.
  • the present technology relates to manufacturing of objects from polymeric and metallic materials.
  • the systems and methods herein can be used to manufacture a dental appliance (e.g., an aligner, palatal expander, retainer, positioner, mouth guard) including a first portion to be formed from a polymeric material and a second portion to be formed from a metallic material.
  • the second portion can encompass one or more regions of the appliance where greater mechanical strength and/or electrical conductivity is desired.
  • the second portion can be or include a reinforcement structure (e.g., a fiber, bar, lattice, layer, patch), a metallic auxiliary structure (e.g., a hook, button, distalizer, power arm, bracket, wire, spring, palatal expander, lingual retainer), and/or a conductive structure (e.g., a wire, trace, contact, electrode, or antenna).
  • a reinforcement structure e.g., a fiber, bar, lattice, layer, patch
  • a metallic auxiliary structure e.g., a hook, button, distalizer, power arm, bracket, wire, spring, palatal expander, lingual retainer
  • a conductive structure e.g., a wire, trace, contact, electrode, or antenna
  • a method includes receiving a digital representation of a dental appliance having a first portion to be formed from a polymeric material and a second portion to be formed from a metallic material.
  • the method can include fabricating the dental appliance via an additive manufacturing process, where the dental appliance is fabricated from a composition including a precursor of the polymeric material (e.g., a photopolymerizable resin) and an activatable filler (e.g., a metal-containing compound).
  • the additive manufacturing process can involve applying first energy to the composition to cure the precursor of the polymeric material, thereby forming the first portion of the dental appliance from the polymeric material.
  • the activatable filler can be configured to be activated by second energy to form a substrate for deposition of the metallic material at the second portion of the dental appliance, e.g., via a laser direct structuring (LDS) process.
  • LDS laser direct structuring
  • the present technology can provide many advantages for the fabrication of dental appliances and other additively manufactured objects.
  • the embodiments herein provide processes that can be used to produce additively manufactured objects made of polymeric and metallic materials, which can exhibit improved characteristics (e.g., mechanical strength, conductivity, formability) compared to objects that are made from a single type of material.
  • dental appliances including polymeric and metallic components can exhibit improved durability, provide larger and/or more sustained forces on the teeth, and/or interface with electronic components.
  • materials may be required that are not only laser-activatable and easy to metallize, but are also characterized by sufficient storage stability and printability, which are often critical challenges.
  • the availability of such materials is still limited, especially for applications that require a high degree of activatability, which may be controlled at least in part by the composition and/or amount of LDS filler.
  • One challenge to finding suitable materials is the fact that materials with fillers may need to maintain their storage stability even at elevated temperatures to avoid sedimentation during processing.
  • the present technology provides compositions for the additive manufacturing of objects via first energy (e.g., light) with a first wavelength range, where the compositions contain fillers that can be activated via second energy (e.g., light) with a second wavelength range different from the first wavelength range, and can subsequently be selectively metallized at these activation sites.
  • the present technology further provides processes for fabricating 3D objects (such as dental appliances, 3D circuit carriers, or MIDs) based on additive manufacturing of the present compositions followed by an LDS process and subsequent metallization of the laser-activated portion of the surface of object, where the metallization forms one or more metallic structures.
  • the present technology further relates to an additively manufactured object, such as a dental appliance, a 3D circuit carrier, or a MID, which is manufactured according to the processes described herein.
  • the present compositions may thus be used as resin formulations for making 3D objects via additive manufacturing.
  • the resulting 3D objects offer the incorporation of selective, conductive tracks vis subsequent LDS process and metallization steps, while also exhibiting superior sedimentation stability, printability, and mechanical performance.
  • Possible applications for such additively manufactured 3D objects include electronic connectors, parts for printed circuit boards, packaging and cooling architectures for electronics, chip mounting, sensors or other electronics integrated into medical devices such as dental appliance, and/or other application examples where there is a demand for MIDs in combination with mechanical durability and thermal stability at temperatures exceeding 50 °C.
  • compositions exhibit improved sedimentation stability and printability via radiation-curing additive manufacturing processes, which is a remarkable achievement.
  • the compositions herein also stand out for their excellent resolution and component precision. This innovative approach opens up new possibilities for the use of additive manufacturing in applications that involve both high precision and improved laser activatability and metallizability, especially for the production of dental appliance and MIDs.
  • the terms “vertical,” “lateral,” “upper,” “lower,” “left,” “right,” etc. can refer to relative directions or positions of features of the embodiments disclosed herein in view of the orientation shown in the Figures.
  • “upper” or “uppermost” can refer to a feature positioned closer to the top of a page than another feature.
  • These terms should be construed broadly to include embodiments having other orientations, such as inverted or inclined orientations where top/bottom, over/under, above/below, up/down, and left/right can be interchanged depending on the orientation.
  • hybrid dental appliances such as aligners, palatal expanders, retainers, attachment placement devices, attachments, oral sleep apnea appliances, positioners, mouth guards, and splints
  • hybrid dental appliances can include one or more portions made from a polymeric material, and one or more portions made from a metallic material.
  • the metallic portions can enhance the functionality of the dental appliance, such as by improving the mechanical properties, applying larger and/or more sustained repositioning forces, engaging other devices to produce repositioning forces, and/or interfacing with electronics to confer additional capabilities such as sensing.
  • 3D objects such as consumer goods, sporting goods, electronics, electrical and electromechanical components, connectors, housings, automotive components, mobility and electromobility devices, aerospace components, communication technology, computer technology, military technology, medical devices and technology (e.g., facial surgery applications), energy industry components, railroad industry components, etc.
  • FIG. 1 is a flow diagram illustrating a method 100 for fabricating a hybrid object, in accordance with embodiments of the present technology.
  • the method 100 can be used to fabricate any suitable 3D object, such a dental appliance.
  • some or all of the processes of the method 100 are implemented as computer-readable instructions (e.g., program code) that are configured to be executed by one or more processors of a computing device, such as a controller of a fabrication system.
  • the method 100 can begin at block 102 with receiving a digital representation of an object to be fabricated.
  • the object can be a dental appliance, such as an aligner, palatal expander, retainer, positioner, sleep apnea appliance, mouth guard, etc.
  • the object can have at least one first portion to be formed from a polymeric material, and at least one second portion to be formed from a metallic material.
  • the number, geometry, and spatial location of the first portion(s) and second portion(s) can be selected to produce the desired functionality for the object.
  • the object can include one, two, three, four, five, 10, 20, 50 or more polymeric first portions; and/or one, two, three, four, five, 10, 20, 50 or more metallic second portions.
  • the polymeric first portion(s) and metallic second portion(s) can differ from each other with respect to one or more properties, such as any of the following: stiffness, modulus (e.g., elastic modulus, flexural modulus, storage modulus), strength, hardness, electrical conductivity, magnetism, scratch resistance, creep resistance, roughness, durability, degradability, elongation to break, elongation to yield, color, refractive index, translucency, transparency, porosity, reactivity (e.g., photoreactivity, thermal reactivity) antimicrobial properties, and/or antifungal properties.
  • modulus e.g., elastic modulus, flexural modulus, storage modulus
  • strength hardness
  • electrical conductivity magnetism
  • magnetism scratch resistance
  • creep resistance roughness
  • durability durability
  • degradability elongation to break
  • elongation to yield color
  • refractive index e.g., translucency
  • transparency e.g., porosity
  • the metallic second portion(s) can have a greater stiffness, modulus, strength, hardness, scratch resistance, creep resistance, and/or durability than the polymeric first portion(s).
  • the metallic second portion(s) can be electrically conductive, while the polymeric first portion(s) can be electrically insulative.
  • the metallic second portion(s) can exhibit magnetic properties, while the polymeric first portion(s) can exhibit little or no magnetic properties.
  • the polymeric first portion(s) define the overall shape of the object, while the metallic second portion(s) provide desired functionalities at selected regions of the object.
  • the polymeric first portion(s) can form a polymeric shell including a plurality of tooth-receiving cavities configured to fit over some or all of the teeth on the patient’s arch.
  • the polymeric shell can include one or more polymeric appliance features, such a receptacle to engage a toothmounted attachment, a palatal expander, a mandibular advancement device, a hook, a button, a receptacle for receiving electronic components, etc.
  • the metallic second portion(s) can be disposed at any of the following locations on or within the polymeric shell: an inner surface of the shell, an exterior surface of the shell, a distal region of the shell, a mesial region of the shell, an occlusal region of the shell, a gingival region of the shell, an interproximal region of the shell, a buccal region of the shell, a lingual region of the shell, a location at or proximate to a tooth-receiving cavity, a location spaced apart from a tooth-receiving cavity, a location at or proximate to a polymeric appliance feature (e.g., a receptacle for engaging a tooth-mounted attachment, a palatal expander, a mandibular advancement device, a hook, a button, an receptacle for receiving electronic components), or suitable combinations thereof.
  • a polymeric appliance feature e.g., a receptacle for engaging a tooth-mounted attachment,
  • the metallic second portion(s) can form one or more reinforcement structures such as fibers, bars, lattices, layers, patches, etc., that are disposed on or within the shell to provide enhanced mechanical properties, such as increased stiffness, strength, hardness, durability, scratch resistance, and/or creep resistance.
  • the reinforcement structures can also provide increased forces at selected locations on the patient’s dentition (e.g., relative to locations where forces are applied by the polymeric shell only).
  • the metallic second portion(s) can form one or more auxiliary structures integrated with the shell that provide additional functionality for treating the patient’s teeth, such as hooks, buttons, distalizers, power arms, brackets, wires, springs, palatal expanders, or lingual retainers.
  • the auxiliary structure can directly apply a force to the patient’s teeth, modify a force applied by the shell to the patient’s teeth, and/or interact with another component (e.g., an elastic, another region of the shell, another appliance) to apply force to the patient’s teeth.
  • the metallic second portion(s) can form one or more conductive structures that are disposed on or within the shell, such as wires, traces, contacts, electrodes, or antennas.
  • the conductive structure can be configured to electrically couple to at least one electronic component of the dental appliance, such as a battery, a sensor, a monitoring device (e.g., an electronic compliance indicator), or an actuator.
  • the metallic second portion(s) can provide other types of functionalities, such as antimicrobial and/or antifungal properties, magnetic properties (e.g., for sensing, interacting with another magnetic component), aesthetic properties (e.g., ornamental metal plating), etc. Additional details and examples of hybrid dental appliances that may be produced using the methods and compositions herein are provided in U.S. Publication No. 2025/0017695, the disclosure of which is incorporated by reference herein in its entirety.
  • the digital representation received in block 102 can be a digital file or other digital data structure suitable for controlling the operation of an additive manufacturing system to fabricate the object.
  • the digital representation is or includes a 3D digital model representing the geometry of the object, including the geometry and locations of the first and second portions.
  • the 3D digital model can be a surface model, mesh model, non-parametric model, parametric model, etc.
  • the 3D digital model can be composed of a plurality of 3D elements (e.g., voxels) representing the shape of the object.
  • the 3D digital model can be provided in any suitable file format, such as a computer-aided design (CAD) file format that can be used to transfer information to and/or control the operation of an additive manufacturing system (e.g., STL file, OBJ file, AMF file, 3MF file).
  • CAD computer-aided design
  • the digital representation can be or include a series of 2D cross-sections (e.g., slices) that are generated from a 3D digital model of the object.
  • the 2D crosssections can correspond to the individual layers of the object.
  • the 2D cross-sections can be provided in any suitable file format, such as an image file format (e.g., BMP file, PNG file).
  • the digital representation can be or include fabrication instructions generated from the 3D digital model and/or 2D cross-sections.
  • the method 100 can include fabricating the object via an additive manufacturing process.
  • the object may be fabricated from a composition (e.g., a resin) that includes a precursor of the polymeric material and an activatable filler.
  • the composition may also include a photoinitiator and optional additives.
  • the precursor of the polymeric material can be a polymerizable component (e.g., one or more monomers, oligomers, and/or reactive polymers) that is capable of forming bonds (e.g., curing and/or polymerizing) to form the polymeric material.
  • the photoinitiator can create reactive species when exposed to energy (e.g., radiation) to promote the bond-forming reactions (e.g., curing and/or polymerization) of the polymerizable component.
  • the activatable filler can remain present in the polymeric material and be selectively activated after the additive manufacturing process is complete to form a substrate for depositing the metallic material.
  • the additives can serve various functions, such as modifying the chemistry and/or properties of the fabricated object. Additional details and examples of each of these components are provided in Section I.B below.
  • the additive manufacturing process can include depositing the composition onto a build platform.
  • the composition can be cured, polymerized, melted, sintered, fused, and/or otherwise solidified to form a portion of the object and/or to combine the portion with previously formed portions of the object.
  • the additive manufacturing techniques provided herein build up the object geometry in a layer-by-layer fashion, with successive layers being formed in discrete build steps. Alternatively or in combination, the additive manufacturing techniques described herein can allow for continuous build-up of some or all of the object geometry.
  • the additive manufacturing process is a radiation-curing additive manufacturing process.
  • liquid or viscous reactive resins are usually exposed to radiation (e.g., light) locally and in high resolution at a process temperature, and thus cured.
  • the first layer may be cured on a build platform or other substrate for supporting the object; subsequent layers are sequentially cured and adhere to previous layers in a layer-by-layer manner.
  • This layer-by-layer build-up can take place in a bottom-up or top-down process.
  • Achievable curing depths and the layer thicknesses of each layer in the additive manufacturing process can be, for example, be within a range from 1 pm to 1000 pm, from 10 pm to 500 pm, or from 25 pm to 300 pm.
  • Examples of radiation-curing additive manufacturing processes include, without limitation, stereolithography (SLA), digital light processing (DLP), liquid crystal display (LCD), two-photon lithography, inkjet, volumetric 3D printing, area-wise vat polymerization, material jetting, area- wise film polymerization, thermoset deposition, continuous fiber thermoset deposition, vat vulcanization, various nozzle-based technologies, and various process combinations thereof.
  • SLA stereolithography
  • DLP digital light processing
  • LCD liquid crystal display
  • two-photon lithography inkjet
  • volumetric 3D printing area-wise vat polymerization
  • material jetting area-wise film polymerization
  • thermoset deposition continuous fiber thermoset deposition
  • vat vulcanization various nozzle-based technologies, and various process combinations thereof.
  • the aforementioned technologies and process combinations can also be combined with additional technologies, for example with other generative or additive manufacturing processes, such as fused deposition modeling, subtractive processes, fiber placement and fiber coating processes, drilling and soldering processes, dye coating and bonding processes, cold and hot plasma treatment processes, wire bonding processes, spray coating and micro-droplet processes, casting processes, cutting and milling processes, and other processes. Additional examples and details of additive manufacturing processes that may be used to fabricate the object are provided in Section II below.
  • the curing is performed using energy (e.g., radiation such as light) having a first wavelength range.
  • the first wavelength range may be within a range from 150 nm to 750 nm, from 200 nm to 550 nm, or from 320 nm to 480 nm, for example.
  • the composition used to fabricate the object may be configured accordingly (e.g., by selection of the various components of the composition) to be compatible with the first wavelength range.
  • the activatable filler can be made of materials that exhibit low absorption in the first wavelength range, to avoid interfering with curing.
  • the activatable filler can have a particle size that is configured to avoid absorbing and/or scattering light in the first wavelength range, which may prevent curing and/or reduce curing accuracy, while also maintaining storage stability (e.g., little to no sedimentation over time).
  • Post-processing can include various processes performed on the object after additive manufacturing, such as cleaning using centrifugal forces in centrifuges, cleaning using fluids (e.g. with solvents using turbulent flows, directed jets, ultrasound, steam, aerosols and/or in pressure cycling processes), cleaning using gases and/or directed gas flows (e.g.
  • the process of block 106 can include removing residual material from the object.
  • the residual material can include excess material (e.g., uncured resin) and/or other unwanted material (e.g., debris) that remains on or within the object after the additive manufacturing process.
  • the residual material can be removed in many different ways, such as by exposing the object to a solvent (e.g., via spraying, immersion), heating or cooling the object, applying a vacuum to the object, blowing a pressurized gas onto the object, applying mechanical forces to the object (e.g., vibration, agitation, centrifugation, tumbling, brushing), and/or other suitable techniques.
  • the residual material can be collected and/or processed for reuse. Additional details and examples of techniques for removing residual material are provided in International Publication Nos. WO 2023/214319 and WO 2023/095047, the disclosures of which are incorporated by reference in their entirety.
  • the process of block 106 can also include post-curing the object.
  • Post-curing is an additional curing process that can be used in situations where the object is still in a partially cured “green” state after fabrication.
  • the energy used to fabricate the object in block 102 may only partially polymerize the precursor material forming the object.
  • the post-curing step may be needed to fully cure (e.g., fully polymerize) the object to its final, usable state.
  • Post-curing can provide various benefits, such as improving the mechanical properties (e.g., stiffness, strength) and/or temperature stability of the object.
  • Post-curing can be performed by heating the object, applying radiation (e.g., UV, visible, microwave) to the object, or suitable combinations thereof.
  • the process of block 106 can include removing sacrificial components that are not intended to be part of the final object (e.g., support structures may be removed using blades, lasers, etc.), cleaning the object (e.g., washing, solvent extraction), annealing the object, separating the object from a build platform, and/or performing surface modifications and/or treatments.
  • the process of block 106 includes inserting additional components (e.g., metal parts, pins, electrical contacts, cables, sensors, microchips) into the object.
  • additional components e.g., metal parts, pins, electrical contacts, cables, sensors, microchips
  • Such components may be inserted into the green state object before post-curing, since the green state object is still soft and may have a lower modulus. This can allow the object geometry, which may shrink during the post-curing process, to adapt to the geometry of the inserted components.
  • the additional components may be inserted into the object after post-curing.
  • the method 100 can include applying energy to the object to selectively activate the activatable filler at the second portion of the object.
  • the energy may be radiation, such as light energy (e.g., visible light, ultraviolet (UV) light, infrared (IR) light, near IR light) output by a light source (e.g., a laser).
  • a laser beam can be applied to the object to selectively activate the activatable filler at locations where a metallic material is to be deposited (the second portion of the object), in a process known as “laser direct structuring” (LDS).
  • LDS laser direct structuring
  • the laser can have a wavelength and power that is configured to cause the activatable filler to form a substrate (e.g., surface or volume) for subsequent metallization.
  • the activatable filler can be a metal-containing compound that forms metal nuclei when activated (e.g., via reduction of a metal oxide to a metal), and metallization can be grown on the remaining metal nuclei.
  • the activation is performed using energy having a second wavelength range.
  • the second wavelength range can be an IR or near IR spectral range, such a wavelength range that is greater or equal to than 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 1050 nm, or more.
  • the LDS process can be performed via an IR laser with a wavelength of 1064 nm, using a laser beam having a cross-section of about 80 pm, a laser power within a range from 8 W to 14 W, a pulsed frequency within a range from 80 kHz to 100 kHz, and a laser speed of about 1 m/s.
  • the second wavelength range can be different from the first wavelength range used in the additive manufacturing process (e.g., the second wavelength range may not overlap the first wavelength range). Accordingly, the additive manufacturing process can be performed without inadvertently activating the filler, and the activation process can be performed without unwanted curing of the polymeric material.
  • the first wavelength range may be within or overlap a wavelength range from 150 nm to 750 nm, while the second wavelength range can have a lower threshold of at least 850 nm.
  • the wavelengths of the first wavelength range can be shorter than the wavelengths of the second wavelength range, or vice-versa.
  • the energy can be selectively applied to the second portion of the object that is to be formed from a metallic material, while the remaining portions (e.g., first portion) of the object are not exposed to the energy (or at least not exposed to energy of sufficient power to cause activation of the filler).
  • This can be accomplished, for example, using a controller that targets the laser only onto the second portion of the object (e.g., based on the digital representation of block 102).
  • the filler may be activated only at the second portion of the object and may remain unactivated at the remaining portions of the object, such that the second portion contains metal nucleation sites for metallization while the remaining portions do not.
  • the precursor of the polymeric material and/or the polymeric material is configured to degrade and thus be removed when exposed to the energy in second wavelength range. Accordingly, the laser can also ablate the polymeric material to form a rough surface that further facilitates metallization.
  • the method 100 can include depositing the metallic material at the second portion of the object where the filler was activated.
  • the metallic material may be deposited, for example, using metallization processes such as chemical (electroless) or electrochemical plating methods.
  • metallic materials that may be deposited include copper, nickel, gold, silver, tin (e.g., soldering tin), palladium, platinum, ruthenium, cobalt, indium, titanium, chromium, tantalum, niobium, and lead.
  • a single layer of a single metallic material may be deposited, or multiple layers of the same or different metallic materials may be deposited.
  • the object may be cleaned between process steps (e.g., after activation and before metallization, between different deposition of different metallization layers).
  • the metallic material may be selectively deposited only at the second portion of the object (containing metal nucleation sites resulting from the activated filler) and not at the remaining portions (e.g., first portion) of the object (which do not contain metal nucleation sites). Accordingly, depending on the resolution of the laser used in the LDS process, the resulting metallic material can be deposited according to a desired geometry with a high degree of accuracy.
  • the method 100 illustrated in FIG. 1 can be modified in many different ways. For example, although the above steps of the method 100 are described with respect to a single object, the method 100 can be used to sequentially or concurrently fabricate and postprocess any suitable number of objects, such as tens, hundreds, or thousands of additively manufactured objects. As another example, the ordering of the processes shown in FIG. 1 can be varied. Some of the processes of the method 100 can be omitted (e.g., the processes of blocks 102, 106, 108, and/or 110), and/or the method 100 can include additional processes not shown in FIG. 1.
  • the present technology provides a method for manufacturing an object from a composition (e.g., resin composition) of the present technology, where the composition is subjected to a light-induced structuring step, optionally followed by a heat-induced curing step (e.g., thermal post-curing).
  • a light-induced structuring step is followed by a light-induced curing step (e.g., UV post-curing).
  • the light-induced structuring step may be an additive manufacturing process, followed by postprocessing (e.g., thermal and/or UV post-curing steps) to obtain a final product having the desired chemical, mechanical, and thermal properties.
  • the light-induced structuring step is carried out using light having a first wavelength in a range from 150 nm to 750 nm.
  • the light-induced structuring step is carried out utilizing a UV/Vis light source and corresponding optics, and the UV/Vis configuration is selected from the group consisting of laser/DLP, LED/DLP, laser/LCD, and LED/LCD.
  • compositions with a viscosity below 1 Pa s at ambient conditions or slightly higher temperatures are used in radiation-curing additive manufacturing processes, and temperatures above 35 °C are rarely reached nor suitable.
  • radiation-curing additive manufacturing processes for highly viscous resins at elevated temperatures e.g., hot lithography
  • the light-induced structuring step is carried out at elevated processing temperatures, such as at a temperature within a range from 25 °C to 150 °C, such as from 35 °C to 100 °C, or from 40 °C to 90 °C. This may be done, for example, to improve processability for compositions having a high content of the polymeric precursor and/or activatable filler, with potentially high molecular weight, high softening or melting temperatures, and/or high surface area, and/or to reduce the viscosity of the composition during the light-induced structuring step.
  • a layer of the composition is formed on a carrier plate or film, e.g., using a recoater blade.
  • the layer being formed may have a thickness of less than 2 mm, 1 mm, 0.8 mm, 0.5 mm, or 0.2 mm, for example.
  • the present composition may have a viscosity at the processing temperature within a range from 0.5 Pa s to 70 Pa s, or from 1 Pa s to 30 Pa s. At 20 °C, the viscosity of the present composition may be within a range from 1 Pa s to 1,000,000 Pa s, from 2 Pa s to 1,000 Pa s, or from 5 Pa s to 100 Pa s.
  • the light-induced structuring step involves building the object on a build platform in a layer-by-layer manner to obtain a stack of structured layers, wherein each structured layer is obtained by the steps of: (1) forming an unstructured layer of a predetermined thickness of the composition, and (2) selectively projecting light onto the unstructured layer according to a desired pattern, thereby curing the composition to obtain the structured layer.
  • layers of the object can be formed one after the other and one on top of each other by each forming a material layer of predetermined thickness of the composition between a transparent or at least partially transparent carrier such as a plate, a carrier film, or a bottom of a vat, and a mechanically adjustable build platform, or the object is at least partially formed on the build platform and where the so-defined material layer is cured in a position-selective manner, in particular by irradiation through the transparent or at least partially transparent carrier, to provide the desired shape of the layer.
  • a transparent or at least partially transparent carrier such as a plate, a carrier film, or a bottom of a vat
  • a mechanically adjustable build platform or the object is at least partially formed on the build platform and where the so-defined material layer is cured in a position-selective manner, in particular by irradiation through the transparent or at least partially transparent carrier, to provide the desired shape of the layer.
  • the light-induced structuring step is carried out using a first radiation source, where the radiation of the first radiation source is applied to the composition through the transparent carrier plate, and heating of the layer of resin composition to be structured is carried out using a second radiation source, where the carrier plate is substantially impermeable to the radiation of the second radiation source.
  • the carrier plate is heated by the radiation of the second radiation source, said radiation substantially not entering into the layer of the composition, and the composition thus indirectly heated via the carrier plate is structured by the radiation of the first radiation source.
  • a layer of the composition is formed on a carrier plate (e.g., via a recoater blade), and the layer is cured via the light-induced structuring step, where the thickness of the formed layer is greater than 10 pm, 25 pm, or 40 pm, and/or is smaller than 1000 pm, 800 pm, 500 pm, or 400 pm, and the curing depth is at least 1.1 times the layer height.
  • an object is produced from the composition of the present technology, where the light-induced structuring step is an additive manufacturing process, such as stereolithography (SLA), digital light processing (DLP), material jetting, or inkjet printing, e.g., using a hot lithography technique.
  • SLA stereolithography
  • DLP digital light processing
  • material jetting material jetting
  • inkjet printing e.g., using a hot lithography technique.
  • a heat-curing step may be performed to yield further cure (e.g., post-curing).
  • the heat-induced curing step can involve direct application of heat to the object via active heating in an oven (e.g., electric, gas, or solar oven), indirect application of heat by subjecting the object to electromagnetic radiation (e.g., microwave radiation, IR light), and/or inducing secondary exothermic reactions such as thermal polymerization in the object.
  • an oven e.g., electric, gas, or solar oven
  • electromagnetic radiation e.g., microwave radiation, IR light
  • secondary exothermic reactions such as thermal polymerization in the object.
  • the heat-induced curing step is performed at a temperature that is higher than the processing temperature of the light-induced structuring step, such as a temperature within a range from 100 °C to 400 °C, from 120 °C to 400 °C, from 100 °C to 350 °C, or from 100 °C to 300 °C.
  • the heat-induced curing step may be divided into one or more individual curing steps with defined time intervals at respectively defined temperatures and defined heating rates (e.g., 10 K/min).
  • Non-limiting examples for such heat-curing steps include:
  • the heat-induced curing step is performed after the light- induced structuring step and/or after an additional UV post-processing step, where the printed objects are cured at a temperature higher than the initial processing temperature of the light- induced structuring step, such as at a temperature greater than 100 °C, 120 °C, or 140 °C, and/or at a temperature where the formed material still exhibits sufficient thermal stability, such as less than 350 °C, 300 °C, or 200°C.
  • a part cleaning step is performed between the light- induced structuring step and the heat-induced curing step.
  • the part cleaning step may be performed physically (e.g., via centrifuge, shaking, pressured air, vacuum) and/or chemically (e.g., solvent or vapor cleaning using isopropyl alcohol, glycol ethers, aromatic solvents, and/or alkanes).
  • a cured material and/or object is formed, where the material/object is characterized in that it exhibits an improved heat deflection temperature (HDT) according to DIN EN ISO 75 (HDT-A tests were performed), such as an HDT-A of greater than 50 °C, 70 °C, or 90 °C.
  • HDT heat deflection temperature
  • the cured material and/or obj ect may be characterized in that the material/obj ect exhibits the following mechanical properties:
  • the present technology provides a composition (e.g., a resin composition) for additive manufacturing of a hybrid object including one or more polymeric portions composed of a polymeric material, and one or more metallic portions composed of a metallic material.
  • the composition can include a precursor of the polymeric material (“polymeric precursor,” “polymerizable matrix component,” “component A”) that is configured to be cured and/or polymerized according to an additive manufacturing process to form the polymeric material.
  • the composition can also include an activatable filler (“component B”) that is configured to be activated to form a substrate for deposition of the metallic material.
  • the composition can also include a photoinitiator (“component C”) that forms a reactive species when exposed to energy to induce curing and/or polymerization of the polymeric precursor during the additive manufacturing process.
  • component C a photoinitiator
  • component D one or more additives that serve various functions, such as modulating the chemistry and/or properties of the composition and/or the fabricated object.
  • the composition includes from 10 wt% to 99 wt%, from 20 wt% to 98 wt%, from 30 wt% to 97 wt%, or from 50 wt% to 95 wt% of the polymeric precursor. In some embodiments, the composition includes from 0.1 wt% to 50 wt%, from 1 wt% to 30 wt%, from 3 wt% to 20 wt%, or from 5 wt% to 15 wt% of the activatable filler.
  • the composition includes from 0.001 wt% to 20 wt%, from 0.1 wt% to 10 wt%, or from 0.5 wt% to 5 wt% of the photoinitiator. In some embodiments, the composition includes from 0.0001 wt% to 90 wt% of the additive.
  • the polymeric precursor can include one or more polymerizable components, such as one or more monomers, oligomers, and/or reactive polymers.
  • the polymerizable components can be any molecule or compound capable of forming bonds with other polymerizable components, thus resulting in a larger molecule with increased molecular weight.
  • the bond-forming reaction occurs multiple times, such that the molecular weight of the resultant molecule increases with each successive bond-forming reaction.
  • bond-forming reactions suitable for use with the techniques described herein include, but are not limited to, free radical polymerization, ionic polymerization (e.g., cationic polymerization, anionic polymerization), condensation polymerization, metathesis polymerization, ring opening polymerization, Diels-Alder reactions, photodimerization, carbene formation, nitrene formation, acetal formation, and suitable combinations thereof.
  • ionic polymerization e.g., cationic polymerization, anionic polymerization
  • condensation polymerization e.g., metathesis polymerization, ring opening polymerization, Diels-Alder reactions, photodimerization, carbene formation, nitrene formation, acetal formation, and suitable combinations thereof.
  • the polymerizable components include one or more light-curable components, which may be susceptible to layer-by-layer photopolymerization for manufacturing a component (e.g., radiation-curing additive manufacturing processes).
  • the additive manufacturing process can include providing a composition including the light-curable components in a production bath (e.g., a vat), on a production bed (e.g., on a carrier film, plate, or other substrate), and/or as a wet layer, and selectively curing the composition in a layer-by-layer manner by polymerization in the production bath, on the production bed and/or in the wet layer by selective light irradiation via a light source in a first wavelength range to form an additively manufactured object, as described elsewhere herein.
  • the polymerizable components include one or more of the following: an acrylate monomer, a (meth)acrylate monomer, a thiol monomer, a vinyl acetate monomer, a vinyl ether monomer, a vinyl chloride monomer, a vinyl silane monomer, a vinyl siloxane monomer, a styrene monomer, an allyl ether monomer, an acrylonitrile monomer, a butadiene monomer, a norbornene monomer, a maleate monomer, a fumarate monomer, an epoxide monomer, an anhydride monomer, a cyclic ether monomer, a cyclic ester monomer, a cyclic carbonate monomer, a cyclic carbamate monomer, or a hydroxyl monomer.
  • the polymerizable components include one or more of the following: a free radically polymerizable group, a cationically polymerizable group, or an anionically polymerizable group.
  • the polymerizable components include one or more reactive functional groups, such as one or more of the following: an acrylate, a (meth)acrylate, an acrylamide, a vinyl group, a vinyl ether, a thiol, an allyl ether, a vinyl silane, an allyl silane, a norbomene, a vinyl acetate, a maleate, a fumarate, a methylenemalonate, a maleimide, an epoxide, a ring-strained cyclic ether, a ring-strained thioether, a cyclic ester, a cyclic carbonate, a cyclic silane, a cyclic siloxane, a hydroxyl, an amine, an is
  • the polymeric precursor includes one or more (meth)acrylates, (meth)acrylamides, allyl components, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, citraconimides, itaconimides, itaconates, fumarates, styrene compounds, cyclic ethers such as epoxy compounds or oxetanes, benzoxazines, oxazolines, and/or cyanoacrylates.
  • the polymeric precursor includes one or more (meth)acrylates, (meth)acrylamides, and/or allyl components.
  • the polymeric precursor is selected from the group consisting of curable mono- and/or multi-functional monomer, oligomer, prepolymer and/or polymer resin components with reactive end groups and/or side groups, such as:
  • (Meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n- propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n- hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl(meth)acrylate, n-decyl(meth)acrylate, n-dodecyl(meth)acrylate, 2- hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2- or 3- hydroxypropyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, 2- ethoxyethyl(meth)acrylate, 2- or 3-ethoxypropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, isobornyl(
  • (acryloyloxy)ethyl] isocyanurate tris[2-(methacryloyloxy)ethyl] isocyanurate, bis[2-(methacryloyloxy)ethyl] isocyanurate, bis[2- (acryloyloxy)ethyl] isocyanurate, dentritic (meth)acrylate oligomers (e.g., Bomar BDT-4330, Bomar XDT-1018, Bomar BDT-1015, BDT-1006, Miramer SP1106, AOHUI HP6310, AOHUI HP6610), melamine acrylate (e.g., Miramer SC9610), Raylok 1722, tetrahydrodi cyclopentadienyl (meth)acrylate, and isobornylcyclohexyl (meth)acrylate.
  • dentritic (meth)acrylate oligomers e.g., Bomar BDT-4330, Bomar XDT-1018
  • (Meth)acrylamides such as N,N-di(methyl)acrylamide, N- isopropylacrylamide, butyl acrylamide, N,N'-methylenebis(acrylamide), N- hydroxyethyl acrylamide, 3-dimethylaminopropylacrylamide, N, N-diethyl acrylamide, N,N-diphenyl acrylamide and acrylamides such as 4- acryloylmorpholine (ACMO), and l,3,5-triacryloylhexahydro-l,3,5- tri azine,
  • ACMO 4- acryloylmorpholine
  • ACMO 4- acryloylmorpholine
  • Allyl compounds such as allylphenol, triallylamines, 2,2’-bis[4- allyloxyphenyl]propane, l,l,l-tris(hydroxymethyl)-propane diallyl ether, diallyl isophthalate, diallyl phthalate, diallyl terephthalate, cyclohexanedicarboxylic acid diallyl ester, diallyl diglycol carbonate, diallyl polycarbonate, diallyl 2,2’ -oxy di ethyldicarbonate and oligomers, triallyl trimellitate, particularly l,3,5-triallyl-l,3,5-triazine- 2,4,6(lH,3H,5H)-trione, o, o’ -diallylbisphenol- A, 2,4,6-tris(allyloxy)-l,3,5- triazine, 4,4’-bis(o-propenylphenoxy)-benzophenones, 2,2’-bis
  • the polymeric precursor includes a combination of components such as at least one monofunctional reactive diluent (e.g., isobomyl acrylate); at least one multifunctional oligomer, prepolymer or polymer (e.g., a difunctional urethane acrylate with a molecular weight greater than 500 g/mol); and optionally at least one low molecular-weight, multifunctional crosslinker (e.g., triethylene glycol dimethacrylate, tris[2- (methacryloyloxy)ethyl] isocyanurate) or a crosslinker, which includes at least one second polymerizable group other than (meth)acrylates (e.g., allyl, vinyl, maleimide, epoxy) to form a hybrid photopolymer network.
  • at least one monofunctional reactive diluent e.g., isobomyl acrylate
  • at least one multifunctional oligomer, prepolymer or polymer e.g.,
  • the polymeric precursor includes polymerizable isocyanurate, cyanurate, and/or melamine groups (e.g., l,3,5-triallyl-l,3,5-triazine- 2,4,6(lH,3H,5H)-trione, 2,4,6-tris(allyloxy)-l,3,5-triazine, tris[2-(acryloyloxy)ethyl] isocyanurate, tris[2-(methacryloyloxy)ethyl] isocyanurate, melamine (meth)acrylates).
  • polymerizable isocyanurate, cyanurate, and/or melamine groups e.g., l,3,5-triallyl-l,3,5-triazine- 2,4,6(lH,3H,5H)-trione, 2,4,6-tris(allyloxy)-l,3,5-triazine, tris[2-(acryloyloxy)ethyl] is
  • the polymeric precursor includes a mixture of at least one (meth)acrylate and at least one maleimide, or a mixture of at least one (meth)acrylate and at least one citraconimide, or a mixture of at least one (meth)acrylate and at least one allyl compound.
  • the (meth)acrylate and allyl compound include an isocyanurate, cyanurate, and/or melamine group, whereby the maleimide and citraconimide are at least difunctional.
  • the polymeric precursor is composed of at least one monofunctional reactive diluent, which ranges from 5 wt% to 60 wt%; at least one multifunctional oligomer, prepolymer or polymer, which ranges from 5 wt% to 95 wt%; and optionally at least one low molecular-weight, multifunctional crosslinker, which ranges from 5 wt% to 95 wt%, based on the total weight of all components making up the polymeric precursor
  • the polymeric precursor has the formulation of Table 1 below. [0076] Table 1 : Polymeric Precursor Formulation
  • any light-curable component or correspondingly behaving material which cross-links and cures structurally by photochemical processes under light irradiation e.g., in the presence of suitable photoinitiator systems
  • any light-curable component or correspondingly behaving material which cross-links and cures structurally by photochemical processes under light irradiation (e.g., in the presence of suitable photoinitiator systems) can be used herein as the polymeric precursor.
  • the polymeric material formed from the polymeric precursor can have properties that are compatible with metallic materials.
  • the polymeric material can have a coefficient of thermal expansion (CTE) that is similar to the CTE of the metallic material, e.g., to avoid separation from the metallic material under varying temperature conditions.
  • CTE of the polymeric material is within a range from 20 ppm/°C to 160 ppm/°C, or from 40 ppm/°C to 120 ppm/°C.
  • the polymeric material can have a glass transition temperature (Tg) that is sufficiently high to avoid deforming due to heat produced by the electronics.
  • Tg glass transition temperature
  • the Tg of the polymeric material can be greater than or equal to 100 °C, 105 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, or 200 °C.
  • the activatable filler can be any compound that is configured to be activated by energy to form a substrate for deposition of a metallic material.
  • the activatable filler is a filler that is suitable for use in an LDS process (“LDS filler”).
  • LDS filler can allow for laser structuring via irradiation with a laser in a second wavelength range, as described herein.
  • the LDS filler is a metal-containing compound that is sensitive to (e.g., may be reduced by) IR laser radiation, such as an IR-laser-sensitive pigment. Subsequently, in a chemical process, metal ions, such as copper, can then grow at the sites activated by IR radiation to form the corresponding metallic conductive paths.
  • the activatable filler is a mixed oxide or mixed metal oxide.
  • the activatable filler can be a mixed oxide selected from the group consisting of indium oxide, tin oxide (e.g., doped tin oxide such as indium tin oxide or tin antimony oxide), titanium oxide, ferric oxide, rutile titanium dioxide, tin antimony oxide, tin antimony grey cassiterite, antimony trioxide, bismuth(III) oxide, tungsten oxide, copper tungstate, copper phosphate, and mica.
  • tin oxide e.g., doped tin oxide such as indium tin oxide or tin antimony oxide
  • titanium oxide ferric oxide
  • rutile titanium dioxide titanium dioxide
  • tin antimony oxide tin antimony grey cassiterite
  • antimony trioxide antimony trioxide
  • bismuth(III) oxide bismuth(III) oxide
  • tungsten oxide copper tungstate
  • copper phosphate copper phosphate
  • mica such as
  • the activatable filler includes a high-performance metal based seed-forming LDS filler, for example, a copper based seed-forming LDS filler such as copper chromite black spinel.
  • a high-performance metal based seed-forming LDS filler for example, a copper based seed-forming LDS filler such as copper chromite black spinel.
  • Such components are typically beneficial in terms of compatibility with the polymeric precursor. However, in some instances, the high UV-light absorption of these components may limit the amount in which such substances can be used within the compositions described herein.
  • the activatable filler is a pigment containing doped tin oxide (e.g., doped with non-metallic elements), e.g., as described in International Publication No. WO 2015/197157, the disclosure of which is incorporated by reference herein in its entirety.
  • doped tin oxide e.g., doped with non-metallic elements
  • the activatable filler is a pigment having a substrate and a coating located on the substrate, where the coating contains iron in the oxidation state (0) and/or (II), e.g., as described in International Publication No. WO 2018/141769, the disclosure of which is incorporated by reference herein in its entirety.
  • EP 3460005 describes non-conductive compounds that are present within a range from 3% to 20% by mass with respect to the total amount of the resin composition used for LDS; European Publication No.
  • the activatable filler may be embedded in a polymer matrix or carrier, coated with a metal oxide such as ferric oxide or antimony-doped tin oxide.
  • the activatable filler is light in color, compatible with the polymeric precursor, maintains exceptional LDS activity across a broad power range, and is non-conductive, non-magnetic, non-bleeding, non-migratory, and non-warping.
  • the activatable filler is not blue and/or does not include copper complexes, which may exhibit excessively high light absorption that interferes with curing.
  • the amount of the activatable filler in the composition may be sufficiently high amount to allow for laser activation and metallization, while also being sufficiently low to avoid interfering with curing of the polymeric precursor (e.g., large amounts of activatable filler may inhibit curing due to high energy absorption).
  • the activatable filler may be present in the composition at an amount within a range from 0.01 wt% to 20 wt%, 0.02 wt% to 10 wt%, 0.05 wt% to 5 wt%, 1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 15 wt%, 1 wt% to 20 wt%, 5 wt% to 10 wt%, 5 wt% to 15 wt%, 5 wt% to 20 wt%, 10 wt% to 15 wt%, or 10 wt% to 20 wt%.
  • the activatable filler can have any suitable geometry, such as spheres, platelets and/or fibers and/or mixtures thereof, spheres, fractures and/or defined three-dimensional and/or two-dimensional structures.
  • the activatable filler is composed of a plurality of particles, such as rounded and/or spherical particles.
  • Rounded and/or spherical particles may improve flowability and/or reduction abrasion behavior in the processes described herein, which can have a beneficial effect on the processing of the compositions of the present technology.
  • rounded and/or spherical particles can reduce the anisotropy of properties of the printed object (e.g., physical, chemical, mechanical, and/or electrical properties).
  • the particle size of the activatable filler can be sufficiently large to avoid interfering with the curing of the polymeric precursor (e.g., small particles with a high surface area may inhibit curing due to high energy absorption), while also being sufficiently small to ensure a high printing resolution of the printed object (e.g., the particle size can be smaller than the height of an individual layer of the object), sedimentation stability, and printability.
  • the particle size of the activatable filler can be determined, for example, via static light scattering methods using the Mie theory according to DIN/ISO 13320 to determine the average particle size and particle size distribution.
  • the activatable filler has an average particle size (e.g., average diameter) that is greater than or equal to 1 pm, 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, or 100 pm; and/or less than or equal to 100 pm, 95 pm, 90 pm, 85 pm, 80 pm, 75 pm, 70 pm, 65 pm, 60 pm, 55 pm, 50 pm, 45 pm, 40 pm, 35 pm, 30 pm, 25 pm, 20 pm, 15 pm, 10 pm, 5 pm, or 1 pm.
  • average particle size e.g., average diameter
  • the particle size can be within a range from 1 pm to 100 pm, 1 pm to 75 pm, 1 pm to 50 pm, 1 pm to 25 pm, 1 pm to 10 pm, 10 pm to 100 pm, 10 pm to 75 pm, 10 pm to 50 pm, 10 pm to 25 pm, 25 pm to 100 pm, 25 pm to 75 pm, 25 pm to 50 pm, 40 pm to 50 pm, 50 pm to 100 pm, 50 pm to 75 pm, or 75 pm to 100 pm.
  • the particle size distribution can also be significant.
  • the particle size distribution of a sample can be measured using laser diffraction, for example, and characterized using different D xx values indicating that xx% of the particles are smaller than the specified value (e.g., Dso means that 50% of the particles are smaller than the specified value).
  • D xx values indicating that xx% of the particles are smaller than the specified value (e.g., Dso means that 50% of the particles are smaller than the specified value).
  • Other relevant parameters include Dio as a measure for the smallest particles, and Dso, D90, D95, D99, and/or D100 for the larger particles in the sample. For example, the closer Dio and D90 are to each other, the narrower the particle size distribution.
  • the activatable filler has a particle size distribution characterized by a Dso value within a range from 0.01 pm to 100 pm, or from 1 pm to 50 pm.
  • the Dso value can be less than or equal to 50 pm, 25 pm, or 10 pm.
  • the Dso value can be greater or equal than 1 pm.
  • Activatable fillers with Dso values smaller than 1 pm may have improved sedimentation stability, but printability may be compromised due to the high light absorption of the activatable fillers at a comparable size to the spectral range of the first wavelength range for curing the polymeric precursor (e.g., wavelengths from 320 nm to 480 nm).
  • the absorption effect of activatable fillers of such small sizes can limit the achievable curable layer thickness.
  • This limitation may be strongly dependent on the amount of filler and the particle size, shape, and/or distribution.
  • the higher the amount of filler and/or the smaller the particle size the greater the obstacle to light penetrating into the composition and enabling polymerization and thus structuring of the polymeric precursor. For this reason, in some embodiments, the amount of small-sized particles may be advantageously kept low in the compositions herein.
  • the activatable filler can have a particle size distribution characterized by a Dso value less than 0.2 pm. Particles in this size range may exhibit improved printability, as they may show lower light absorption within the spectral range of the first wavelength range for curing the polymeric precursor (e.g., wavelengths from 320 nm to 480 nm).
  • the particle size of the smallest particles is greater than 0.5 pm.
  • the upper particle size limit e.g., D90 value
  • the desired layer height during the additive manufacturing process may be defined by the desired layer height during the additive manufacturing process, the wall thickness and feature sizes of the final printed object, and/or the desired surface roughness (e.g., less than 50 pm).
  • the activatable filler can have a particle size distribution characterized by a Dio value greater than 0.5 pm and a D90 value less than 50 pm, a Dio value greater than 0.5 pm and a D90 value less than 20 pm, a Dio value greater than 0.5 pm and a D90 value less than 10 pm, a Dio value greater than 1 pm and a D90 value less than 10 pm, a Dio value greater than 1 pm and a D90 value less than 20 pm, or a Dio value greater than 1 pm and a D90 value less than 50 pm.
  • the activatable filler can have any suitable particle size distribution, such as a distribution having a single maximum value in the density distribution (monomodal) or having multiple maximum values in the density distribution (multimodal, such as bimodal (two maximum values), trimodal (three maximum values), etc.). Multimodal distributions may be beneficial if high amounts of filler are to be present in the composition and/or to facilitate the processability of the composition.
  • a bimodal distribution may have maximum values of about 10 pm and about 50 pm, about 10 pm and about 20 pm, about 5 pm and about 10 pm, about 1 pm and about 5 pm, about 0.5 pm and about 3 pm, or about 5 pm and 20 pm.
  • a trimodal distribution may have maximum values of about 5 pm, about 10 pm, and about 30 pm; about 1 pm, about 5 pm, and about 10 pm; or about 1 pm, about 3 pm, and about 5 pm.
  • the surface of the activatable fillers is modified. Such modifications may be used to control and/or influence phenomena such as agglomeration, mixing stability, and/or particle binding to the polymer matrix.
  • surface modifiers include silane coupling agents; cationic, anionic, and/or nonionic surfactants; alkyl-based phosphonic or carboxylic acids; polymeric dispersants like polyacrylic acid or polyvinylpyrrolidone; and modifiers with reactive polymerizable end groups like vinyl, (meth)acrylate, or epoxide.
  • the compositions herein can also contain a rheology additive, such as a nanoparticle filler with particle sizes smaller than 1 pm.
  • a rheology additive such as a nanoparticle filler with particle sizes smaller than 1 pm.
  • the particles of the activatable filler can be stabilized in the resin composition by adding rheology additives to prevent the particles from sinking within the polymeric precursor, e.g., by forming a network of physical bonds.
  • Rheology additives may be present in an amount within a range from 0.01 phr to 20 phr relative to the polymeric precursor.
  • compositions herein may have a corresponding sedimentation stability (e.g., more than four weeks at the storage temperature and/or more than two days at the process temperature) in order to ensure the storage stability of the composition and a substantially isotropic distribution of the activatable filler in the layers of the printed object during the additive manufacturing process.
  • a corresponding sedimentation stability e.g., more than four weeks at the storage temperature and/or more than two days at the process temperature
  • the photoinitiator can be any compound that forms a reactive species when exposed to energy (e.g., in the first wavelength range) to induce curing and/or polymerization of the polymeric precursor during the additive manufacturing process.
  • Example photoinitiators include Norrish type I photoinitiators selected alone or in combination with each other from the group consisting of a-hydroxy ketones; phenylglyoxylates; benzyldimethyl ketals; a-aminoketones; mono- or bisacylphosphines; - phosphine oxides; mono-, bis- or tetraacylsilanes; -germanes; -stannanes; and metallocenes.
  • Norrish type I photoinitiators selected alone or in combination with each other from the group consisting of a-hydroxy ketones; phenylglyoxylates; benzyldimethyl ketals; a-aminoketones; mono- or bisacylphosphines; - phosphine oxides; mono-, bis- or tetraacylsilanes; -germanes; -stannanes; and metallocenes.
  • photoinitiators include 2-hydroxy-2-methylpropiophenone, 1 -hydroxy cyclohexylphenyl ketone, methylphenylglyoxylates, 2-benzyl-2-(dimethylamino)- 4 ’-morpholinobutyrophenone, [l-(4-phenylsulfanylbenzoyl) heptylideneamino]benzoate, [1- [9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethylideneamino]acetate, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (TPO), ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (TPO-L), phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (BAPO), ethyl (3-benzoyl-2,4,6
  • photoinitiators include Norrish type II photoinitiators, such as benzophenones (e.g., benzophenone, 4-methylbenzophenone, 4,4’- bis(diethylamino)benzophenone), benzoin, diketones (e.g., 9,10-phenanthrenquinone, 1- phenylpropane- 1,2-dione, diacetyl or 4,4’ -di chlorobenzil and/or derivatives thereof), and thioxanthones (e.g., chloropropoxythioxanthones, isopropylxanthones, or 2,4-diethyl-9H- thioxanthen-9-one).
  • benzophenones e.g., benzophenone, 4-methylbenzophenone, 4,4’- bis(diethylamino)benzophenone
  • benzoin e.g., benzoin, diketones (e.g., 9,10-
  • Such type II photoinitiators can be used in combination with coinitiators such as tertiary amines (e.g., aromatic tertiary amines such as N,N-dialkylaniline, p-toluidine, 3,5-xylidine, p-N,N-dialkylamino-phenylethanol, benzoic acid derivatives, benzaldehyde, or triethanolamine).
  • coinitiators such as tertiary amines (e.g., aromatic tertiary amines such as N,N-dialkylaniline, p-toluidine, 3,5-xylidine, p-N,N-dialkylamino-phenylethanol, benzoic acid derivatives, benzaldehyde, or triethanolamine).
  • tertiary amines e.g., aromatic tertiary amines such as N,N-dialkylaniline, p-toluidine, 3,5-xyl
  • a combination of Norrish type I and type II photoinitiators can also be used.
  • any combination of radical, ionic, and/or insertion polymerization initiators can also be used in the context of the present technology.
  • one or more additives can be added to the composition to serve various functions, such as modulating the chemistry and/or properties of the composition and/or the fabricated object.
  • the additives can include other polymerizable components, such as monomers, oligomers, and/or polymers.
  • polymerizable additives include unsaturated carbon compounds, alkanes, alkynes, (meth)acrylates, (meth)acrylamides, fumarates, styrene derivatives, cinnamic acid derivatives, vinylamines, vinyl ethers, vinyl carbamates, vinyl esters, allyl compounds, vinyl compounds, cyanoacrylates, epoxides, oxetanes, cyanate esters, cyclic ring-opening polymerizable compounds, and/or cyclopolymerizable compounds.
  • the additives can include one or more of the following: polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, dyes, surface modifiers, flame retardants, additives to reduce polymerization shrinkage and/or shrinkage stress (e.g., network modifiers), and mixtures thereof.
  • the polymerization inhibitors may be quinones, such as hydroquinones and benzoquinones, phenothiazines, diethylhydroylamine, 4-tert-butylcathecol, butylated hydroxytoluene, pyrogallol, TEMPO.
  • the polymerization inhibitors may be present in amounts within a range from 0.001 wt% to 3 wt%, from 0.005 wt% to 0.5 wt%, or from 0.01 wt% to 1 wt%.
  • the additives include additional organic and/or inorganic fillers.
  • organic fillers include core-shell polymer particles, block copolymers, PTFE, high performance polymers, thermoplastics, such as polyimides, polyamides, polycarbonates, polystyrene, polyoxymethylene, liquid crystal polymer, polybenzimidazoles, polyetherimides, polybutylene terephthalate, polyethylene terephthalate, polyether sulphones, polyphenylene ethers (poly(oxy-2,6-dimethyl-l,4-phenylene)), polyphenylene sulfide or polysulfones, rubbers and the like. These can also be modified with polymerizable groups.
  • the organic fillers can be mixed into the composition, particularly if they have molecular weights (Mn) less than or equal to 10000 g/mol, 5000 g/mol, or 2500 g/mol (e.g., where Mn corresponds to the number average molecular weight and can be determined by gel permeation chromatography according to ISO 16014).
  • Mn molecular weights
  • Examples inorganic fillers include metals; metal oxides and/or ceramics (e.g., SiO2, ZrO2, TiO2, ZnO or mixtures thereof with an average particle size within a range from 0.5 pm to 10 pm); glass fibers and/or glass beads and/or wollastonite (e.g., in amounts within a range from 0.1 wt.% to 40 wt% based on the total weight of the composition); silicates such as talc, clays, silicic acid and/or mica; glass powder (e.g., quartz, glass ceramics as nano- or micro fillers with an average particle size within a range from 0.05 pm to 100 pm); carbon black, graphene, graphite and/or electrically conductive additives, such as carbon nanotubes (e.g., in amounts within a range from 0.001 wt% to 10 wt% based on the total weight of the composition).
  • the average particle size of the inorganic fillers can be determined, for example, via static light
  • the organic and/or inorganic fillers may be spheres, platelets, and/or fibers, which may, for example, lead to an increase in tensile strength and/or tensile modulus (e.g., wollastonite, nanofibers, whiskers and/or mixtures thereof, spheres, fractures and/or defined 3D structures (e.g., graphite) and/or 2D structures (e.g., monolayers of graphene).
  • tensile strength and/or tensile modulus e.g., wollastonite, nanofibers, whiskers and/or mixtures thereof, spheres, fractures and/or defined 3D structures (e.g., graphite) and/or 2D structures (e.g., monolayers of graphene).
  • the surface of the fillers can be modified (e.g., silanization via radical polymerizable silanes such as 3- methacryloyloxypropyltrimethoxysilane).
  • Functionalized acidic phosphates e.g., 10- methacryloyloxydecyl dihydrogen phosphate
  • ZrCh or TiCh agglomeration, mixing stability, and/or particle binding to the polymer matrix.
  • composition according to the present technology may additionally contain, alone or in combination with each other, the following components as additives: stabilizers (e.g., UV stabilizers or anti-aging agents), antioxidants, dyes or pigments, defoamers, thermal initiators, catalysts, antibacterial agents, antistatic agents, plasticizers or lubricants, wetting agents, matting agents, adhesion promoters, rheology modifiers, thixotropic agents, dispersing agents, optical brighteners, opacifiers, antifoaming agents, additional synergistic flame retardants, cyclopolymerizable monomers, and/or UV absorbers.
  • stabilizers e.g., UV stabilizers or anti-aging agents
  • antioxidants e.g., dyes or pigments
  • defoamers e.g., thermal initiators, catalysts, antibacterial agents, antistatic agents, plasticizers or lubricants, wetting agents, matting agents, adhesion promoters, rheology modifier
  • thermal initiators or catalysts as additives that can be activated in a process downstream of additive manufacturing
  • thermal initiators include peroxides, hydroperoxides, percarbonates, peroxyacetates, azo compounds (such as azobis(isobutyronitrile), l,r-azobis(cyclohexane-l-carbonitrile), 2,2’-azobis(2,4,4- trimethylpentane), 2,2’-azobis(N-butyl-2-methylpropionamide)), 2,3-dimethyl-2,3- diphenylbutane, tert-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, di-isopropylbenzene mono hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5- dimethyl-2,5-di(tert-butylperoxy)
  • network modifiers or network regulators such as transfer reagents such as thiols, addition-fragmentation chain transfer (AFCT) reagents, reversible-addition-fragmentation chain-transfer (RAFT) reagents, nitroxide-mediated radical polymerization (NMP) reagents
  • transfer reagents such as thiols
  • AFCT addition-fragmentation chain transfer
  • RAFT reversible-addition-fragmentation chain-transfer
  • NMP nitroxide-mediated radical polymerization
  • thiols include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3- mercaptopropionate), and tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate.
  • the composition according to the present technology further includes additives that provide improved flame retardancy, reduced smoke toxicity, and/or smoke formation.
  • additives that provide improved flame retardancy, reduced smoke toxicity, and/or smoke formation.
  • Such flame retardant and/or smoke suppressing additives may be selected from groups of substances known in the polymer industry.
  • Such flame-retardant and/or smoke-suppressing additives may include, for example, inorganic fillers or mineral flame retardants (such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony oxide, tin oxide, borax and/or zinc borate, red phosphorus, expandable graphite), organic additives (such as nitrogen donors and/or halogenated (e.g., brominated) inorganic and organic flame retardants such as halogenated phosphates, halogenated diphenyl ethers, halogenated styrene, halogenated epoxides, halogenated (meth)acrylates, trischi or oisopropyl phosphonate), aluminum hydroxide, aluminum oxide hydroxide, magnesium hydroxide, dipentaeritrol, pentaeritrol, expandable graphite, organic additives such as nitrogen donors and/or phosphorus-containing substances such as melamine, melem, melon, melamine
  • such organic flame retardant additives are functionalized with a polymerizable group, such as vinyl groups, allyl groups, epoxides, acrylamides, and/or (meth)acrylate.
  • the additive includes liquid flame-retardant chemical compounds or flame retardants with a melting point less than or equal to 90 °C, 70 °C, or 50 °C. Flame-retardant chemical compounds with polymerizable groups may be beneficial. Oligomeric or polymeric flame-retardant chemical compounds that cannot migrate out of the composition according to the present technology may also be beneficial.
  • flame retardants or flame-retardant chemical compounds with high hydrolysis resistance or high thermal stability may also be beneficial.
  • beneficial flame-retardant chemical compounds in this context are polymerizable DOPO derivatives, for example o-allyl-DOPO, 6-(2-allylphenoxy)dibenzo[c,e][l, 2]oxaphosphinine-6-oxide or 6-(3-(allyloxy)-2- hydroxypropyl)dibenzo[c,e][l,2]oxaphosphinine-6-oxide, bisphenol-A bis(diphenylphosphate), (l-methylethylidene)di-4,l -phenylenetetraphenyl diphosphate and oligomers thereof, polymers of phosphorus trichloride with 1,3 -benzenediol phenyl ester, polymers of phosphoric acid and mixed esters of [l,l’-biphenyl]-4,4’-d
  • DOPO derivatives for example
  • an amide-containing phosphinate salt such as aluminum P-(N-phenyl carb ami de)ethyl methyl phosphinate, aluminum P-(N-cyclohexylcarbamide)ethyl methylphosphinate, and/or aluminum P-(N-butylcarbamide)ethyl methylphosphin
  • the addition of flame retardants to the compositions herein results in photopolymers passing the UL94 standard with a V-0 rating at thicknesses less than or equal to 5 mm, 3 mm, 2 mm, or 1 mm.
  • the composition according to the present technology contains additional toughness modifiers as additives selected from the group consisting of thermoplastic and duromeric resins.
  • resins may be, for example, polypropylene, polyethylene, polyamide, polyethylene oxide and/or polypropylene oxide, reactive rubbers, polybutadienes (such as butadiene-acrylonitrile copolymers), and/or natural polymers (such as cellulose and/or gelatin).
  • Such components may optionally be terminated or functionalized with one or more reactive, free-radically, or ionically polymerizable groups (e.g., (meth)acrylate (meth)acrylamide, vinyl ester, vinyl ether or styrene compounds, cyclic ethers such as epoxy compounds or oxetanes), and/or monomers which contain these reactive groups with flexible linkers, in particular long aliphatic chains and/or ethylene glycol spacers, particularly core-shell polymer particles and/or TPU particles (thermoplastic polyurethane).
  • Such additives may be present in an amount from 0.5 wt% to 30 wt%, from 2 wt% to 15 wt%, or from 5 wt% to 10 wt% based on the total weight of the composition.
  • silicones may be added as additives to the composition.
  • these silicones are end group and/or side group modified, where typical chemical groups for modification are selected from the group consisting of vinyl groups, allyl groups, (meth)acrylates, silanols, siloxanes, alkoxy groups, alkoxides, hydrides, amines, epoxides, oxetanes, mercapto groups, carbinols, maleimides, and acetoxy groups.
  • vat photopolymerization in which an object is constructed from a vat or other bulk source of liquid photopolymer resin, including techniques such as stereolithography (SLA), digital light processing (DLP), continuous liquid interface production (CLIP), two-photon induced photopolymerization (TPIP), and volumetric additive manufacturing
  • material jetting in which material is jetted onto a build platform using either a continuous or drop on demand (DOD) approach
  • binder jetting in which alternating layers of a build material (e.g., a powder-based material) and a binding material (e.g., a liquid binder) are deposited by a print head
  • material extrusion in which material is drawn though a nozzle, heated, and deposited layer-by-layer, such as fused deposition modeling (FDM) and direct ink writing
  • the additively manufactured object can be fabricated using a vat photopolymerization process in which light is used to selectively cure a vat or other bulk source of a curable material (e.g., a polymeric resin).
  • a curable material e.g., a polymeric resin.
  • Each layer of curable material can be selectively exposed to light in a single exposure (e.g., DLP) or by scanning a beam of light across the layer (e.g., SLA).
  • Vat polymerization can be performed in a “top-down” or “bottom-up” approach, depending on the relative locations of the material source, light source, and build platform.
  • the additively manufactured object can be fabricated using high temperature lithography (also known as “hot lithography”).
  • High temperature lithography can include any photopolymerization process that involves heating a photopolymerizable material (e.g., a polymeric resin).
  • high temperature lithography can involve heating the material to a temperature of at least 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, or 120 °C.
  • the material is heated to a temperature within a range from 50 °C to 120 °C, from 90 °C to 120 °C, from 100 °C to 120 °C, from 105 °C to 115 °C, or from 105 °C to 110 °C.
  • the heating can lower the viscosity of the photopolymerizable material before and/or during curing, and/or increase reactivity of the photopolymerizable material.
  • high temperature lithography can be used to fabricate objects from highly viscous and/or poorly flowable materials, which, when cured, may exhibit improved mechanical properties (e.g., stiffness, strength, stability) compared to other types of materials.
  • high temperature lithography can be used to fabricate objects from a material having a viscosity of at least 5 Pa-s, 10 Pa-s, 15 Pa-s, 20 Pa-s, 30 Pa-s, 40 Pa-s, or 50 Pa-s at 20 °C.
  • Representative examples of high-temperature lithography processes that may be incorporated in the methods herein are described in International Publication Nos. WO 2015/075094, WO 2016/078838, WO 2018/032022, WO 2020/070639, WO 2021/130657, and WO 2021/130661, the disclosures of each of which are incorporated herein by reference in their entirety.
  • the additively manufactured object is fabricated using continuous liquid interphase production (also known as “continuous liquid interphase printing”) in which the object is continuously built up from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the building surface of the object and a polymerization-inhibited “dead zone.”
  • a semi-permeable membrane is used to control transport of a photopolymerization inhibitor (e.g., oxygen) into the dead zone in order to form the polymerization gradient.
  • a photopolymerization inhibitor e.g., oxygen
  • a continuous additive manufacturing method can achieve continuous build-up of an object geometry by continuous movement of the build platform (e.g., along the vertical or Z-direction) during the irradiation phase, such that the hardening depth of the irradiated photopolymer is controlled by the movement speed. Accordingly, continuous polymerization of material on the build surface can be achieved.
  • a continuous additive manufacturing method can involve extruding a composite material composed of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path in order to form the object.
  • a continuous additive manufacturing method can utilize a “heliolithography” approach in which the liquid photopolymer is cured with focused radiation while the build platform is continuously rotated and raised. Accordingly, the object geometry can be continuously built up along a spiral build path.
  • a “heliolithography” approach in which the liquid photopolymer is cured with focused radiation while the build platform is continuously rotated and raised. Accordingly, the object geometry can be continuously built up along a spiral build path.
  • the additively manufactured obj ect can be fabricated using a volumetric additive manufacturing (VAM) process in which an entire object is produced from a 3D volume of resin in a single print step, without requiring layer-by-layer build up.
  • VAM volumetric additive manufacturing
  • the entire build volume is irradiated with energy, but the projection patterns are configured such that only certain voxels will accumulate a sufficient energy dosage to be cured.
  • VAM processes that may be incorporated into the present technology include tomographic volumetric printing, holographic volumetric printing, multiphoton volumetric printing, and xolography.
  • a tomographic VAM process can be performed by projecting 2D optical patterns into a rotating volume of photosensitive material at perpendicular and/or angular incidences to produce a cured 3D structure.
  • a holographic VAM process can be performed by projecting holographic light patterns into a stationary reservoir of photosensitive material.
  • a xolography process can use photoswitchable photoinitiators to induce local polymerization inside a volume of photosensitive material upon linear excitation by intersecting light beams of different wavelengths. Additional details of VAM processes suitable for use with the present technology are described in U.S. Patent No. 11,370,173, U.S. Patent Publication No. 2021/0146619, U.S. Patent Publication No.
  • the additively manufactured object can be fabricated using a powder bed fusion process (e.g., selective laser sintering) involving using a laser beam to selectively fuse a layer of powdered material according to a desired cross-sectional shape in order to build up the object geometry.
  • the additively manufactured object can be fabricated using a material extrusion process (e.g., fused deposition modeling) involving selectively depositing a thin filament of material (e.g., thermoplastic polymer) in a layer-by- layer manner in order to form an object.
  • the additively manufactured object can be fabricated using a material jetting process involving jetting or extruding one or more materials onto a build surface in order to form successive layers of the object geometry.
  • the additively manufactured object can be made of any suitable material or combination of materials. As discussed above, in some embodiments, the additively manufactured object is made partially or entirely out of a polymeric material, such as a curable polymeric resin.
  • the resin can be composed of one or more monomer components that are initially in a liquid state. The resin can be in the liquid state at room temperature (e.g., 20 °C) or at an elevated temperature (e.g., a temperature within a range from 50 °C to 120 °C). When exposed to energy (e.g., light), the monomer components can undergo a polymerization reaction such that the resin solidifies into the desired object geometry.
  • curable polymeric resins and other materials suitable for use with the additive manufacturing techniques herein are described in International Publication Nos. WO 2019/006409, WO 2020/070639, and WO 2021/087061, the disclosures of each of which are incorporated herein by reference in their entirety.
  • the additively manufactured object can be fabricated from a plurality of different materials (e.g., at least two, three, four, five, or more different materials).
  • the materials can differ from each other with respect to composition, curing conditions (e.g., curing energy wavelength), material properties before curing (e.g., viscosity), material properties after curing (e.g., stiffness, strength, transparency), and so on.
  • the additively manufactured object is formed from multiple materials in a single manufacturing step.
  • a multi-tip extrusion apparatus can be used to selectively dispense multiple types of materials from distinct material supply sources in order to fabricate an object from a plurality of different materials. Examples of such methods are described in U.S. Patent No.
  • the additively manufactured object can be formed from multiple materials in a plurality of sequential manufacturing steps. For instance, a first portion of the object can be formed from a first material in accordance with any of the fabrication methods herein, then a second portion of the object can be formed from a second material in accordance with any of the fabrication methods herein, and so on, until the entirety of the object has been formed.
  • FIG. 2 is a partially schematic diagram providing a general overview of an additive manufacturing process, in accordance with embodiments of the present technology.
  • Additive manufacturing includes a variety of technologies which fabricate 3D objects directly from digital models through an additive process.
  • additive manufacturing can be used to directly fabricate orthodontic appliances (e.g., aligners, palatal expanders, retainers, attachment placement devices, attachments), restorative objects (e.g., crowns, veneers, implants), and/or other dental appliances (e.g., oral sleep apnea appliances, mouth guards). Additional examples of dental appliances and associated methods that are applicable to the present technology are described in Section I above and in Section III below.
  • additive manufacturing includes depositing a precursor material (e.g., a polymeric resin) onto a build platform.
  • the precursor material can be cured, polymerized, melted, sintered, fused, and/or otherwise solidified to form a portion of the object and/or to combine the portion with previously formed portions of the object.
  • the additive manufacturing techniques provided herein build up the object geometry in a layer-by-layer fashion, with successive layers being formed in discrete build steps. Alternatively or in combination, the additive manufacturing techniques described herein can allow for continuous build-up of an object geometry.
  • an object 202 is fabricated on a build platform 204 from a series of cured material layers, with each layer having a geometry corresponding to a respective cross-section of the object 202.
  • a layer of curable material 206 e.g., polymerizable resin
  • the curable material 206 is formed on and supported by a substrate (not shown), such as a film.
  • Energy 208 (e.g., light) from an energy source 210 (e.g., a laser, projector, or light engine) is then applied to the curable material 206 to form a cured material layer 212 on the build platform 204 or on the object 202.
  • the remaining curable material 206 can then be moved away from the build platform 204 (e.g., by lowering the build platform 204, by moving the build platform 204 laterally, by raising the curable material 206, and/or by moving the curable material 206 laterally), thus leaving the cured material layer 212 in place on the build platform 204 and/or object 202.
  • the fabrication process can then be repeated with a fresh layer of curable material 206 to build up the next layer of the object 202.
  • the illustrated embodiment shows a “top down” configuration in which the energy source 210 is positioned above and directs the energy 208 down toward the build platform 204, such that the object 202 is formed on the upper surface of the build platform 204. Accordingly, the build platform 204 can be incrementally lowered relative to the energy source 210 as successive layers of the object 202 are formed. In other embodiments, however, the additive manufacturing process of FIG. 2 can be performed using a “bottom up” configuration in which the energy source 210 is positioned below and directs the energy 208 up toward the build platform 204, such that the object 202 is formed on the lower surface of the build platform 204. Accordingly, the build platform 204 can be incrementally raised relative to the energy source 210 as successive layers of the object 202 are formed.
  • FIG. 2 illustrates a representative example of an additive manufacturing process
  • this is not intended to be limiting, and the embodiments described herein can be adapted to other types of additive manufacturing systems (e.g., vat-based systems) and/or other types of additive manufacturing processes (e.g., material jetting, binder jetting, material extrusion, powder bed fusion, sheet lamination, directed energy deposition).
  • additive manufacturing systems e.g., vat-based systems
  • additive manufacturing processes e.g., material jetting, binder jetting, material extrusion, powder bed fusion, sheet lamination, directed energy deposition.
  • FIG. 3 A illustrates a representative example of a tooth repositioning appliance 300 configured in accordance with embodiments of the present technology.
  • the appliance 300 can be manufactured using any of the systems, methods, and devices described herein.
  • the appliance 300 (also referred to herein as an “aligner”) can be worn by a patient in order to achieve an incremental repositioning of individual teeth 302 in the jaw.
  • the appliance 300 can include a shell (e.g., a continuous polymeric shell or a segmented shell) having teeth-receiving cavities that receive and resiliently reposition the teeth.
  • the appliance 300 or portion(s) thereof may be indirectly fabricated using a physical model of teeth.
  • an appliance e.g., polymeric appliance
  • a physical appliance is directly fabricated, e.g., using additive manufacturing techniques, from a digital model of an appliance.
  • the appliance 300 can fit over all teeth present in an upper or lower jaw, or less than all of the teeth.
  • the appliance 300 can be designed specifically to accommodate the teeth of the patient (e.g., the topography of the tooth-receiving cavities matches the topography of the patient’s teeth), and may be fabricated based on positive or negative models of the patient’s teeth generated by impression, scanning, and the like.
  • the appliance 300 can be a generic appliance configured to receive the teeth, but not necessarily shaped to match the topography of the patient’s teeth. In some cases, only certain teeth received by the appliance 300 are repositioned by the appliance 300 while other teeth can provide a base or anchor region for holding the appliance 300 in place as it applies force against the tooth or teeth targeted for repositioning.
  • teeth can be repositioned at some point during treatment. Teeth that are moved can also serve as a base or anchor for holding the appliance as it is worn by the patient. In preferred embodiments, no wires or other means are provided for holding the appliance 300 in place over the teeth. In some cases, however, it may be desirable or necessary to provide individual attachments 304 or other anchoring elements on teeth 302 with corresponding receptacles 306 or apertures in the appliance 300 so that the appliance 300 can apply a selected force on the tooth.
  • Representative examples of appliances including those utilized in the Invisalign® System, are described in numerous patents and patent applications assigned to Align Technology, Inc. including, for example, in U.S. Patent Nos.
  • FIG. 3B illustrates a tooth repositioning system 310 including a plurality of appliances 312, 314, 316, in accordance with embodiments of the present technology.
  • Any of the appliances described herein can be designed and/or provided as part of a set of a plurality of appliances used in a tooth repositioning system.
  • Each appliance may be configured so a tooth-receiving cavity has a geometry corresponding to an intermediate or final tooth arrangement intended for the appliance.
  • the patient’s teeth can be progressively repositioned from an initial tooth arrangement to a target tooth arrangement by placing a series of incremental position adjustment appliances over the patient’s teeth.
  • the tooth repositioning system 310 can include a first appliance 312 corresponding to an initial tooth arrangement, one or more intermediate appliances 314 corresponding to one or more intermediate arrangements, and a final appliance 316 corresponding to a target arrangement.
  • a target tooth arrangement can be a planned final tooth arrangement selected for the patient’s teeth at the end of all planned orthodontic treatment.
  • a target arrangement can be one of some intermediate arrangements for the patient’s teeth during the course of orthodontic treatment, which may include various different treatment scenarios, including, but not limited to, instances where surgery is recommended, where interproximal reduction (IPR) is appropriate, where a progress check is scheduled, where anchor placement is best, where palatal expansion is desirable, where restorative dentistry is involved (e.g., inlays, onlays, crowns, bridges, implants, veneers, and the like), etc.
  • IPR interproximal reduction
  • a target tooth arrangement can be any planned resulting arrangement for the patient’ s teeth that follows one or more incremental repositioning stages.
  • an initial tooth arrangement can be any initial arrangement for the patient’s teeth that is followed by one or more incremental repositioning stages.
  • FIG. 3C illustrates a method 320 of orthodontic treatment using a plurality of appliances, in accordance with embodiments of the present technology.
  • the method 320 can be practiced using any of the appliances or appliance sets described herein.
  • a first orthodontic appliance is applied to a patient’s teeth in order to reposition the teeth from a first tooth arrangement to a second tooth arrangement.
  • a second orthodontic appliance is applied to the patient’s teeth in order to reposition the teeth from the second tooth arrangement to a third tooth arrangement.
  • the method 320 can be repeated as necessary using any suitable number and combination of sequential appliances in order to incrementally reposition the patient’s teeth from an initial arrangement to a target arrangement.
  • the appliances can be generated all at the same stage or in sets or batches (e.g., at the beginning of a stage of the treatment), or the appliances can be fabricated one at a time, and the patient can wear each appliance until the pressure of each appliance on the teeth can no longer be felt or until the maximum amount of expressed tooth movement for that given stage has been achieved.
  • a plurality of different appliances e.g., a set
  • the appliances are generally not affixed to the teeth and the patient may place and replace the appliances at any time during the procedure (e.g., patient-removable appliances).
  • the final appliance or several appliances in the series may have a geometry or geometries selected to overcorrect the tooth arrangement.
  • one or more appliances may have a geometry that would (if fully achieved) move individual teeth beyond the tooth arrangement that has been selected as the “final.”
  • Such over-correction may be desirable in order to offset potential relapse after the repositioning method has been terminated (e.g., permit movement of individual teeth back toward their pre-corrected positions).
  • Over-correction may also be beneficial to speed the rate of correction (e.g., an appliance with a geometry that is positioned beyond a desired intermediate or final position may shift the individual teeth toward the position at a greater rate). In such cases, the use of an appliance can be terminated before the teeth reach the positions defined by the appliance.
  • over-correction may be deliberately applied in order to compensate for any inaccuracies or limitations of the appliance.
  • FIG. 4 illustrates a method 400 for designing an orthodontic appliance, in accordance with embodiments of the present technology.
  • the method 400 can be applied to any embodiment of the orthodontic appliances described herein. Some or all of the steps of the method 400 can be performed by any suitable data processing system or device, e.g., one or more processors configured with suitable instructions.
  • a movement path to move one or more teeth from an initial arrangement to a target arrangement is determined.
  • the initial arrangement can be determined from a mold or a scan of the patient’s teeth or mouth tissue, e.g., using wax bites, direct contact scanning, x-ray imaging, tomographic imaging, sonographic imaging, and other techniques for obtaining information about the position and structure of the teeth, jaws, gums and other orthodontically relevant tissue.
  • a digital data set can be derived that represents the initial (e.g., pretreatment) arrangement of the patient’s teeth and other tissues.
  • the initial digital data set is processed to segment the tissue constituents from each other. For example, data structures that digitally represent individual tooth crowns can be produced.
  • digital models of entire teeth can be produced, including measured or extrapolated hidden surfaces and root structures, as well as surrounding bone and soft tissue.
  • the target arrangement of the teeth (e.g., a desired and intended end result of orthodontic treatment) can be received from a clinician in the form of a prescription, can be calculated from basic orthodontic principles, and/or can be extrapolated computationally from a clinical prescription.
  • the final position and surface geometry of each tooth can be specified to form a complete model of the tooth arrangement at the desired end of treatment.
  • a movement path can be defined for the motion of each tooth.
  • the movement paths are configured to move the teeth in the quickest fashion with the least amount of round-tripping to bring the teeth from their initial positions to their desired target positions.
  • the tooth paths can optionally be segmented, and the segments can be calculated so that each tooth’s motion within a segment stays within threshold limits of linear and rotational translation.
  • the end points of each path segment can constitute a clinically viable repositioning, and the aggregate of segment end points can constitute a clinically viable sequence of tooth positions, so that moving from one point to the next in the sequence does not result in a collision of teeth.
  • a force system to produce movement of the one or more teeth along the movement path is determined.
  • a force system can include one or more forces and/or one or more torques. Different force systems can result in different types of tooth movement, such as tipping, translation, rotation, extrusion, intrusion, root movement, etc.
  • Biomechanical principles, modeling techniques, force calculation/measurement techniques, and the like, including knowledge and approaches commonly used in orthodontia, may be used to determine the appropriate force system to be applied to the tooth to accomplish the tooth movement.
  • sources may be considered including literature, force systems determined by experimentation or virtual modeling, computer-based modeling, clinical experience, minimization of unwanted forces, etc.
  • Determination of the force system can be performed in a variety of ways. For example, in some embodiments, the force system is determined on a patient-by-patient basis, e.g., using patient-specific data. Alternatively or in combination, the force system can be determined based on a generalized model of tooth movement (e.g., based on experimentation, modeling, clinical data, etc.), such that patient-specific data is not necessarily used. In some embodiments, determination of a force system involves calculating specific force values to be applied to one or more teeth to produce a particular movement. Alternatively, determination of a force system can be performed at a high level without calculating specific force values for the teeth.
  • block 404 can involve determining a particular type of force to be applied (e.g., extrusive force, intrusive force, translational force, rotational force, tipping force, torquing force, etc.) without calculating the specific magnitude and/or direction of the force.
  • a particular type of force to be applied e.g., extrusive force, intrusive force, translational force, rotational force, tipping force, torquing force, etc.
  • the determination of the force system can include constraints on the allowable forces, such as allowable directions and magnitudes, as well as desired motions to be brought about by the applied forces.
  • allowable forces such as allowable directions and magnitudes
  • desired motions to be brought about by the applied forces For example, in fabricating palatal expanders, different movement strategies may be desired for different patients.
  • the amount of force needed to separate the palate can depend on the age of the patient, as very young patients may not have a fully-formed suture.
  • palatal expansion can be accomplished with lower force magnitudes.
  • Slower palatal movement can also aid in growing bone to fill the expanding suture.
  • a more rapid expansion may be desired, which can be achieved by applying larger forces.
  • the determination of the force system can also include modeling of the facial structure of the patient, such as the skeletal structure of the jaw and palate.
  • Scan data of the palate and arch such as X-ray data or 3D optical scanning data, for example, can be used to determine parameters of the skeletal and muscular system of the patient’s mouth, so as to determine forces sufficient to provide a desired expansion of the palate and/or arch.
  • the thickness and/or density of the mid-palatal suture may be measured, or input by a treating professional.
  • the treating professional can select an appropriate treatment based on physiological characteristics of the patient.
  • the properties of the palate may also be estimated based on factors such as the patient’s age — for example, young juvenile patients can require lower forces to expand the suture than older patients, as the suture has not yet fully formed.
  • a design for an orthodontic appliance configured to produce the force system is determined.
  • the design can include the appliance geometry, material composition and/or material properties, and can be determined in various ways, such as using a treatment or force application simulation environment.
  • a simulation environment can include, e.g., computer modeling systems, biomechanical systems or apparatus, and the like.
  • digital models of the appliance and/or teeth can be produced, such as finite element models.
  • the finite element models can be created using computer program application software available from a variety of vendors.
  • CAE computer aided engineering
  • CAD computer aided design
  • one or more designs can be selected for testing or force modeling.
  • a desired tooth movement as well as a force system required or desired for eliciting the desired tooth movement, can be identified.
  • a candidate design can be analyzed or modeled for determination of an actual force system resulting from use of the candidate appliance.
  • force modeling can be further analyzed as described, e.g., in order to iteratively determine an appliance design that produces the desired force system.
  • instructions for fabrication of the orthodontic appliance incorporating the design are generated.
  • the instructions can be configured to control a fabrication system or device in order to produce the orthodontic appliance with the specified design.
  • the instructions are configured for manufacturing the orthodontic appliance using direct fabrication (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct fabrication, multi-material direct fabrication, etc.), in accordance with the various methods presented herein.
  • the instructions can be configured for indirect fabrication of the appliance, e.g., by thermoforming.
  • FIG. 5 illustrates a method 500 for digitally planning an orthodontic treatment and/or design or fabrication of an appliance, in accordance with embodiments.
  • the method 500 can be applied to any of the treatment procedures described herein and can be performed by any suitable data processing system.
  • a digital representation of a patient’s teeth is received.
  • the digital representation can include surface topography data for the patient’s intraoral cavity (including teeth, gingival tissues, etc.).
  • the surface topography data can be generated by directly scanning the intraoral cavity, a physical model (positive or negative) of the intraoral cavity, or an impression of the intraoral cavity, using a suitable scanning device (e.g., a handheld scanner, desktop scanner, etc.).
  • one or more treatment stages are generated based on the digital representation of the teeth.
  • the treatment stages can be incremental repositioning stages of an orthodontic treatment procedure designed to move one or more of the patient’s teeth from an initial tooth arrangement to a target arrangement.
  • the treatment stages can be generated by determining the initial tooth arrangement indicated by the digital representation, determining a target tooth arrangement, and determining movement paths of one or more teeth in the initial arrangement necessary to achieve the target tooth arrangement.
  • the movement path can be optimized based on minimizing the total distance moved, preventing collisions between teeth, avoiding tooth movements that are more difficult to achieve, or any other suitable criteria.
  • At least one orthodontic appliance is fabricated based on the generated treatment stages.
  • a set of appliances can be fabricated, each shaped according to a tooth arrangement specified by one of the treatment stages, such that the appliances can be sequentially worn by the patient to incrementally reposition the teeth from the initial arrangement to the target arrangement.
  • the appliance set may include one or more of the orthodontic appliances described herein.
  • the fabrication of the appliance may involve creating a digital model of the appliance to be used as input to a computer-controlled fabrication system.
  • the appliance can be formed using direct fabrication methods, indirect fabrication methods, or combinations thereof, as desired.
  • design and/or fabrication of an orthodontic appliance may include use of a representation of the patient’s teeth (e.g., including receiving a digital representation of the patient’ s teeth (block 502)), followed by design and/or fabrication of an orthodontic appliance based on a representation of the patient’s teeth in the arrangement represented by the received representation.
  • Aligners can include mandibular repositioning elements, such as those described in U.S. Patent No. 10,912,629, entitled “Dental Appliances with Repositioning Jaw Elements,” filed November 30, 2015; U.S. Patent No. 10,537,406, entitled “Dental Appliances with Repositioning Jaw Elements,” filed September 19, 2014; and U.S. Patent No. 9,844,424, entitled “Dental Appliances with Repositioning Jaw Elements,” filed February 21, 2014; all of which are incorporated by reference herein in their entirety.
  • attachment placement devices e.g., appliances used to position prefabricated attachments on a person’s teeth in accordance with one or more aspects of a treatment plan.
  • attachment placement devices also known as “attachment placement templates” or “attachment fabrication templates”
  • attachment placement templates can be found at least in: U.S. Application No. 17/249,218, entitled “Flexible 3D Printed Orthodontic Device,” filed February 24, 2021; U.S. Application No. 16/366,686, entitled “Dental Attachment Placement Structure,” filed March 27, 2019; U.S. Application No. 15/674,662, entitled “Devices and Systems for Creation of Attachments,” filed August 11, 2017; U.S. Patent No.
  • the techniques described herein can be used to make incremental palatal expanders and/or a series of incremental palatal expanders used to expand a person’s palate from an initial position toward a target position in accordance with one or more aspects of a treatment plan.
  • Examples of incremental palatal expanders can be found at least in: U.S. Application No. 16/380,801, entitled “Releasable Palatal Expanders,” filed April 10, 2019; U.S. Application No. 16/022,552, entitled “Devices, Systems, and Methods for Dental Arch Expansion,” filed June 28, 2018; U.S. Patent No. 11,045,283, entitled “Palatal Expander with Skeletal Anchorage Devices,” filed June 8, 2018; U.S. Application No.
  • Table 2 A provides the radiation-curable base formulation (component A) incorporated in the present resin compositions.
  • Sedimentation stability was assessed by filling the composition into a glass vial with a diameter of 3 cm and a height of 5 cm about halfway. Then, the sedimentation stability was assessed visually after two weeks storage at ambient conditions (room temperature was approximately 22 °C). The sedimentation stability was judged on a scale from A-C being:
  • the hatching distance was set to 10 pm in one direction and the laser spot had a diameter of approximately 20 pm (FWHM) on the upper surface of the material vat.
  • One repetition of laser irradiation per layer was performed, indicating a high reactivity of the respective resin compositions.
  • the printed samples were mechanically detached from the building platform with a blade, and excess resin was removed from the samples with a wipe and/or via solvent cleaning with isopropanol.
  • a UV-post curing step was performed with all printed samples in a Uvitron IntelliRay 600 at 100% intensity (approximately 150 mW cm’ 2 , approximately 280-550 nm broadband) for 2 x 5 min, and samples were flipped in between exposure cycles to ensure the light-curing step was completed.
  • Thermal post-processing was conducted in a Heratherm OMH60 oven from Thermo Scientific with a temperature protocol according to listed methods (heating rate set to 10 K/min): Method A — > 30 min at 170 °C and passive cooling to 80 °C, for El-El l.
  • Printability was assessed by determining the curing depth at set irradiation conditions for each resin composition (ideally, the curing depth is approximately at 2 to 3 times the layer height) and via evaluation of the printed samples. The printability was judged on a scale from A-C:
  • thermomechanical performance was performed via tensile tests and evaluation of heat deflection temperature.
  • a ProLine Z010 TH material tester from Zwick/Roell was used for tensile tests of the printed samples. The test was performed according to DIN EN ISO 527 using 5A samples. The tensile modulus was measured within 0.05-0.25% of elongation at a strain rate of 1 mm/min, and then the measurement was continued with a strain rate of 10 mm/min.
  • HDT Heat deflection temperature
  • filler geometry is a significant characteristic and typically is dependent on the production process.
  • LDS fillers are available in multiple shapes. Spherical and or close to spherical structures may be desired, as sharp filler edges may lead to unwanted abrasion effects during the printing process, and flaky or platelet-like filler geometries (El and E2) may lead to a significant orientation of the filler throughout the layerwise fabricated 3D object, which may result in an undesired anisotropic material performance.
  • fillers having a Dso values less than 1 pm may not be beneficial in terms of printability, as this led to dramatically lowered curing depth, and consequently lower achievable layer height during the print process. As a result, either overall print times may become longer or print failures may dramatically increase. Also, resin compositions with higher filler loadings (E8) may not be properly printed with such small fillers.
  • a method comprising: receiving a digital representation of a dental appliance having a first portion to be formed from a polymeric material and a second portion to be formed from a metallic material; and fabricating the dental appliance via an additive manufacturing process, wherein the dental appliance is fabricated from a composition including a precursor of the polymeric material and an activatable filler, wherein the additive manufacturing process comprises applying first energy to the composition to cure the precursor of the polymeric material, thereby forming the first portion of the dental appliance from the polymeric material, and wherein the activatable filler is configured to be activated by second energy to form a substrate for deposition of the metallic material at the second portion of the dental appliance.
  • Clause 3 The method of Clause 1 or 2, wherein the activatable filler is a metal-containing compound that forms metal nuclei when activated by the second energy.
  • Clause 4 The method of any one of Clauses 1 to 3, wherein the activatable filler comprises a mixed oxide or a mixed metal oxide.
  • Clause 5 The method of any one of Clauses 1 to 4, wherein the activatable filler is selected from the group consisting of indium oxide, tin oxide, indium tin oxide, titanium oxide, ferric oxide, rutile titanium dioxide, tin antimony oxide, tin antimony grey cassiterite, antimony trioxide, bismuth(III) oxide, tungsten oxide, copper tungstate, and mica.
  • the activatable filler is selected from the group consisting of indium oxide, tin oxide, indium tin oxide, titanium oxide, ferric oxide, rutile titanium dioxide, tin antimony oxide, tin antimony grey cassiterite, antimony trioxide, bismuth(III) oxide, tungsten oxide, copper tungstate, and mica.
  • Clause 6 The method of any one of Clauses 1 to 5, wherein the activatable filler constitutes from 5 wt% to 15 wt% of the composition.
  • Clause 7 The method of any one of Clauses 1 to 6, wherein the activatable filler comprises a plurality of particles.
  • Clause 8 The method of Clause 7, wherein the plurality of particles have a substantially spherical shape.
  • Clause 9 The method of Clause 7 or 8, wherein the plurality of particles have a Dso value within a range from 1 pm to 50 pm.
  • Clause 10 The method of any one of Clauses 7 to 9, wherein the plurality of particles have a monomodal distribution.
  • Clause 11 The method of any one of Clauses 7 to 9, wherein the plurality of particles have a multimodal distribution.
  • Clause 12 The method of any one of Clauses 1 to 11, wherein the activatable filler is substantially uniformly distributed in the dental appliance after the additive manufacturing process.
  • Clause 13 The method of any one of Clauses 1 to 12, wherein the additive manufacturing process comprises applying the first energy to the composition in a layer-by- layer manner to form the first portion from a plurality of layers of the polymeric material.
  • Clause 14 The method of any one of Clauses 1 to 13, wherein the additive manufacturing process comprises stereolithography or digital light processing.
  • Clause 15 The method of any one of Clauses 1 to 14, wherein the first energy has a different wavelength range than the second energy.
  • Clause 16 The method of any one of Clauses 1 to 15, wherein the first energy has a first wavelength range from 150 nm to 750 nm.
  • Clause 17 The method of any one of Clauses 1 to 16, wherein the second energy has a second wavelength range greater than or equal to 850 nm.
  • Clause 18 The method of any one of Clauses 1 to 17, wherein the precursor of the polymeric material comprises one or more monomers, oligomers, or reactive polymers.
  • Clause 19 The method of any one of Clauses 1 to 18, wherein the precursor of the polymeric material comprises a photopolymerizable resin.
  • Clause 20 The method of any one of Clauses 1 to 19, wherein the precursor of the polymeric material comprises one or more of an isocyanurate group, a cyanurate group, or a melamine group.
  • Clause 21 The method of any one of Clauses 1 to 20, wherein the precursor of the polymeric material comprises a mixture of at least one (meth)acrylate and at least one maleimide, a mixture of at least one (meth)acrylate and at least one citraconimide, or a mixture of at least one (meth)acrylate and at least one allyl compound.
  • Clause 22 The method of any one of Clauses 1 to 21, wherein the composition further comprises a photoinitiator.
  • Clause 23 The method of any one of Clauses 1 to 22, wherein the composition further comprises one or more additives.
  • Clause 24 The method of any one of Clauses 1 to 23, wherein the one or more additives comprise one or more flame retardants.
  • Clause 25 The method of Clause 24, wherein the one or more flame retardants are configured to cause to have a UL 94 rating of V-0 at a thickness less than or equal to 5 mm.
  • Clause 26 The method of any one of Clauses 1 to 25, further comprising post-processing the dental appliance.
  • Clause 27 The method of Clause 26, wherein the post-processing comprises one or more of post-curing the dental appliance or removing residual composition from the dental appliance.
  • Clause 28 The method of any one of Clauses 1 to 27, further comprising applying the second energy to the dental appliance to selectively activate the activatable filler at the second portion of the dental appliance.
  • Clause 29 The method of Clause 28, wherein the second energy is applied using an LDS process.
  • Clause 30 The method of Clause 28 or 29, wherein the second energy causes ablation of the polymeric material at or near the second portion of the dental appliance.
  • Clause 31 The method of any one of Clauses 28 to 30, further comprising depositing the metallic material at the second portion of the object.
  • Clause 32 The method of Clause 31, wherein the metallic material is deposited using chemical or electrochemical plating.
  • Clause 33 The method of any one of Clauses 1 to 32, wherein the dental appliance is an aligner, a retainer, a palatal expander, or a mouth guard.
  • Clause 34 The method of any one of Clauses 1 to 33, wherein the first portion comprises a polymeric shell including a plurality of cavities for receiving a patient’s teeth.
  • Clause 35 The method of any one of Clauses 1 to 34, wherein the second portion comprises one or more of a reinforcement structure, an auxiliary structure, or a conductive structure.
  • a composition for fabricating an additively manufactured dental appliance comprising: a precursor of a polymeric material, wherein the precursor is configured to be cured when exposed to first energy to form the polymeric material at a first portion of the additively manufactured dental appliance; and an activatable filler, wherein the activatable filler is configured to be activated when exposed to second energy to form a substrate for deposition of a metallic material at a second portion of the additively manufactured dental appliance.
  • Clause 37 The composition of Clause 36, wherein the activatable filler is a laser direct structuring (LDS) filler.
  • LDS laser direct structuring
  • Clause 38 The composition of Clause 36 or 37, wherein the activatable filler is a metal-containing compound that forms metal nuclei when activated by the second energy.
  • Clause 39 The composition of any one of Clauses 36 to 38, wherein the activatable filler comprises a mixed oxide or a mixed metal oxide.
  • Clause 40 The composition of any one of Clauses 36 to 39, wherein the activatable filler is selected from the group consisting of indium oxide, tin oxide, indium tin oxide, titanium oxide, ferric oxide, rutile titanium dioxide, tin antimony oxide, tin antimony grey cassiterite, antimony trioxide, bismuth(III) oxide, tungsten oxide, copper tungstate, and mica.
  • Clause 41 The composition of any one of Clauses 36 to 40, wherein the activatable filler constitutes from 5 wt% to 15 wt% of the composition.
  • Clause 42 The composition of any one of Clauses 36 to 41, wherein the activatable filler comprises a plurality of particles.
  • Clause 43 The composition of Clause 42, wherein the plurality of particles have a substantially spherical shape.
  • Clause 44 The composition of Clause 42 or 43, wherein the plurality of particles have a Dso value within a range from 1 pm to 50 pm.
  • Clause 45 The composition of any one of Clauses 42 to 44, wherein the plurality of particles have a monomodal distribution.
  • Clause 46 The composition of any one of Clauses 42 to 44, wherein the plurality of particles have a multimodal distribution.
  • Clause 47 The composition of any one of Clauses 36 to 46, wherein the activatable filler is substantially uniformly distributed in the additively manufactured dental appliance.
  • Clause 48 The composition of Clause 36, wherein the additively manufactured dental appliance comprises a plurality of layers of the polymeric material.
  • Clause 49 The composition of any one of Clauses 36 to 48, wherein the first energy has a different wavelength range than the second energy.
  • Clause 50 The composition of any one of Clauses 36 to 49, wherein the first energy has a first wavelength range from 150 nm to 750 nm.
  • Clause 51 The composition of any one of Clauses 36 to 50, wherein the second energy has a second wavelength range greater than or equal to 850 nm.
  • Clause 52 The composition of any one of Clauses 36 to 51, wherein the precursor of the polymeric material comprises one or more monomers, oligomers, or reactive polymers.
  • Clause 53 The composition of any one of Clauses 36 to 52, wherein the precursor of the polymeric material comprises a photopolymerizable resin.
  • Clause 54 The composition of any one of Clauses 36 to 53, wherein the precursor of the polymeric material comprises one or more of an isocyanurate group, a cyanurate group, or a melamine group.
  • Clause 55 The composition of any one of Clauses 36 to 54, wherein the precursor of the polymeric material comprises a mixture of at least one (meth)acrylate and at least one maleimide, a mixture of at least one (meth)acrylate and at least one citraconimide, or a mixture of at least one (meth)acrylate and at least one allyl compound.
  • Clause 56 The composition of any one of Clauses 36 to 55, further comprising a photoinitiator.
  • Clause 57 The composition of any one of Clauses 36 to 56, further comprising one or more additives.
  • Clause 58 The composition of any one of Clauses 36 to 57, wherein the one or more additives comprise one or more flame retardants.
  • Clause 59 The composition of Clause 58, wherein the one or more flame retardants are configured to cause to have a UL 94 rating of V-0 at a thickness less than or equal to 5 mm.
  • Clause 60 The composition of any one of Clauses 36 to 59, wherein the dental appliance is an aligner, a retainer, a palatal expander, or a mouth guard.
  • Clause 61 The composition of any one of Clauses 36 to 60, wherein the first portion comprises a polymeric shell including a plurality of cavities for receiving a patient’s teeth.
  • An additively manufactured dental appliance comprising: a plurality of additively manufactured layers of a polymeric material; and an activatable filler, wherein the activatable filler is configured to be activated when exposed to energy to form a substrate for deposition of a metallic material.
  • Clause 64 A method comprising: receiving a digital representation of an object having a first portion to be formed from a polymeric material and a second portion to be formed from a metallic material; and fabricating the object via an additive manufacturing process, wherein the object is fabricated from a composition including a precursor of the polymeric material and an activatable filler, wherein the additive manufacturing process comprises applying first energy to the composition to cure the precursor of the polymeric material, thereby forming the first portion of the object from the polymeric material, and wherein the activatable filler is configured to be activated by second energy to form a substrate for deposition of the metallic material at the second portion of the object.
  • a composition for fabricating an additively manufactured object comprising: a precursor of a polymeric material, wherein the precursor is configured to be cured when exposed to first energy to form the polymeric material at a first portion of the additively manufactured object; and an activatable filler, wherein the activatable filler is configured to be activated when exposed to second energy to form a substrate for deposition of a metallic material at a second portion of the additively manufactured object.
  • An additively manufactured object comprising: a plurality of additively manufactured layers of a polymeric material; and an activatable filler, wherein the activatable filler is configured to be activated when exposed to energy to form a substrate for deposition of a metallic material.
  • a resin composition for the 3D printing of objects comprising: a curable component A comprising one or more light-curable components; a component B comprising at least one additive that can selectively be activated after 3D printing by radiation to form a surface or volume that serves as a substrate for selectively depositing at least a second material; at least one component C comprising a photoinitiator; and optionally at least one component D comprising an additive, which may be added in an amount from 0.0001 to 90% by weight relative to the total formulation, wherein, component B is a filler, which has a primary particle size (Dso value) from 0.01 pm to 100 pm.
  • Dso value primary particle size
  • Clause 68 The resin composition of Clause 67, wherein the curable component A ranges from 10 wt% to 99 wt%, from 20 wt% to 98 wt%, from 30 wt% to 97 wt%, or from 50 wt% to 95 wt%.
  • Clause 69 The resin composition of Clause 67 or 68, wherein the component B ranges from 0.1 wt% to 50 wt%, from 1 wt% to 30 wt%, from 3 wt% to 20 wt%, or from 5 wt% to 15 wt%.
  • Clause 70 The resin composition of any one of Clauses 67 to 69, wherein the at least one component C ranges from 0.001 wt% to 20 wt%, from 0.1 wt% to 10 wt%, or from 0.5 wt% to 5 wt%.
  • Clause 71 The resin composition of any one of Clauses 67 to 69, wherein the at least one component C ranges from 0.001 wt% to 20 wt%, from 0.1 wt% to 10 wt%, or from 0.5 wt% to 5 wt%.
  • the curable component A comprises one or more light-curable components, which are susceptible to layer-by-layer photopolymerization for manufacturing a component
  • the 3D printing process comprises providing the filled resin composition in a production bath, on a production bed and/or as a wet layer and selectively curing the filled resin composition layer by layer by polymerization in the production bath, on the production bed and/or in the wet layer by means of selective light irradiation via a light source in a first wavelength range to form the 3D printed part.
  • Clause 72 The resin composition of any one of Clauses 67 to 71, wherein the curable component A is selected from the group consisting of (meth)acrylates, (meth)acrylamides, allyl components, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, citraconimides, itaconimides, itaconates, fumarates, styrene compounds, cyclic ethers such as epoxy compounds or oxetanes, benzoxazines, oxazolines, and cyanoacrylates.
  • the curable component A is selected from the group consisting of (meth)acrylates, (meth)acrylamides, allyl components, vinyl esters, vinyl ethers, vinyl amides, N-vinyl compounds, vinyl carbonates, vinyl carbamates, maleimides, citraconimides, itaconimides, itaconates, fumarates, styrene
  • Clause 73 The resin composition of any one of Clauses 67 to 72, wherein the curable component A is selected from the group consisting of (meth)acrylates, (meth)acrylamides, and allyl components.
  • Clause 74 The resin composition of any one of Clauses 67 to 73, wherein the curable component A comprises at least one monofunctional reactive diluent (e.g., isobornyl acrylate), at least one multifunctional oligomer, prepolymer or polymer (e.g., difunctional urethane acrylate with a molecular weight less than 500 g/mol), and optionally at least one low molecular-weight, multifunctional crosslinker (e.g., triethylene glycol dimethacrylate, tris[2-(methacryloyloxy)ethyl] isocyanurate).
  • the curable component A comprises at least one monofunctional reactive diluent (e.g., isobornyl acrylate), at least one multifunctional oligomer, prepolymer or polymer (e.g., difunctional urethane acrylate with a molecular weight less than 500 g/mol), and optionally at least one low molecular-weight, multi
  • Clause 75 The resin composition of any one of Clauses 67 to 74, wherein the curable component A comprises at least one monofunctional reactive diluent, which ranges from 5 wt% to 60 wt%; at least one multifunctional oligomer, prepolymer or polymer, which ranges from 5 wt% to 95 wt%; and optionally at least one low molecular-weight, multifunctional crosslinker, which ranges from 5 wt% to 95 wt%; based on the total weight of all substances making up component A.
  • the curable component A comprises at least one monofunctional reactive diluent, which ranges from 5 wt% to 60 wt%; at least one multifunctional oligomer, prepolymer or polymer, which ranges from 5 wt% to 95 wt%; and optionally at least one low molecular-weight, multifunctional crosslinker, which ranges from 5 wt% to 95 wt%; based on the total weight of all substances making up
  • Clause 76 The resin composition of any one of Clauses 67 to 75, wherein the component B is designed to enable laser structuring under irradiation with a laser in a second wavelength range, in which laser-activatable compounds are activated in the resin composition.
  • Clause 77 The resin composition of Clause 76, wherein the second wavelength range is different from the first wavelength range.
  • Clause 78 The resin composition of Clause 76 or 77, wherein laser structuring under irradiation with a laser is applied with the second wavelength range being different from the first wavelength range and falling within the infrared spectral range, optionally being at least greater than 850 nm.
  • Clause 79 The resin composition of any one of Clauses 67 to 78, comprising a base that is a UV-curing photopolymer (component A), which simultaneously contains component B (e.g., activatable additives, IR-laser-sensitive pigments, LDS fillers), which are selected from the group of mixed metal oxides, mica, copper phosphates, titanium oxide, doped tin oxide, which is doped with non-metallic elements, indium tin oxide and/or tin antimony oxide, which are reduced by means of IR laser radiation.
  • component A e.g., activatable additives, IR-laser-sensitive pigments, LDS fillers
  • component B e.g., activatable additives, IR-laser-sensitive pigments, LDS fillers
  • Clause 80 The resin composition of Clause 79, wherein subsequently, in a chemical process, at these sites activated by IR radiation, metal ions, such as copper, grow in a chemical process to form the corresponding metallic conductive paths.
  • Clause 81 The resin composition of Clause 79 or 80, wherein the type of LDS filler as the component B is present at a content of 0.01 to 20 volume percent, a content of 0.02 to 10 volume percent, or a content of 0.05 to 5 volume percent.
  • Clause 82 The resin composition of any one of Clauses 79 to 81, wherein the LDS filler comprises a mixed oxide or mixed metal oxide.
  • Clause 83 The resin composition of Clause 82, wherein the mixed oxide or mixed metal oxide is selected from the group consisting of indium oxide, tin oxide, indium tin oxide, titanium oxide, ferric oxide, rutile titanium dioxide, tin antimony oxide, tin antimony grey cassiterite, antimony trioxide, bismuth(III) oxide, tungsten oxide, copper tungstate, and mica.
  • Clause 84 The resin composition of any one of Clauses 79 to 83, wherein the LDS fillers are embedded in a polymer matrix or carrier, coated with a metal oxide such as ferric oxide or antimony-doped tin oxide.
  • Clause 85 The resin composition of any one of Clauses 79 to 84, wherein the LDS fillers are spheres, platelets and/or fibers and/or mixtures thereof, spheres, fractures and/or defined 3D and/or 2D structures.
  • Clause 86 The resin composition of any one of Clauses 79 to 85, wherein the LDS filler comprises a particle size characterized by a Dso value of less than 50 pm, less than 25 pm, or less than 10 pm.
  • Clause 87 The resin composition of any one of Clauses 79 to 86, wherein the LDS filler comprises a particle size characterized by a Dso value of higher than 1 pm.
  • Clause 88 The resin composition of any one of Clauses 79 to 87, wherein the LDS filler has a particle size distribution with a Dio value greater than 0.5 pm and a D90 value less than 20 pm, a Dio value greater than 1 pm and a D90 value less than 20 pm, or a Dio value greater than 0.5 pm and a D90 value less than 10 pm.
  • Clause 89 The resin composition of any one of Clauses 79 to 88, wherein the LDS filler has a bimodal or multimodal particle size distribution in addition to a monomodal one.
  • Clause 90 The resin composition of any one of Clauses 79 to 89, wherein the LDS filler has rounded and/or spherical particles.
  • Clause 91 The resin composition of any one of Clauses 79 to 90, wherein the LDS-filled resin formulation also contains a rheology additive, a nanoparticle filler with particle sizes smaller than 1 pm.
  • Clause 92 The resin composition of Clause 91, wherein the respective additives are present in a content within a range from 0.01 phr to 20 phr relative to the photopolymerizable matrix component.
  • Clause 93 The resin composition of any one of Clauses 67 to 92, wherein the resin composition is mixed with polymerization initiators, polymerization inhibitors, solvents, fillers, antioxidants, pigments, dyes, surface modifiers, flame retardants, additives to reduce polymerization shrinkage and/or shrinkage stress (e.g., network modifiers) and mixtures thereof and thus contain them as an additive.
  • polymerization initiators polymerization inhibitors
  • solvents solvents
  • fillers antioxidants, pigments, dyes, surface modifiers, flame retardants
  • additives to reduce polymerization shrinkage and/or shrinkage stress e.g., network modifiers
  • 3D printing of a resin composition of any one of Clauses 67 to 93 via layer-by-layer photopolymerization for manufacturing a component, in particular a component, using a filled resin formulation wherein the 3D printing process comprises providing the filled resin formulation in a production bath, on a production bed and/or as a wet layer and selectively curing the filled resin formulation layer by layer by polymerization in the production bath, on the production bed and/or in the wet layer by means of selective light irradiation via a light source in a first wavelength range to form the 3D printed part; optionally post-processing the 3D printed part; and a laser direct structuring (LDS) process, wherein the filler from the resin formulation is adapted to enable laser patterning of the formed component under irradiation with a laser in a second wavelength range in which laser- activatable compounds in the resin formulation are activated, the second wavelength range being different from the first wavelength range and wherein one or more conductor structures are formed on the 3D printed part by laser activating
  • Clause 95 An additively manufactured component, in particular a three- dimensional circuit carrier or MID, which is manufactured using the process of Clause 94.
  • the various processes described herein can be partially or fully implemented using program code including instructions executable by one or more processors of a computing system for implementing specific logical functions or steps in the process.
  • the program code can be stored on any type of computer-readable medium, such as a storage device including a disk or hard drive.
  • Computer-readable media containing code, or portions of code can include any appropriate media known in the art, such as non-transitory computer-readable storage media.
  • Computer-readable media can include volatile and non-volatile, removable and non-removable media implemented in any method or technology for storage and/or transmission of information, including, but not limited to, random-access memory (RAM), read-only memory (ROM), electrically erasable programmable read-only memory (EEPROM), flash memory, or other memory technology; compact disc read-only memory (CD-ROM), digital video disc (DVD), or other optical storage; magnetic cassettes, magnetic tape, magnetic disk storage, or other magnetic storage devices; solid state drives (SSD) or other solid state storage devices; or any other medium which can be used to store the desired information and which can be accessed by a system device.
  • RAM random-access memory
  • ROM read-only memory
  • EEPROM electrically erasable programmable read-only memory
  • flash memory or other memory technology
  • CD-ROM compact disc read-only memory
  • DVD digital video disc
  • magnetic cassettes magnetic tape
  • magnetic disk storage or other magnetic storage devices
  • SSD solid state drives
  • polymer refers to a molecule composed of repeating structural units connected by covalent chemical bonds and characterized by a substantial number of repeating units (e.g., equal to or greater than 10 repeating units and often equal to or greater than 50 repeating units and often equal to or greater than 100 repeating units) and a high molecular weight (e.g., greater than or equal to 5000 Da, 10000 Da or 20000 Da). Polymers are commonly the polymerization product of one or more monomer precursors.
  • polymer includes homopolymers, or polymers consisting essentially of a single repeating monomer subunit.
  • polymer also includes copolymers which are formed when two or more different types of monomers are linked in the same polymer.
  • Copolymers may comprise two or more monomer subunits, and include random, block, alternating, segmented, grafted, tapered and other copolymers.
  • an “oligomer” refers to a molecule composed of repeating structural units connected by covalent chemical bonds and characterized by a number of repeating units less than that of a polymer (e.g., equal to or less than 10 repeating units) and a lower molecular weight than polymers (e.g., less than 20,000 Da or 10,000 Da). Oligomers may be the polymerization product of one or more monomer precursors. In an embodiment, an oligomer or a monomer cannot be considered a polymer in its own right.
  • a “prepolymer” refers to a polymer or oligomer, the molecules of which are capable of entering, through reactive groups, into further polymerization.
  • Oligomers and polymer mixtures may additionally form crosslinks, thus creating polymer networks. Oligomers and polymer mixtures can be characterized and differentiated from other mixtures of oligomers and polymers by measurements of molecular weight and molecular weight distributions.
  • molecular weight refers to the number average molecular weight as measured by gel permeation chromatography (GPC) or size exclusion chromatography (SEC) calibrated with polystyrene standards in a suitable solvent (typically tetrahydrofuran).
  • GPC gel permeation chromatography
  • SEC size exclusion chromatography

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Dentistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

L'invention concerne des compositions et des procédés de fabrication d'objets fabriqués de manière additive. Dans certains modes de réalisation, un procédé consiste à : recevoir une représentation numérique d'un appareil dentaire comportant une première partie à former à partir d'un matériau polymère et une seconde partie à former à partir d'un matériau métallique ; et fabriquer l'appareil dentaire par le biais d'un procédé de fabrication additive, l'appareil dentaire étant fabriqué à partir d'une composition comprenant un précurseur du matériau polymère et une charge activable. Le procédé de fabrication additive peut consister à appliquer une première énergie à la composition pour durcir le précurseur du matériau polymère, formant ainsi la première partie de l'appareil dentaire à partir du matériau polymère. La charge activable peut être conçue pour être activée par une seconde énergie pour former un substrat pour le dépôt du matériau métallique au niveau de la seconde partie de l'appareil dentaire.
PCT/US2025/033816 2024-06-17 2025-06-16 Compositions pour la fabrication additive au moyen de charges activables Pending WO2025264579A1 (fr)

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