Process and apparatus for fabrication of three-dimensional objects

ES 2 823 975 T3

DESCRIPTION

Process and apparatus for the manufacture of three-dimensional objects

Field of the invention

The present description refers to a method and an apparatus for the manufacture of three-dimensional objects from polymer-based material. In particular, the present invention relates to a three-dimensional manufacturing apparatus having a print head and ink supply system.

Background of the invention

With the increasing use of computer-aided design (CAD) solid modeling systems, a new frontier of manufacturing technology has emerged that allows CAD output data to be translated into a three-dimensional physical object. This technology is commonly called solid freeform fabrication or layer fabrication, which involves building an object on a layer-by-layer or point-by-point basis. Examples of commercially available solid free form fabrication systems include stereolithography, selective laser sintering, rolled object fabrication, and fused deposition modeling. Other examples of solid free form fabrication systems are known to those of skill in the art.

Automatic three-dimensional object shaping is useful in CAD database verification, aesthetic assessment, design ergonomics check, tool and accessory design assistance, conceptual model creation and sales / marketing tools, generation of models for precision casting, reduction or elimination of engineering changes in production and provision of small production cycles.

US 6 165 406 A describes a free-form manufacturing process and an apparatus for manufacturing a full-color 3-D object. The process includes (1) operating a multi-channel droplet deposition device to deliver and, as requested, eject droplets of multiple liquid compositions containing a solidifiable starting body construction material and different colorants; (2) providing a support platform with a distance from said deposition device to receive the drops therefrom; and (3) during the droplet ejection process, moving the deposition device and platform relative to each other in an XY plane and in a Z direction orthogonal to the XY plane so that the droplets are deposited to form multiple layers. to build a full color 3-D object. US 2010/195122 A1 describes a method for printing a painted three-dimensional object. Each layer of the object is printed so that only the outer circumference of the layer contains colored material. The building material used can be transparent and a white colored material can be used as a barrier between the building material and the colored material.

US 2004/251574 A1 describes a method of producing a formed object through the manufacture of a solid free form, it includes dispensing a binder over successive layers of building material with a single first dispensing member; and coloring successive layers with at least one second dispensing member, where the second dispensing member dispenses on top of the first dispensing member.

US 2007/108664 A1 describes a process for chemically etching a stereolithography resin, it involves the chemical etching of a shaped object of the resin at a temperature in the range of about 20 ° C to about 30 ° C for a period of time. from about 30 seconds to about 60 seconds with a saturated aqueous permanganate solution.

EP 1 925 428 A1 describes a method and a system for manufacturing a partially coated product having at least one coated area and at least one uncoated area.

Document WO 98/09798 describes the features of the preamble of claim 1.

Compendium

Aspects of the invention are directed to the manufacture of three-dimensional objects. Three-dimensional objects can have high-resolution color.

The present invention provides a three-dimensional manufacturing method comprising: (a) depositing a first polymer layer; (b) printing a first ink layer on the first polymer layer; (c) depositing a second layer of polymer on the first layer of ink; (d) printing a second layer of ink on the second layer of polymer; and (e) repeating steps (a) - (d) to form a three-dimensional object, wherein at least one of the first and second ink layers includes an ink comprising chemical metallization catalyst.

In certain embodiments, each of the first and second ink layers may include a plurality of ink layers. In certain embodiments, each of the first and second polymer layers includes a plurality of polymer layers. In certain embodiments, the formation of at least one of the first and second ink layers may include the use of an ink that further comprises at least one of pigments, colorants, and catalysts.

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In some embodiments, the chemical metallization catalysts can be selected from the group that includes palladium, ruthenium, platinum, silver, osmium, iridium, and cobalt. In certain embodiments, the chemical metallization catalyst is palladium or silver. In certain embodiments, the formation of at least one of the first and second ink layers includes the use of a colored ink. In certain embodiments, at least one of the first and second ink layers is deposited along a circumferential edge of at least one of the first and second polymer layers. In certain embodiments, the formation of at least one of the first and second ink layers may include the use of an ink that is selected on the basis of its solubility parameter relative to a polymer solubility parameter.

In certain embodiments, the formation of at least one of the first and second polymer layers includes the use of a polymeric material selected from acrylonitrile butadiene styrene, polyacrylates, polyolefins, cyclic olefin polymers and copolymers, polycarbonates, polyamides, polyimides, polyethylene. and polybutylene teraphthalate, liquid crystal polymer resins, polyether ether ketone, thermoplastic elastomers, polystyrenes, polyvinyl chloride, polysulfones, polyurethane, polyamides, polyesters, epoxy resins, silicon resin, a diallyl phthalate resin, a cellulosic plastic, a rosin modified maleic acid resin, copolymers thereof, collagen, elastin, hydrogels, xerogels, polycaprolactone, poly (D, L-lactide-co-glycolide), polylactide, poly (lactide-co-caprolactone), or combinations thereof. In certain embodiments, the formation of at least one of the first and second polymer layers includes the use of acrylonitrile butadiene styrene ("ABS").

In some embodiments, a support structure is formed adjacent to the three-dimensional object during the manufacturing process. In certain embodiments, the support structure of the three-dimensional object can be removed. In some embodiments, a releasable ink layer may be printed between the three-dimensional object and the support structure. In certain embodiments, the formation of the support structure may include the use of a polymeric material that is similar to a polymeric material used to form the three-dimensional object. In some embodiments, the polymeric material can be a water-soluble, solvent-soluble, or alkali-soluble polymer. In some embodiments, the support structure has an outer ink layer that includes at least one ingredient that is soluble in a polymeric material included in the support structure. In certain embodiments, the at least one ingredient accelerates dissolution of the polymeric material from the support structure or, in alternative embodiments, the at least one ingredient causes the outer ink layer to dissolve prior to dissolution of the polymeric material from the structure. of support.

In certain embodiments, a coating layer is applied to at least one of the first and second ink layers. In some embodiments, the coating layer is a lacquer, in some embodiments, the coating layer is applied to the three-dimensional object. In some embodiments, the coating layer is a translucent or transparent polymeric material. In certain embodiments, at least one of the first and second ink layers is treated with a heat source, an energy source, or combinations thereof. In some embodiments, the heat source is selected from the group having conventional, conduction, radiant, and combinations thereof. In some embodiments, the energy source can be an electromagnetic energy source. In some embodiments, the electromagnetic energy source can be selected from the group having near infrared, visible, ultraviolet, radio frequency, microwave, or combinations thereof. In some embodiments, the printing of at least one of the first or second ink layers forms a target pattern that can be used to optically align a three-dimensional printing apparatus.

In certain embodiments, at least one of the first and second ink layers includes a releasable ink or a plasticizer ink. In certain embodiments, forming a first portion of at least one of the first and second ink layers includes using a first ink and a second portion of at least one of the first and second ink layers is formed using a second. ink. In some embodiments, the first ink is a plasticizer ink and the second ink is a plasticizer ink with a higher concentration of plasticizer than the first ink. In some embodiments, the first ink and the second ink provide different surface properties between the first portion and the second portion of the ink layer. In some embodiments, the formation of at least one of the first and second ink layers includes the use of a plasticizing ink that creates a smooth surface on the three-dimensional object. In certain embodiments, the formation of at least one of the first and second ink layers includes the use of an ink that comprises at least one ingredient that is soluble in the first and second polymer layer. In certain embodiments, the formation of at least one of the first and second ink layers includes the use of an ink that comprises an active ingredient. In some embodiments, the active ingredient can be a pharmaceutical ingredient including an anti-inflammatory ingredient, a neointimal growth inhibitor ingredient, an anticoagulant, an antibody, an immunosuppressive ingredient, chemotherapeutic drugs, or combinations thereof. In alternative embodiments, the active ingredient can be a cell culture including stem cells, cartilage cells, bone cells, muscle cells, skin cells, pancreatic cells, kidney cells, liver cells, neurons, and combinations thereof.

In an aspect not claimed in the present patent, a three-dimensional manufacturing apparatus is provided including: (a) a polymer deposition apparatus; and (b) a printing apparatus including a printing head and ink supply system. In certain examples, the printing apparatus may be attached to the polymer deposition apparatus. In certain examples, the polymer deposition apparatus includes an extruder and the print head and ink supply system is attached to the extruder. In alternative examples, the polymer deposition apparatus includes an extruder and the print head and ink supply system is attached to the polymer deposition apparatus separate from the extruder.

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In certain examples, the polymer deposition apparatus is selected from the group having a melt deposition modeling apparatus, a laminated object manufacturing apparatus, and a three-dimensional photopolymer deposition apparatus. In certain examples, the printhead and ink supply system includes a printhead selected from the group that includes a thermal printhead, a piezo printhead, a MEMS printhead, and an electrostatic printhead. In certain embodiments, the print head and ink supply system includes a print head selected from the group having a plotter style single nozzle unit (plotter), a continuous ink jet, and a drop-on-demand system.

In an aspect not claimed in the present patent, a method of selecting an ink for the three-dimensional manufacture of a three-dimensional object is provided including: (a) selecting a polymer; (b) calculating the Hansen solubility parameter of the polymer; (c) selecting an ink; (d) calculating the Hansen solubility parameter of the ink, (e) comparing the Hansen solubility parameter of the polymer with the Hansen solubility parameter of the ink to determine whether the ink is a releasable ink or a plasticizer ink; and (f) using the polymer and ink to form a three-dimensional object by three-dimensional manufacturing.

In an aspect not claimed in the present patent, a method is provided that includes (a) depositing a first layer of polymer to form a three-dimensional object; (b) printing a layer of ink on the three-dimensional object to form a cover. In certain examples, the three-dimensional manufacturing method further includes depositing at least a second layer of polymer on the cover. In certain examples, the second polymer layer is formed using a translucent or transparent polymeric material.

These and other aspects, along with the advantages and features of the present invention described herein, will become apparent with reference to the following detailed description. Also, it should be understood that the features of the various embodiments described herein are not exclusive to one another and various combinations and permutations may exist.

Brief description of the drawings

In the drawings, the same reference symbols generally refer to the same parts throughout the different views. Also, the drawings are not necessarily to scale, but the emphasis is generally placed on illustrating the principles of the invention. In the following description, various embodiments of the present invention are described with reference to the following drawings, in which:

Figure 1 depicts a schematic configuration of a prior art filament deposition modeling apparatus.

Figure 2 represents a schematic configuration of a manufacturing apparatus according to one aspect of the present invention.

Figure 3 represents a schematic configuration of a manufacturing process according to one aspect of the present invention.

Figure 4 represents a schematic representation of a plasticizer ink between two polymer layers.

Figure 5 represents a schematic representation of an ink releasable between two polymer layers.

Figure 6 represents a graphical representation of the interaction of an ink and a polymer as defined in the equation.

D (ip) = [4 (δdi - δdp)² + (δμί - δpp)² + (óhi - δhp)²]⁰,⁵

Detailed description of the invention

It would be desirable to provide a three-dimensional manufacturing method capable of producing various three-dimensional objects. At least certain embodiments of the new method can produce high resolution color manipulation capabilities. At least certain embodiments of the new method and apparatus can provide functional three-dimensional objects. Additional features and advantages of some or all of the three-dimensional fabrication methods described herein will be apparent to those skilled in three-dimensional fabrication given the benefit of the following compendium and the description of non-exhaustive illustrative examples.

The present invention provides a method for manufacturing a three-dimensional object.

As used herein, "three-dimensional fabrication" is used to refer to a method of constructing a three-dimensional object layer by layer. Three-dimensional manufacturing refers to the combination of deposition of at least one layer of a polymer and printing of at least one layer of an ink to form a three-dimensional object. As used herein, a "layer" is formed by a single pass of a deposition apparatus or a printing apparatus. In some embodiments, the at least one layer can be deposited and printed.

ES 2 823 975 T3 of polymer and the at least one ink layer in order. For example, in certain embodiments, multiple layers of polymer can be deposited prior to printing the ink layer. In alternative embodiments, the polymer and ink layers can alternate with single or multiple layers. Various deposition methods are known in the art, including, but not limited to melt deposition modeling, rolled object fabrication, stereolithography, and selective laser sintering.

For example, the invention can be carried out with a three-dimensional deposition apparatus, such as that used for melt deposition modeling, including an extruder assembly that disperses a polymer. In some embodiments, the polymer forms a three-dimensional object in a layer-by-layer process on a print bed. In some embodiments, after the construction of the three-dimensional object is complete, the object can be removed from the build platform and a new project can begin. In certain embodiments, the extruder assembly may be stationary or may allow XY-axis motion, only X-axis or Y-axis motion, and / or rotational and angular motions. In certain embodiments, the build platform generally has indexed Z-axis movement options. In alternative embodiments, other movements may also be provided. In certain embodiments, each Z-axis movement may correspond to a specific layer thickness for manufacturing a three-dimensional object. In addition, in certain embodiments, the build platform may allow optional XY axis movement, only for X axis or Y axis movement, and / or rotational or angular movements.

A known melt deposition modeling apparatus is shown in Figure 1. Extruder assembly 12 dispenses polymer 14 onto printing bed 18, in a layer-by-layer process, to form three-dimensional object 16. After the three-dimensional object 16 is completed, it can be removed from the build platform 18 and a new project can begin.

In certain examples, a three-dimensional manufacturing apparatus includes a deposition apparatus and a printing apparatus. In some embodiments, the deposition apparatus may be similar to that used for the fused deposition examples. In some examples, the deposition apparatus includes an extruder assembly that dispenses a polymer. In certain examples, the polymer forms a three-dimensional object in a layer-by-layer process on a printing bed. In certain examples, the printing apparatus includes a print head and ink supply system for depositing various inks during the production of any three-dimensional object using the three-dimensional manufacturing apparatus. In some examples, the extruder head may be stationary or it may allow movement in the XY axes, only X-axis or Y-axis movement, and / or rotational or angular movements. In certain examples, the build platform generally has Z-axis movement indexed options. Additionally, in certain examples, the build platform may allow optional XY-axis movement, only X-axis or Y-axis movement, and / or rotational or angular movements.

In some embodiments, when the three-dimensional object is manufactured, the print head and ink supply system can deposit inks on a layer-by-layer basis. In certain embodiments, the inks can be color inks and / or functional inks. In certain embodiments, the print head and ink supply system may be stationary or, in alternate embodiments, it may allow movement in the XY axes, only X-axis or Y-axis movement, and / or rotational movements or angular. In certain embodiments, printing of the inks can be triggered by an optical limit switch or a linear encoder.

A schematic of a three-dimensional manufacturing apparatus is provided in Fig. 2, including a deposition apparatus similar to that used for melt deposition patterning and a recording apparatus having a print head and ink supply system. A three-dimensional manufacturing apparatus includes an extruder assembly 32 that dispenses polymer 34, in a layer-by-layer process, to form a three-dimensional object 36 on the printing bed 38. Furthermore, the manufacturing apparatus includes a print head and ink supply system 40, which dispenses ink onto the three-dimensional object 36 in a layer-by-layer process during the build process.

In certain examples, the printing apparatus having a print head and ink supply system is attached to the same mechanism as the deposition apparatus having the extruder so that it moves with the deposition apparatus. In alternative examples, the printing apparatus is attached to an independent or stationary motion mechanism that is attached to the three-dimensional manufacturing apparatus. In alternative examples, the printing apparatus is aligned with the deposition apparatus, but is not attached to the deposition apparatus. In certain examples, the recording apparatus includes a print head (s) which may be for example a piezoelectric print head, a thermal print head, a MEMS print head, an electrostatic print head, or combinations thereof. . In alternative examples, the recording apparatus includes a recording head which may be a plotter type simple nozzle unit, a continuous ink jet, or a drop-on-demand system. In certain examples, the recording head of the recording apparatus can be positioned at any angle within the range of +45 to -45 degrees relative to the extruder of the deposition apparatus.

In alternate examples, the printing apparatus is paired with any solid free-form fabrication apparatus that constructs three-dimensional polymer objects using a layer-by-layer construction process. Non-exhaustive examples of such apparatus include a laminated object manufacturing apparatus or a three-dimensional photopolymer apparatus.

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The invention provides a three-dimensional manufacturing method that includes deposition of a first layer of polymer, printing of a first layer of ink on the first layer of polymer, deposition of a second layer of polymer on the first layer of ink, and printing a second layer of ink on the second layer of polymer. In some embodiments, the manufacturing process can be repeated to form a complete three-dimensional object. In certain embodiments, each of the first and second polymer layers can include a plurality of polymer layers. The plurality of polymer layers that form a first (or second) polymer layer need not be made up of the same polymers, but may include one or more different polymers. In certain embodiments, each of the first and second ink layers can include a plurality of ink layers. The plurality of ink layers that make up a first (or second) ink layer need not be made up of the same inks, but may include one or more different inks. In certain embodiments, the polymer layers or ink layers can be deposited in varying numbers and in varying order when manufacturing a three-dimensional object. Also, it is not necessary to fully spread the polymer layers and / or ink layers over the previously deposited layer. In some cases, an ink layer may be deposited only on a portion of the previously deposited polymer (or ink) layer. For example, an ink layer can be encapsulated between two surrounding polymer layers. In certain embodiments, printing or deposition of one layer on another can cause the two layers to bond with one another. In some embodiments, the bonding of one layer to another means that the layers do not separate from each other during the construction process. In some embodiments, an ink layer printed between two polymer layers may have at least one ingredient that is soluble in the polymeric material of the two polymer layers and causes a bond to form between the two polymer layers by joining one with the other. other. In certain embodiments, an ink layer can be printed on a complete three-dimensional object to form a coating. In certain embodiments, the liner can act as a cover having a thickness of 0.01 to 5mm, for example. In certain embodiments, the coating layer can be applied over an ink layer. In some embodiments, the coating layer can be a lacquer, and in alternative embodiments, it can be a translucent or transparent polymer.

In certain embodiments, an ink layer can be printed along the perimeter edge of the polymer layer. In some embodiments, the ink layer includes an ink that diffuses toward the perimeter edge of the polymer layer. In certain embodiments, the perimeter ink layer may be printed on a polymer, the polymer including a transparent or translucent polymeric material. In some embodiments, the perimeter ink layer printed on the transparent or translucent polymer can create an optical illusion so that the ink layer appears to extend into the polymer layer. In certain embodiments, an additional polymeric layer may be applied to the perimeter of the ink layer, thus providing protection against delamination or scratching, the polymeric material including a transparent or translucent polymeric material.

The three-dimensional manufacturing method can be used in certain embodiments to optically align the three-dimensional manufacturing apparatus. In certain embodiments, an ink layer pattern, such as a target pattern, is printed on one or more layers of a sacrificial three-dimensional object or harmlessly printed on any three-dimensional object. In some embodiments, the ink layer pattern is scanned with an optical sensor and the results of the optical alignment analysis are used to position the inkjet printhead and supply system as well as the extruder relative to the object. three-dimensional.

In certain embodiments, a polymer layer may be completely deposited prior to printing an ink layer on the polymer layer. In alternative embodiments, while the polymer is in the process of being deposited, an ink layer can be printed on the same polymer layer. In some embodiments, a first portion of at least one ink layer can include a first ink and a second portion of at least one ink layer can include a second ink. In certain embodiments, a first portion of at least one polymer layer can include a first polymeric material and a second portion of at least one polymeric layer can include a second polymeric material.

A schematic of a three-dimensional manufacturing process is provided in Figure 3. An ink layer is formed on a polymer layer by causing a print head and ink supply system 54 to deposit ink droplets 52, optionally including colorants or pigments, on the polymer 56. The ink droplets 52 form an area 58 where the ink comes into contact with the polymer 56.

In certain embodiments, an adjacent or attached support structure is formed to a three-dimensional object during the three-dimensional manufacturing process. In certain embodiments the three-dimensional apparatus is formed of a polymeric material. In some embodiments, the deposition apparatus is used to form the support structure. In alternative embodiments, a second deposition apparatus is used to form the support structure. In certain embodiments, the support structure can be removed from the three-dimensional object. In certain embodiments, a releasable ink layer is printed between the three-dimensional object and the support structure, in some embodiments, the releasable ink layer can be printed on the three-dimensional object only at the location where the support structure is attached. In certain embodiments, the support structure can be broken into smaller pieces for removal.

In certain embodiments, the polymeric material of the support structure is similar or, in some embodiments, is the same as the polymeric material used to form the three-dimensional object. The support structure and / or the three-dimensional object can be formed of one or more polymeric materials. In some embodiments, the structure

The support ES 2 823 975 T3 may include a polymeric material that is a water-soluble, solvent-soluble or alkali-soluble polymer, such as for example a water-soluble wax, polyethylene oxide and glycol-based polymers, polymers based on polyvinyl pyrrolidone, methyl vinyl ether or maleic acid based polymers.

In some embodiments, the support structure may have an outer ink layer. In certain embodiments, the outer ink layer has at least one ingredient that is soluble in a polymeric material included in the support structure. In some embodiments, the at least one ingredient in the polymeric material can accelerate dissolution of the polymeric material. In certain embodiments, the at least one ingredient may consist for example of low molecular weight compounds, such as polyethylene glycols, polypropylene glycols, polyalkylene glycols or polyethylene oxide. In alternative embodiments, the at least one ingredient in the polymeric material causes the outer ink layer to dissolve prior to dissolution of the polymeric material from the support structure. In some embodiments, the at least one ingredient can consist, for example, of salts such as potassium chloride, potassium oxalate or sodium citrate, water-soluble low molecular weight polymers, such as polyvinyl alcohols or polyethylene oxides, water-soluble organic compounds, as may be dimethyl urea or propylene glycol.

In certain embodiments, the at least one of the polymer layers may include a polymeric material such as acrylonitrile butadiene styrene ("ABS"), polyacrylates, polyolefins, cyclic olefin polymers and copolymers, polycarbonates, polyamides, polyimides, polyethylene. and polybutylene terephthalate, liquid crystal polymer resins ("LCP"), polyether ketone ("PEEK"), thermoplastic elastomers ("TPE"), polystyrenes, polyvinyl chloride, polysulfones, polyacrylates, polyurethanes, polyamides, polyesters, polyolefins, epoxy resins, silicon resin, a diallyl phthalate resin, a cellulosic plastic, a rosin modified maleic acid resin, copolymers thereof, any other macromolecular structure and combinations of the themselves. In certain embodiments, the polymer is acrylonitrile butadiene styrene. In certain embodiments, the polymer layer can include a biocompatible or biodegradable polymeric material, such as collagen, elastin, hydrogels, xerogels, proteins, peptides, or a combination of any of these. In some embodiments, the polymer layer may include a synthetic polymer such as polycaprolactone ("PCL"), poly (D, L-lactide-co-glycolide) ("PLGA"), polylactide ("PLA"), poly (lactide-co-caprolactone) ("PLCL") or a combination of any of them.

In certain embodiments, the first polymer layer is wetted by applying a first layer of ink. In certain embodiments, the ink in the first ink layer is a plasticizing or soluble ink that can diffuse into the first polymer layer (s). In certain embodiments, to obtain better wetting characteristics, the polymer and ink can be treated with plasma or corona discharge, in some embodiments, the layers can be treated by passing the source of the discharge above the surface of the layers to a distance of 1-5 mm for example.

In certain embodiments, the print head and ink supply system of the printing apparatus prints a layer of ink. In certain embodiments, at least one of the ink layers includes an ink having, for example, colorants, pigments, and / or catalysts. In some embodiments, the ink is a colored ink. In certain embodiments, the catalyst can be a chemical metallization catalyst. In certain embodiments, the chemical metallization can be for example an organometallic salt or complex of palladium, ruthenium, platinum, silver, osmium, iridium or cobalt. In some embodiments, other metals from Groups 8, 9, 10, and 11 of the Periodic Table of chemical elements are within the scope of the present invention. In certain embodiments, the ink can include a chemical metallization catalyst that is silver or palladium.

In some embodiments, the ink, the polymeric material, or both the ink and the polymeric material, can include an active ingredient. In some embodiments, the active ingredient can be for example a pharmaceutical active ingredient or a cell culture. In certain embodiments, the pharmaceutical active ingredient can be for example an anti-inflammatory ingredient, such as, for example, corticosteroids, diclofenac sodium, aspirin, ibuprofen or acetaminophen; an ingredient that inhibits neointimal growth, such as, for example, everolimus, paclitaxel or zotarolimus; a blood thinner, such as warfarin, heparin, fondaparinux, ximelagatran, or batroxobin; an immunosuppressive ingredient, such as for example cyclosporine, tacrolimus, sirolimus or mycophenolic acid; an antibody, such as for example monoclonal anti-IL-2Ra receptor antibodies, polyclonal anti-T-lymphocyte antibodies, anti-thymocyte glubulin ("ATG") or anti-lymphocyte glubulin ("ALG"); or chemotherapeutic drugs such as, for example, alkylating agents, antimetabolites, plant alkaloids or topoisomerase inhibitors; or a combination of any of them. In some embodiments, a cell culture can include for example stem cells, cartilage cells, bone cells, muscle cells, skin cells, pancreatic cells, kidney cells, liver cells, neurons, or a combination of any of these. In some embodiments, a cell culture can be a live cell culture.

In some embodiments, a single layer of ink or polymer that has an active ingredient can be printed / deposited. In alternative embodiments, a series of layers of ink or polymer can be printed in a row. It is currently understood that by varying the number of layers of ink or polymer that have an active ingredient, the concentration and / or amount of the active ingredient on the three-dimensional object can be varied. In certain embodiments, the ink layer is formed using an ink that includes a cell culture on a polymer layer formed using a biocompatible or biodegradable polymer. In some embodiments, an ink layer formed using an ink that includes a cell culture can form living tissue on a biocompatible or biodegradable polymer. In certain embodiments, the living tissue will correspond to the type of cells in the cell culture.

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In certain embodiments, the ink may have a viscosity within the range a of 10^-3 Pa ^ s to 2x10^-1 Pa ^ s (1 to 150 cps), within the range of 10^-3 Pa ^ s to 5x10^-2 Pa ^ s (1 to 50 cps), or within the range of 10^-3 Pa ^ s to 2x10^-2 Pa ^ s (1 to 22 cps), at a temperature of 25 ° C. In certain embodiments, the ink may have a surface tension within the range of 0.018-0.072 N / m (18 to 72 dynes / cm), within the range of 0.02-0.04 N / m (20 to 40 dynes / cm). cm) or within the range of 0.022-0.033 N / m (22 to 33 dynes / cm), at a temperature of 25 ° C.

In certain embodiments, the ink may be selected individually based on the solubility parameter of the ink and the solubility parameter of the polymer of the three-dimensional object. It should be understood that solubility parameters, also known as Hildebrand solubility parameters (δ) and Hansen solubility parameters, are a result of various intermolecular forces, including scattering bond energy (ód), intermolecular dipole force- dipole (op) and hydrogen bonds (oh). Specific Hildebrand solubility parameters can be calculated using the equation:

(Equation I) or = (ód² + op² + oh²)°,5

If two materials have similar Hildebrand solubility parameters, they are likely to be able to interact with each other. In some embodiments, the Hansen solubility parameters of the two materials can be used to determine whether one material dissolves in the other, such as a polymer in a solvent or an ink. A value called the radius of interaction (Ro) is given to the material to be dissolved. The interaction radius of the material to be dissolved, such as a polymer, can define a sphere in Hansen's space. If the second material, such as an ink, is within the sphere defined by the interaction radius, then the polymer can be considered to dissolve in the ink. The sphere is defined by the equation:

(Equation 2)

D (IP) = [4 (ódi - ódp)² + (ópi - ópp)² + (óhi - óhp)²]⁰,⁵ where: D (IP) is the distance between the ink and the center of the solubility sphere of polymer oxide, and is the Hansen component (as defined above) for an ink; oxp is the Hansen component (as defined above) for the polymer.

In certain embodiments, a specific ink can be selected based on its solubility interaction with the specific polymer used for the three-dimensional object. In some embodiments, the solubility of the ink in the polymer can be enhanced using sources of heat or energy. In certain embodiments, improved ink solubility provides additional benefits, including, for example, improved ink drying characteristics. In certain embodiments, the heat source can be for example conventional heat, conduction, radiant, or combinations thereof. In certain embodiments, the heat or power source is applied after the three-dimensional object is manufactured. In alternative embodiments, the source of heat or energy is applied during manufacturing of the three-dimensional object. In alternative embodiments, for example, the energy source can be an electromagnetic energy source. In certain embodiments, the source of electromagnetic energy can be, for example, infrared, near infrared, visible, radio frequency, microwave, or combinations thereof. Many polymers and inks are transparent in the infrared visible range, but in certain embodiments the polymer can be supplemented with pigments, colorants, or chemical metallization catalysts, which can absorb energy in the same range, thus increasing the efficiency of the process. Additionally, in certain embodiments, various infrared, near infrared, visible energy, microwave, or radio frequency absorbers can be used to supplement the ink.

In certain embodiments, the ink may have a solubility parameter that falls within the interaction radius, as defined by Equation 2. Reference herein is made to inks that have a solubility parameter that falls within the interaction radius as plasticizer inks. In certain embodiments, a plasticizer ink can be used to provide a colored coating or coating, to provide a functional coating, or to improve the surface quality of a three-dimensional polymeric object. In certain embodiments, the plasticizer ink further includes functional additives including, for example, chemical metallization or other catalysts, antimicrobial agents, or release additives. In certain embodiments, the plasticizer ink provides a coating to a curable three-dimensional polymer object. In certain embodiments, the coating is a UV-curable coating. In some embodiments, the curable coating can create a smoother surface on the three-dimensional polymer object by filling in the interstices in an untreated surface of the object.

In certain embodiments, three-dimensional polymer objects formed with a polymer and a plasticizing ink by the method according to the invention can be used to produce patterns for precision casting, also known as lost wax casting. It is currently understood that in certain embodiments, the plasticizer ink allows for a cleaner burning process during casting.

In certain embodiments, a first portion of at least one of the ink layers is formed using a plasticizer ink and a second portion of the ink layer is formed using a second plasticizer ink that has a higher concentration of plasticizer than the first ink. In some embodiments, a difference in quantity

ES 2 823 975 T3 of plasticizer in two different inks can cause a difference in the surface or material properties of the ink layer. In some embodiments, a three-dimensional object formed by using a plasticizer ink that has a higher concentration of plasticizer can exhibit greater flexibility compared to a three-dimensional object formed using an ink that is not a plasticizer ink. In certain embodiments, a plasticizer ink creates a smooth surface on a three-dimensional object. It is currently understood that plasticizing ink dissolves a portion of the surface of a polymer layer, thus creating a smoother surface.

In alternate examples, the print head and ink supply system includes an ink having a solubility parameter that is outside the interaction radius, as defined by Equation 2. Reference is made herein to inks. They have a solubility parameter that is outside the interaction radius as release inks. In certain embodiments, release inks can be used to promote the release of a support structure from the three-dimensional polymer object. In alternative embodiments, the release inks can provide a covering on a three-dimensional object. In some embodiments, the release inks may further include, for example, colorants, pigments, or catalysts for use in coating formation. In certain embodiments, the cover can be a colored cover. In certain embodiments, three-dimensional objects with a release ink color coating can be treated with a fixative liquid, in certain embodiments, a fixative liquid can be any liquid or solution with a solubility parameter within the interaction radius, as shown. define in Equation 2. In certain embodiments, the process of attaching the colored cover to the three-dimensional object can be accelerated by the application of heat, light, or electromagnetic energy, for example. In certain embodiments, volatile components can be evaporated with or without vacuum.

In alternative embodiments, an ink used in the three-dimensional manufacturing method may have a low binding affinity with the specific polymer being used to form a three-dimensional object thereby resulting in low adhesion of the ink to the polymer. In certain embodiments, if the ink is printed on the polymer to form a colored cover, at least one final polymer layer can be deposited on the colored cover to help retain the ink on the three-dimensional object. In such embodiments, the polymer for the final layer can be for example transparent or translucent and can be selected from the group having acrylates, methacrylates, polycarbonates, poly (acrylonitrile butadiene styrene), polyesters, transparent polyamides, polymers and copolymers of cycloaliphatic olefins, Styrene Acrylonitrile Polymer, Polyvinyl Chloride, Epoxides. In certain embodiments, a reflective or opaque ink layer may be printed on the polymer prior to printing the colored cover.

In alternative embodiments, the low tack inks can be printed onto the polymer of the three-dimensional object to form an outer colored coating, and then the colored coating can be sprayed with a permanent clear lacquer to form a lacquer coating on the surface. color cover. In certain embodiments, the lacquer can protect the outer colored covering of the three-dimensional object, for example. In certain embodiments, the lacquer can be for example a quick-drying polymer solution, such as a translucent or transparent polymer. In certain embodiments, the lacquer can be for example a solution of nitrocellulose in butyl acetate. In certain alternative embodiments, the lacquer can be for example a fast curing, thermosetting, or UV or IR curable resin.

Examples Example 1 - Examination of solvent inks and plasticizers

A Lexmark 22420® ink jet printer was equipped with thermal print heads to provide good color coverage on acrylonitrile butadiene styrene ("ABS") flat plates, ABS plates were obtained from McMaster Can-. A color layer was printed on ABS plates and color adhesion was tested using the ASTM D3359 test to measure adhesion through the adhesive tape test. The result showed that the adhesion of the color layer to the ABS plates was low.

To improve color adhesion, color-coated ABS plates were immersed in tetrahydrofuran, a volatile solvent. The plates were then placed in an oven at 60 ° C for 10 minutes. The plates were removed from the oven and the ASTM D3359 test was repeated. The results showed improved color adhesion for the ABS plates.

The application of a colored layer to ABS plates was repeated, but the colored coated plates were dipped in propylene carbonate, a non-volatile solvent, instead of volatile tetrahydrofuran. The ABS plates were then placed in an oven at 60 ° C for 10 minutes and the color adhesion was analyzed following the test of ASTM D3359. The results were similar to the results obtained with the tetrahydrofuran plates.

Example 2 - Color ink composition test

Ink containing 99.8% diisopropyl adipate and 0.2% zonyl FSO surfactant (DuPont) and trace amounts of black dye extracted from a Sharpie® were deposited with the tip of a ballpoint pen onto ABS plates and 3-D objects. of ABS produced from ABS on a Dimension 1200 ES® printer. The adhesion of the color standards was tested with the test methods of ASTM D3359 for measuring adhesion through the adhesive tape test, and passed.

ES 2 823 975 T3

Example 3 - Examination of plasticizer ink

Ink containing 99.8% propylene carbonate and 0.2% Zonlyl FSO surfactant (Dupont) was deposited with the tip of a ballpoint pen on a polybutylene terephthalate ("PBT") plate. A second PBT plate was placed on the color-coated PBT plate and placed in an oven at 105 ° C. After 30 minutes the two PBT plates were adhered. The adhesion of the two plates occurred at a temperature well below the PBT melting temperature of 223 ° C. The test was repeated with two uncoated PBT plates placed in the oven at 105 ° C. The plates did not adhere to each other.

Example 4 - Release ink test

Dodecamethylpentasiloxane was deposited directly onto an ABS plate using the tip of a ballpoint pen. The coated ABS plate was then covered with a second clean ABS plate and clamped down. The two plates were placed in an oven at 150 ° C for 35 minutes. After removing the plates from the oven, the two ABS plates were easily separated. The test was repeated with two clean ABS plates clamped and placed in the oven at 150 ° C for 35 minutes. Apparently, the two plates were sintered with each other.

Example 5 - Examination of inks containing palladium-based chemical catalyst

An ink containing 1.5% by weight palladium acetate in N-methylpyrrolidone was deposited with the tip of a ballpoint pen in a predetermined pattern on a PBT plate. The coated plate was placed in a 70 ° C oven for 10 minutes. After removing the coated PBT plate from the oven, the designed surface was treated with 2% aqueous dimethylamine borane complex (DMAB) solution for 2 minutes and then washed with distilled water. The treated coated PBT plates were then immersed in chemical nickel plating solution (Caswell) at a temperature of 90 ° C for 25 minutes. The PBT plates revealed bright electrically conductive metal deposits in the designed area.

Example 6 - Examination of inks containing silver-based chemical catalyst

A catalytic ink was prepared by dissolving 1.0 g of silver nitrate in 99 ml of 40% w / w aqueous tetrahydrofuran solution. The catalytic ink was deposited in a predetermined pattern using the tip of a ballpoint pen on the surface of the ABS plates. The designed ABS plates were then placed in a 70 ° C oven for 15 minutes. After removing the ABS plates from the oven, the designed surface was treated with 2% aqueous dimethylamine borane complex (DMAB) solution for 2 minutes at 45 ° C and then washed with distilled water. Next, the treated coated ABS plates were immersed in chemical copper plating solution A (Table 1) at a temperature of 60 ° C for 15 minutes. The ABS plates revealed shiny electrically conductive metal deposits in the designed area.

<td colspan="2">Table 1</td>

<td colspan="2">200 ml chemical copper plating solution</td>

<td>Copper sulfate pentahydrate</td><td>8.00 g</td>

<td>Formalin</td><td>20.80 g</td>

<td>Sodium hydroxide</td><td>12.50 g</td>

<td>Tetrahydroxypropyl ethylenediamine</td><td>12.00 g</td>

<td>Triisopropanol amine</td><td>2.00 g</td>

<td>Nickel sulphate</td><td>0.03 g</td>

<td>Triton X-100 surfactant</td><td>0.02 g</td>

Example 7 - Color-design adhesion test

A Cannon Pixma IP 2702® printer was equipped with thermal ink jet print heads. A color-pattern layer was printed on ABS plates that were 0.12 mm (5 mils) thick, and color adhesion was tested using the ASTM D3359 test to measure adhesion by tape test. The result showed that the adhesion of the color-design layer to the ABS plates was low.

To improve the color adhesion of the color-design layer, a color-design layer was printed on 0.12 mm (5 mils) thick ABS plates and a second layer of ABS was placed on top of the color layer. printed and the two layers were fused using a hot electric iron. Image quality was apparently good on both sides of the ABS plates. The fused ABS plates were subjected to a test for excessive flexing and adhesion using the ASTM D3359 test to measure adhesion through a tape test. The image was not distorted during excessive bending and exhibited good adhesion.

Example 8 - Adhesion test with color-design

A 0.12 mm (5 mils) thick ABS plate was spray coated with Krylon Flat® spray paint and then dried. The Cannon Pixma IP 2702® printer from Example 7 was then used to print a

ES 2 823 975 T3 color-patterned coating on a 5 mm thick untreated ABS plate. Next, the color-design ABS plate with the color-design face down was placed on the spray-coated ABS plate and sintered with a hot electric iron. The image quality of the color-patterned layer was apparently more prominent and sharper than the image produced in Example 7.

Example 9 - Color-design adhesion test

The Cannon Pixma IP 2702® printer of Example 7 was used to print a color-pattern layer on a 0.12 mm (5 mils) thick ABS plate. Image quality was good. The color-pattern side of the ABS plate was then spray coated with Krylon Crystal Clear® acrylic and dried for one hour. After the treated ABS sheets had dried, they were subjected to a test for excessive flexing and adhesion using a Scotch adhesive tape. The image was not distorted during excessive bending and exhibited good adhesion to the ABS plate.

Example 10 Examination of multilayer color printing on a transparent polymer

A fused deposition modeling machine was assembled to form a three-dimensional object from version 3 of the commercially available Rap Man USA® kit. The machine was then equipped with proprietary evaluation equipment, which allows printing with a thermal jet ("TO") print head. The hardware and firmware of the machine was modified so that the TIJ print head could be used for the layers of printing ink during layer-by-layer construction of the three-dimensional object. TIJ printing was triggered by an optical limit switch attached to the X axis of the machine.

A PLA polymer three-dimensional object, obtained from Ultimachine, South Pittsburg, TN, was formed using the modified machine. The three-dimensional object was 20 x 20 x 6 mm and the thickness of each individual layer was 0.25 mm (24 layers).

Example 10a- Insufficient adhesion with traditional printing

An image of a cross was printed on the top layer (layer No. 24) of the black ink of the trademark three-dimensional PLA polymer object. The image of the three-dimensional object was easily removed with a paper towel.

Example 10b - Subsurface printing of a part

An image of a cross was printed on a layer below the top layer (layer # 23) of the three-dimensional PLA polymer object using HP 45® ink. The image was sharp, had good contrast, and the integrity of the machine did not change when the surface of the object was rubbed with a paper towel. The image failed the ASTM D3359 test.

Example 10- Printing along the Z axis

An image of a cross was printed on multiple layers (layers # 3-23) of the three-dimensional PLA polymer object using HP 45® ink. The image was placed 0.25 mm from the perimeter edge of the three-dimensional object. The image was sharp, had good contrast and integrity in the two XY and Z axes that did not change when the surface of the object was rubbed with a paper towel. The image also passed the test of ASTM D3359.

Example 11- Examination of multilayer color printing on a transparent polymer

A fused deposition modeling machine was assembled to form a three-dimensional object from version 3.1.0 of the commercially available Rap Man USA® kit. The machine was then equipped with an HP 2.5® evaluation equipment that allows printing with a Thermal Jet ("TIJ") print head. The hardware and firmware of the machine were modified so that the TIJ print head could be used to print layers of ink during layer-by-layer construction of a three-dimensional object. TIF printing was triggered by a linear encoder attached to the X axis of the machine.