Method and apparatus for three-dimensional fabrication with feed through carrier.
Abstract
A method for forming a three-dimensional object is carried out by (a) providing a carrier and a construction plate, the construction plate comprises a semipermeable member, the semipermeable member comprises a construction surface with the construction surface and the carrier defining a construction region therebetween, and with the construction surface in fluid communication by means of the semipermeable member with a source of polymerization inhibitor; (b) filling the construction region with a polymerizable liquid, the polymerizable liquid making contact with the construction surface, (c) irradiating the construction region through the construction plate to produce a solid polymerized region in the construction region , while forming or maintaining a liquid film release layer composed of the polymerizable liquid formed between the solid polymerized region and the construction surface, the polymerization of such a liquid film is inhibited by the polymerization inhibitor; and (d) advancing the carrier with the polymerized region adhered thereto away from the construction surface on the construction plate to create a region of subsequent construction between the polymerized region and the construction surface; (e) wherein the carrier has at least one channel formed therein, and the filling step is carried out by passing or forcing the polymerizable liquid in the construction region through the at least one channel; The apparatus for carrying out the method is also described.

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30 claims: 4 independent, 26 dependent
- 1NOVEDAD DE LA INVENCION IMPI INSTTTUTO MUK NO ·· LA mO*1£DA0 lAW.'miAL REIVINDICACIONES 1 .- Un método para formar un objeto tridimensional, que comprende los pasos de:(a) proporcionar un portador y una placa de construcción, dicha placa de construcción comprende un miembro semipermeable, dicho miembro semipermeable comprende una superficie de construcción, con dicha superficie de construcción y dicho portador definiendo una región de construcción entre los mismos, y con dicha superficie de construcción en comunicación fluida por medio del miembro semipermeable con una fuente de inhibidor de polimerización;(b) llenar dicha región de construcción con un líquido polimerizable, dicho líquido polimerizable haciendo contacto con dicha superficie de construcción;(c) irradiar dicha región de construcción a través de dicha placa de construcción para producir una región polimerizada sólida en dicha región de construcción, mientras forma o mantiene una capa de liberación de película líquida compuesta por dicho líquido polimerizable formado entre dicha región polimerizada sólida y dicha superficie de construcción, la polimerización de tal película líquida se inhibe por medio de dicho inhibidor de polimerización;y (d) avanzar dicho portador con dicha región polimerizada adherida al mismo lejos de dicha superficie de construcción sobre dicha placa de construcción para crear una región de construcción subsecuente entre dicha región polimerizada y dicha superficie de construcción;(e) continuar y/o repetir los pasos (b) a (e) para producir una región polimerizada subsecuente adherida a una región polimerizada previa hasta que la deposición continua o repetida de las regiones polimerizadas adheridas entre sí forme dicho objeto tridimensional;(f) en donde dicho portador tiene al menos un canal formado en el mismo, y dicho paso de llenado se lleva a cabo pasando o forzando dicho líquido polimerizable en dicha región de construcción a través del al menos un canal y a través de dicho objeto.
- 2- El método de conformidad con la reivindicación 1, caracterizado además porque dicho portador tiene una pluralidad de canales formados en el mismo, y en donde diferentes líquidos polimerizables se fuerzan a través de diferentes canales de la pluralidad de canales.
- 3- El método de conformidad con la reivindicación 1, caracterizado además porque comprende adicionalmente formar de manera concurrente al menos uno, o una pluralidad de conductos de alimentación externa separados de dicho objeto, cada uno del al menos un conducto de alimentación en comunicación fluida con un canal en dicho portador, para abastecer al menos uno, o una pluralidad de diferentes líquidos polimerizables desde dicho portador a dicha zona de construcción.
- 4- Un método para formar un objeto tridimensional, que comprende los pasos de:(a) proporcionar un portador y una placa de construcción, dicha placa de construcción comprende un IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL miembro semipermeable, dicho miembro semipermeable comprende una superficie de construcción, con dicha superficie de construcción y dicho portador definiendo una región de construcción éntre' los mismos, y con dicha superficie de construcción en comunicación fluida por medio del miembro semipermeable con una fuente de inhibidor de polimerización;(b) llenar dicha región de construcción con un líquido polimerizable, dicho líquido polimerizable haciendo contacto con dicha superficie de construcción;(c) irradiar dicha región de construcción a través de dicha placa de construcción para producir una región polimerizada sólida en dicha región de construcción, mientras forma o mantiene una capa de liberación de película líquida compuesta por dicho líquido polimerizable formado entre dicha región polimerizada sólida y dicha superficie de construcción, la polimerización de tal película líquida se inhibe por medio de dicho inhibidor de polimerización;y (d) avanzar dicho portador con dicha región polimerizada adherida al mismo lejos de dicha superficie de construcción sobre dicha placa de construcción para crear una región de construcción subsecuente entre dicha región polimerizada y dicha superficie de construcción;(e) continuar y/o repetir los pasos (b) a (e) para producir una región polimerizada subsecuente adherida a una región polimerizada previa hasta que la deposición continua o repetida de las regiones polimerizadas adheridas entre sí forme dicho objeto tridimensional;(f) en donde dicho portador tiene al menos un canal formado en el mismo, y dicho paso de llenado se lleva a cabo pasando o forzando dicho líquido polimerizable en dicha región de construcción a través del al menos un canal y a través de dicho objeto;en donde los pasos (b) a (e) se llevan a cabo de manera concurrente.
- 5- El método de conformidad con la reivindicación 1, caracterizado además porque la placa de construcción es estacionaria.
- 6- El método de conformidad con la reivindicación 1, caracterizado además porque la fuente del inhibidor de polimerización es un depósito de inhibidor de polimerización dentro del miembro semipermeable.
- 77 ,- El método de conformidad con la reivindicación 1, caracterizado además porque el miembro semipermeable comprende además una superficie de alimentación separada de dicha superficie de construcción.
- 8- El método de conformidad con la reivindicación 7, caracterizado además porque la superficie de alimentación está en contacto fluido con un inhibidor de polimerización para proporcionar dicha fuente de inhibidor de polimerización.
- 9- El método de conformidad con la reivindicación 1, caracterizado además porque dicho paso o pasos de avance se lleva(n) a cabo a una velocidad acumulativa de por lo menos 10 mieras por segundo.
- 10- El método de conformidad con la reivindicación 1, caracterizado además porque líquido polimerizable en exceso se suministra a dicha región de construcción, se elimina o se drena IMPI IHJTTWTO MEXICANO BB LA MOHEDA» INDUSTRIAL de la misma para enfriar dicha región de construcción, y luego se rodrfiila nprinnalmpntp de regreso a dicha región de construcción.
- 11- El método de conformidad con la reivindicación 1, caracterizado además porque dicho paso de avance se lleva a cabo al hacer avanzar dicho portador verticalmente desde dicha superficie de construcción.
- 12- El método de conformidad con la reivindicación 7, caracterizado además porque:dicho miembro semipermeable comprende una porción de superficie superior, una porción de superficie inferior, y una porción de superficie de borde;dicha superficie de construcción está en dicha porción de superficie superior;y dicha superficie de alimentación está en por lo menos una de dicha porción de superficie superior, dicha porción de superficie inferior, y dicha porción de superficie de borde.
- 13- El método de conformidad con la reivindicación 1, caracterizado además porque dicho paso de irradiación se lleva a cabo con radiación actínica.
- 14- El método de conformidad con la reivindicación 1, caracterizado además porque:un área de superficie total de la región de construcción ocupa al menos setenta por ciento de un área de superficie total de la superficie de construcción;y/o en donde el movimiento lateral del portador y el objeto en cualquier dirección no es mayor que treinta por ciento de un ancho de dicha región de construcción en la dirección correspondiente.
- 15- El método de conformidad con la reivindicación 1, caracterizado además porque (a) dicho líquido polimerizable comprende un líquido polimerizable de radicales libres y dicho inhibidor comprende oxígeno, o (b) dicho líquido polimerizable comprende un líquido catiónicamente polimerizable o catalizado con ácido, y dicho inhibidor comprende una base.
- 16- El método de conformidad con la reivindicación 1, caracterizado además porque dicho líquido polimerizable comprende además un agente activo, un agente detectable, partículas sólidas, o una combinación de los mismos.
- 17- El método de conformidad con la reivindicación 1, caracterizado además porque dicho paso de irradiación se lleva a cabo por fotolitografía sin máscara.
- 18- Un método para formar un objeto tridimensional, que comprende los pasos de:(a) proporcionar un portador y una placa de construcción, dicha placa de construcción comprende un miembro semipermeable, dicho miembro semipermeable comprende una superficie de construcción, con dicha superficie de construcción y dicho portador definiendo una región de construcción entre los mismos, y con dicha superficie de construcción en comunicación fluida por medio del miembro semipermeable con una fuente de inhibidor de polimerización;(b) llenar dicha región de construcción con un líquido polimerizable, dicho líquido polimerizable haciendo contacto con dicha superficie de construcción;(c) irradiar dicha región de construcción a través de dicha placa de IMPI INSTITUTO MEXICANO DE LA MONEDAD INDUSTRIAL construcción para producir una región polimerizada sólida en dicha región de construcción, mientras forma o mantiene una capa de liberación de película líquida compuesta por dicho liquido polimerizable formado entre dicha región polimerizada sólida y dicha superficie de construcción, la polimerización de tal película líquida se inhibe por medio de dicho inhibidor de polimerización;y (d) avanzar dicho portador con dicha región polimerizada adherida al mismo lejos de dicha superficie de construcción sobre dicha placa de construcción para crear una región de construcción subsecuente entre dicha región polimerizada y dicha superficie de construcción;(e) en donde dicho portador tiene al menos un canal formado en el mismo, y dicho paso de llenado se lleva a cabo pasando o forzando dicho líquido polimerizable en dicha región de construcción a través del al menos un canal;el método comprende además los pasos de: monitorear o detectar al menos un parámetro del procedimiento y/o proporcionar al menos un parámetro del procedimiento conocido o predeterminado;y luego alterar al menos una condición del procedimiento en respuesta a dicho parámetro del procedimiento monitoreado o parámetro del procedimiento conocido.
- 19- El método de conformidad con la reivindicación 1, caracterizado además porque el portador con dicha región polimerizada adherida al mismo se hace avanzar unidireccionalmente lejos de dicha superficie de construcción en dicha placa de construcción estacionaria.
- 20- Un método para formar un objeto tridimensional, que comprende los pasos de:(a) proporcionar un portador y una placa de construcción, dicha placa de construcción comprende un miembro semipermeable, dicho miembro semipermeable comprende una superficie de construcción, con dicha superficie de construcción y dicho portador definiendo una región de construcción entre los mismos, y con dicha superficie de construcción en comunicación fluida por medio del miembro semipermeable con una fuente de inhibidor de polimerización;(b) llenar dicha región de construcción con un líquido polimerizable, dicho líquido polimerizable haciendo contacto con dicha superficie de construcción;(c) irradiar dicha región de construcción a través de dicha placa de construcción para producir una región polimerizada sólida en dicha región de construcción, mientras forma o mantiene una capa de liberación de película líquida compuesta por dicho líquido polimerizable formado entre dicha región polimerizada sólida y dicha superficie de construcción, la polimerización de tal película líquida se inhibe por medio de dicho inhibidor de polimerización;y (d) avanzar dicho portador con dicha región polimerizada adherida al mismo lejos de dicha superficie de construcción sobre dicha placa de construcción para crear una región de construcción subsecuente entre dicha región polimerizada y dicha superficie de construcción;(e) en donde dicho portador tiene al menos un canal formado en el mismo, y dicho paso de llenado se lleva a cabo pasando o forzando dicho líquido polimerizable en dicha región de construcción a través del al menos un canal;y (f) en donde dicho paso de avanzar se lleva a cabo mientras también de manera concurrente (i) se mantiene continuamente una zona muerta de líquido polimerizable en contacto con dicha superficie IMPI INSTITUTO MOUCANQ M LA TIIOMMMO INDUSTRIAL de construcción, y (¡i) se mantiene continuamente un gradiente de zona de polimerización entre dicha zona muerta y dicho polímero sólido y en contacto cóh 'CaCRTuno dé lóá'mísmós, dicho gradiente de zona de polimerización comprende dicho líquido polimerizable en forma parcialmente curado.
- 21- El método de conformidad con la reivindicación 5, caracterizado además porque dicho miembro semipermeable comprende una película flexible de polímero, y la placa de construcción comprende además un miembro tensor conectado a la película de polímero para fijar y hacer rígida la película.
- 22- El método de conformidad con la reivindicación 21, caracterizado además porque dicha película flexible de polímero comprende una película fluoropolimérica.
- 23- El método de conformidad con la reivindicación 20, caracterizado además porque dicha placa de construcción es estacionaria.
- 24- El método de conformidad con la reivindicación 23, caracterizado además porque dicho miembro semipermeable comprende una película flexible de polímero, y la placa de construcción comprende además un miembro tensor conectado a la película de polímero para fijar y hacer rígida la película.
- 25- El método de conformidad con la reivindicación 18, caracterizado además porque dicho parámetro del procedimiento es consumo esperado de líquido polimerizable;y dicha condición del procedimiento es una velocidad de suministro de líquido polimerizable.
- 26- El método de conformidad con la reivindicación 1, caracterizado además porque dicho miembro semipermeable comprende una película fluoropolimérica.
- 27- El método de conformidad con la reivindicación 4, caracterizado además porque dicho miembro semipermeable comprende una película fluoropolimérica.
- 28- El método de conformidad con la reivindicación 18, caracterizado además porque dicho miembro semipermeable comprende una película fluoropolimérica.
- 29- El método de conformidad con la reivindicación 20, caracterizado además porque dicho miembro semipermeable comprende una película fluoropolimérica.
- 30- El método de conformidad con la reivindicación 18, caracterizado además porque dicha condición del procedimiento es velocidad de suministro de líquido polimerizable, temperatura, presión, tasa o velocidad de avance del portador, intensidad de irradiación, o duración de irradiación.
Independent claims30
413 paragraphs in 66 sections, as filed
(54) Title: METHOD AND APPARATUS FOR THREE-DIMENSIONAL MANUFACTURING WITH POWER SUPPLY THROUGH A CARRIER.
(54) Title: METHOD AND APPARATUS FOR THREE-DIMENSIONAL FABRICATION WITH FEED THROUGH CARRIER.
(57) Summary
A method of forming a three-dimensional object is carried out by (a) providing a carrier and a build plate, the build plate comprises a semi-permeable member, the semi-permeable member comprises a build surface with the build surface and the carrier defining a building region therebetween, and with the building surface in fluid communication via the semipermeable member with a source of polymerization inhibitor; (b) filling the building region with a polymerizable liquid, the polymerizable liquid contacting the building surface, (c) irradiating the building region through the build plate to produce a solid polymerized region in the building region , while forming or maintaining a liquid film release layer composed of the polymerizable liquid formed between the solid polymerized region and the building surface, the polymerization of such a liquid film is inhibited by the polymerization inhibitor; and (d) advancing the carrier with the polymerized region adhered thereto away from the building surface on the build plate to create a subsequent building region between the polymerized region and the building surface; (e) wherein the carrier has at least one channel formed therein, and the filling step is carried out by passing or forcing the polymerizable liquid into the building region through the at least one channel; The apparatus for carrying out the method is also described.
(57) Abstract
A method of forming a three-dimensional object, ¡s carried out by (a) providing a carrier and a build piafe, the build piafe comprising a semipermeable member, the semipermeable member comprising a build surface with the build surface and the carrier defining a build region therebetween, and with the build surface in fluid communication by way of the semipermeable member with a source of polymerization inhibitor; (b) filling the build region with a polymerizable liquid, the polymerizable liquid contacting the build surface; (c) irradiating the build region through the build píate to produce a solid polymerized region in the build region, while forming or maintaining a liquid film release layer comprised of the polymerizable liquid formed between the solid polymerized region and the build surface, the polymerization of which liquid film is inhibited by the polymerization inhibitor; and (d) advancing the carrier with the polymerized region adhered thereto away from the build surface on the build plate to create a subsequent build region between the polymerized region and the build surface; (e) wherein the carrier has at least one channel formed therein, and the filling step is carried out by passing or forcing the polymerizable liquid into the build region through the at least one channel. Apparatus for carrying out the method is also described.
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IMPI i ·. \ 'f-> i * ·, i.' * '? ! "· I 'A i
PATENT TITLE No. 352425
Holders): CARBON3D, INC.
Address: 312 Chestnut Yes, Redwood City, California, 94063, USA
D nomination: METHOD AND APPARATUS FOR THREE-DIMENSIONAL MANUFACTURING WITH FEEDING THROUGH A CARRIER.
Classification:
JOS
International Inventor (s):
Country:
In accordance with the article from the date of presentation
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ERM
NIKITA ERMOSHKIN;
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Industrial.
articulate motto
Istrial. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004,
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CIP:
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Number:
MX / a / 2016>! 0375
Validity: See Date of VF cha of Ex
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Whoever signs this title is (Official Gazette of the Federation (01/25/2006, 05/06/2009, 06/01/2010,
G03F7
B29C3, O03IZ. DESIMONE: SAMUL
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133Y30 / 00; B33Y50 / 02; G03F7 / 00
B29C67 / 0085; B29C67 / 0088;
746 J341 n foundation and of I itud ü of the Regulations of the Mexican Institute of I · articles 1<sup>or</sup>, 3<sup>or</sup>, 4°, 5<sup>or</sup> fraction V subsection a), 16 fl 12/27/1999, amended 10/10/2002, 07/29/2004, 0 Deputy Generals, Coordinator, Directors DnristoriSesT Titul Departamentales and other subordinates of the Instituto Mexicano de la Tarifa .paterna ^ 4*·
6 ° ^ qMpnes III!, 29 1 °, non-extendable, counted at IMperechos.
a Law on Industrial Property / 1999, 01/26/2004, 06/16/2005, subsection a), 4<sup>or</sup> and 12th fractions I and III
002, 07/15/2004, 07/28/2004 and 09/07/2007);
Exican of Industrial Property (DOF agreement that delegates powers to the Tonal Directors, Divisional Deputy Directors, Coordinators
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7)52^5 <sup>1</sup> IMPI
INSTITUTO MEXICANO DI LA H0HEDAD METHOD AND APPARATUS FOR THREE-DIMENSIONAL MANUFACTURING WITH ALIhO ^ ACI
THROUGH CARRIER —-- '-'
RELATED REQUESTS
This application claims the benefit of commonly owned US Provisional Patent Applications Serial No. 61 / 919,903, filed December 23, 2013 (proxy case no. 1151-3PR2); 61 / 865,841, filed on August 14, 2013 (proxy case no. U51-3PR) and 61 / 763,746, filed on February 12, 2013 (proxy case no. 1151-2PR), the descriptions of which are incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
The present invention relates to methods and apparatus for the manufacture of solid three-dimensional objects from liquid polymerizable materials.
BACKGROUND OF THE INVENTION
In conventional three-dimensional or additive manufacturing techniques, the construction of a three-dimensional object is done in a step-by-step or layer-by-layer fashion. In particular, the layer formation is carried out through the solidification of photo-curable resin under the action of irradiation of UV or visible light. Two techniques are known: one in which new layers are formed on the upper surface of the growing object; the other where new layers are formed on the lower surface of the growing object.
If new layers are formed on the upper surface of the growing object, then after each irradiation step the object under construction is lowered into the resin pool, a new layer of resin is coated on top, and carried out a new step in irradiation. An early example of such a technique is given in Hull, US Patent No. 5,236,637, in Figure 3. A drawback of such top-down techniques is the need to immerse the growing object in a (potentially deep) pool of liquid resin and reconstitute a precise coating of liquid resin.
If new layers are formed at the bottom of the growing object, then after each irradiation step the object under construction must be separated from the lower plate in the fabrication pit. An early example of such a technique is given in Hull, US Patent
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IMPI fNSTFrUTO MUICANQ • t LA PROMÍDAD
INDUmUAL
U.S. No. 5,236,637, in Figure 4. While such bottom-up techniques retain the potential to eliminate the need for a deep well where the object is added to remove the object from a relatively shallow well or pool, a problem with such bottom-up fabrication techniques. as they are commercially implemented, extreme care must be taken, and the additional mechanical elements used, when the solidified layer is separated from the bottom plate due to physical and chemical interactions between them. For example, in US Patent No. 7,438,846, an elastic separation layer is used to achieve non-destructive separation of solidified material in the lower construction plane. Other approaches, such as the B9Creator ™ 3-dimensional printer available from B9Creations of Deadwood, South Dakota, USA, employ a sliding build plate. See, for example, M. Joyce, US Patent Sol. 2013/0292862 and Y. Chen et al., US Patent Sol. 2013/0295212 (both Nov. 7, 2013) ; see also Y. Pan et al., J. Manufacturing Sci. and Eng. 134, 051011-1 (Oct. 2012). Such approaches introduce a mechanical step that can complicate the apparatus, slow down the method, and / or potentially deform the final product.
Continuous processes to produce a three-dimensional object are suggested at some length over top-down techniques in US Patent No. 7,892,474, but this reference does not explain how they can be implemented in bottom-up systems. above in a non-destructive way to the article being produced. Accordingly, there is a need for alternate methods and apparatus for three-dimensional fabrication that can obviate the need for mechanical separation steps in bottom-up fabrication.
BRIEF DESCRIPTION OF THE INVENTION
Described herein are methods, systems, and apparatus (including related control methods, systems, and apparatus) for the generally continuous production of a three-dimensional object. In these methods, systems, and apparatus, the three-dimensional object is produced from a liquid interface. Therefore, they are sometimes referred to, for convenience and not for the purpose of limitation, as continuous liquid interface printing. A schematic representation is given in Figure 1 herein.
As discussed below, the interface is between the first and second layers or zones of the same polymerizable liquid. The first layer or zone (sometimes also referred to as a dead zone) contains a polymerization inhibitor (at least in a polymerization inhibiting amount); in the second layer or zone the inhibitor has been consumed (or otherwise not incorporated or penetrated therein) to the point where polymerization is no longer substantially inhibited. The first and second zones do not form a strict interface between the IMPI
MEXICAN INSTITUTE --- a
OF THE PROFIEDa · <sub>(</sub> INDUSTRIAL same but preferably there is a gradient of the composition that can also be described as forming an interface between them as opposed to a sharp-to-measure interface that the phases are miscible with each other, and also create a polymerization gradient (partial or totally overlapped) between them (and also between the three-dimensional object being manufactured and the construction surface through which the polymerizable liquid is irradiated). The three-dimensional object can be manufactured, grown, or produced continuously from that polymerization gradient (rather than being manufactured layer by layer). As a result, the creation of fault or split lines in the object is produced, which can occur in layer-by-layer techniques as described in Y. Pan et al. or 1 Joyce et al. (noted above), can be reduced or avoided. Of course, such fault or split lines can be intentionally introduced when desired as further discussed below.
In some embodiments of continuous liquid interface printing, the first layer or zone is provided immediately on top of, or in contact with, a build plate. The build plate is transparent to irradiation that initiates polymerization (eg structured radiation), but the build plate is preferably semipermeable to the polymerization inhibitor and allows the polymerization inhibitor (eg oxygen) to pass partially or completely through it (for example, to continuously feed inhibitor to the dead zone). The build plate is preferably fixed or stationary in the sense that it does not need to slide, retract, reset or the like to create separate or sequential steps (as in a layer-by-layer process). Of course, the minor build plate movement in the x and / or y directions that does not unduly interrupt the polymerization gradient, but still allows for continuous polymerization of the liquid interface, can still be accommodated in some embodiments, as also discussed below.
Thus the present invention provides a method of forming a three-dimensional object, comprising: providing a carrier and an optically transparent member having a building surface, said carrier and said building surface define a building region therebetween; filling said building region with a polymerizable liquid, irradiating said building region through said optically transparent member to form a solid polymer of said polymerizable liquid while simultaneously advancing said carrier away from said building surface to form said three-dimensional target of said solid polymer, while also at the same time (i) continuously maintaining a polymerizable liquid dead zone in contact with said building surface, and (i) continuously maintaining a polymerization zone gradient between said dead zone and said solid polymer and in contact with each of the same, said gradient of the <sup>4</sup> ΙΜΡΙ ^^ institutomcxcan ·
DE LA MOREDA · r¿3 | ^ C polymerization zone comprises said polymerizable liquid in a parttfeMwrrte c & SaEJgWr form, for example, so that the formation of fault lines or division lines between the solid polymer layers in said three-dimensional object is reduced). In some embodiments, the optically transparent member comprises a semi-permeable member, and said continuous maintenance of a dead zone is accomplished by feeding a polymerization inhibitor through said optically transparent member, thereby creating an inhibitor gradient in said dead zone and optionally in at least a portion of said polymerization zone gradient; In other embodiments, the optically transparent member comprises a semi-permeable member, and is configured to contain a sufficient amount (or pool) of inhibitor to continuously maintain the dead zone for a sufficient period of time, to produce the article being manufactured without additional feeding. of inhibitor during the process (whose pool can be refilled or can be recharged between production runs). In some embodiments, the optically transparent member is formed from a semipermeable fluoropolymer, a rigid gas permeable polymer, porous glass, or a combination thereof. In some embodiments, the irradiation step is carried out with a two-dimensional radiation pattern projected onto said building region, wherein said pattern varies with time while said simultaneous advance step continues for a time sufficient to form said three-dimensional object ( that is, during which time said gradient of the polymerization zone is maintained).
Although the dead zone and polymerization zone gradient do not have a strict boundary between them (in those locations where the two meet), the thickness of the polymerization zone gradient in some embodiments is at least as great as the thickness of the dead zone. Thus, in some modalities, the dead zone has a thickness of 0.01, 0.1,1, 2, or 10 microns up to 100, 200 or 400 microns or more, and / or said gradient of the polymerization zone and said dead zone seals are 1 or 2 microns thick to 400, 600, or 1000 microns, or more. In some embodiments, the polymerization zone gradient is maintained (while the polymerization steps continue) for a time of at least 5, 10, 15, 20 or 30 seconds, up to 5, 10, 15 or 20 minutes or more, or until the completion of the three-dimensional product.
The method may further comprise the step of interrupting said polymerization zone gradient for a time sufficient to form a dividing line on said three-dimensional object (e.g., at a predetermined desired location for intentional division, or at a location on said object in where the prevention of splitting or reduction of splitting is not critical) and then reinstalling said polymerization zone gradient (e.g. by stopping, and restarting, the forward step, increasing, then decreasing, the intensity of irradiation, and their combinations).
<img file="MX352425B_D0010.tif" />
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The method may further comprise heating said Limerizable Liquid ^^ which is delivered to the building region and / or within the building region (for example, by an amount as determined in the Examples below) to reduce the viscosity thereof in the building region (eg, by an amount as determined in Examples 5 below).
The method can be carried out and the apparatus implemented wherein said carrier has at least one channel formed therein, and said filling step is carried out by passing or forcing said polymerizable liquid into said building region through said at least one channel {for example, wherein said carrier has a plurality of liquid channels 10 formed therein and wherein different polymerizable liquids are forced through different of said plurality of channels; for example, further comprising simultaneously forming at least one, or a plurality of, separate external feed conduits of said object, each of said at least one feed conduit in fluid communication with a channel in said carrier, to supplying at least one, or a plurality of different polymerizable liquids 15 from said carrier to said construction zone). In some embodiments, the semipermeable member has a thickness of 0.1 or 1 millimeters to 10 or 100 millimeters; and / or said semi-permeable member has an oxygen permeability of at least 10 Barrers.
A particular aspect of the present invention is a method for forming a three-dimensional object, comprising the steps of:
(a) providing a carrier and a build plate, the build plate comprises a semipermeable member, the semipermeable member comprises a build surface with the build surface and the carrier defining a build region therebetween, and with said surface of construction in fluid communication via the semi-permeable member with a source of polymerization inhibitor;
(b) filling the building region with a polymerizable liquid, the polymerizable liquid making contact with said building surface;
(c) irradiating the building region through the building plate to produce a solid polymerized region in the building region, while forming or maintaining a liquid film release layer composed of the polymerizable liquid formed between the solid polymerized region and the building surface, the polymerization of said liquid film is inhibited by said polymerization inhibitor; and (d) advancing the carrier with the polymerized region adhered thereto away from the building surface on the build plate to create a subsequent building region between the polymerized region and the building surface;
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IMPI <sup>M</sup> the 'industrial setting (e) where the carrier has at least one channel formed in it, and the filling step is carried out by passing or forcing the polymerizable liquid into the region of' construcólóll 3<sup>1</sup> through the at least one channel.
In some embodiments of the foregoing, the carrier has a plurality of channels formed therein, and wherein different polymerizable liquids are forced through different channels of the plurality of channels.
In some embodiments of the foregoing, the method further comprises concurrently forming at least one, or a plurality of, separate external feed conduits from the object, each of the at least one feed conduit in fluid communication with a channel in the carrier. , to supply at least one, or a plurality of different, polymerizable liquids from the carrier to the construction zone.
In some embodiments, the method may further comprise: (e) continuing and / or repeating steps (b) through (e) to produce a subsequent polymerized region adhered to a previous polymerized region until continuous or repeated deposition of the polymerized regions adhered to each other form the three-dimensional object.
In some embodiments, steps (b) to (e) are carried out concurrently.
In some embodiments, the build plate is substantially fixed or stationary.
In some embodiments the source of the polymerization inhibitor is a polymerization inhibitor reservoir within the semipermeable member.
In some embodiments, the semipermeable member further comprises a feed surface separate from the building surface.
In some embodiments the feed surface is in fluid contact with a polymerization inhibitor to provide the source of the polymerization inhibitor.
In some embodiments the method further comprises heating the polymerizable liquid to reduce the viscosity thereof in the region of construction.
In some embodiments, the method further comprises cooling the polymerizable liquid in the building region to dissipate the heat generated by the polymerization reactions.
In some embodiments the advancement step or steps are carried out at a cumulative speed of at least 0.1,1,10,100 or 1000 microns per second.
In some embodiments the excess polymerizable liquid is supplied to the building region, removed or drained therefrom to cool the building region, and then optionally recirculated back to the building region.
In some embodiments, the forward step is carried out by advancing the wearer
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MEXICAN INSTITUTE. M THE PROPERTY vertically from the building surface. indwhual
In some embodiments the semipermeable member comprises an upper surface portion, a lower surface portion, and an edge surface portion; the building surface is in the upper surface portion; and the feed surface is on at least one of the upper surface portion, the lower surface portion, and the edge surface portion.
In some embodiments, the semipermeable member has a thickness of 0.1 to 1 millimeter to 10 or 100 millimeters; and / or the semipermeable member has an oxygen permeability of at least 7.5 x 10 '^ m ^ Pa'<sup>1</sup> (10 Barrers); and / or the semipermeable member is formed from a semipermeable fluoropolymer, a rigid gas permeable polymer, porous glass, or a combination thereof.
In some embodiments, the irradiation step is carried out with actinic radiation.
In some embodiments the wearer has a soluble sacrificial layer thereon, and the three-dimensional object is formed in the soluble sacrificial layer.
In some embodiments, the total surface area of the building region occupies at least seventy percent of the total surface area of the building surface; and / or the lateral movement of the carrier and object in any direction is not more than thirty percent of the width of the construction region in the corresponding direction.
In some embodiments, the polymerizable liquid comprises a free radical polymerizable liquid and the inhibitor comprises oxygen.
In some embodiments, the polymerizable liquid comprises an acid-catalyzed or cationically polymerizable liquid and the inhibitor comprises a base.
In some embodiments the polymerizable liquid further comprises an active agent, a detectable agent, solid particles, or a combination thereof.
In some embodiments, the three-dimensional object comprises a medical device, rod, or fiber.
In some embodiments, the irradiation step is carried out by means of unmasked photolithography.
In some embodiments, the method further comprises the steps of: monitoring or detecting at least one procedure parameter and / or providing at least one known or predetermined procedure parameter; and then altering at least one procedure condition in response to the monitored procedure parameter or known procedure parameter.
In some embodiments the carrier with the polymerized region adhered thereto is advanced unidirectionally away from the building surface on the build plate. <sup>8</sup> IMPI
INSTITUTO MEXICANO Λ stationary.
A further particular aspect of the invention is an apparatus for forming a three-dimensional object from a polymerizable liquid, comprising: (a) a support; (b) lili pUfLJUUr operatively associated with the support on which the three-dimensional object is formed; (c) at least one channel formed in the carrier; (d) a build plate connected to the bracket, the build plate comprises a semipermeable member, the semipermeable member comprises a build surface, with the build surface and the carrier defining a build region between them; (e) a liquid polymer supply operatively associated with the building plate and configured to supply the liquid polymer through the at least one channel in the building region for solidification / polymerization; (f) a radiation source and configured to irradiate the building region through the build plate and form a solid polymerized region therein of the liquid polymer; and (g) the building surface is in fluid communication via the semipermeable member with a source of polymerization inhibitor to promote formation or maintenance of a liquid film release layer comprising the polymerized liquid formed between the solid polymerized region and the building surface, the polymerization of which the liquid film is inhibited by means of the polymerization inhibitor.
In some embodiments of the foregoing, the carrier has a plurality of channels formed therein, configured to supply different polymerizable liquids through different channels of the plurality of channels.
In some embodiments, the apparatus further comprises at least one, or a plurality of, external supply conduits for the object (e.ff., which can be constructed in the course of manufacturing the object), each of the at least one conduit feed in fluid communication with a channel in the carrier, configured to supply the at least one, or a plurality of different, polymerizable liquids from the carrier to the construction zone.
In some embodiments of the foregoing, the build plate is substantially fixed or stationary.
In some embodiments of the foregoing, the source of the polymerization inhibitor is a reservoir of polymerization inhibitor within the semipermeable member.
In some embodiments of the foregoing, the semipermeable member further comprises a feed surface separate from the building surface.
In some embodiments of the foregoing, the feed surface is in fluid contact with a polymerization inhibitor to provide the source of polymerization inhibitor.
In some embodiments of the foregoing, the apparatus further comprises a controller operatively associated with the carrier and the light source to advance the <sub>9</sub> IMPI ^^ tNrrrruro Mexican Λ
HEARD THE CARRIER Away from the build plate during or after liquid polymerization in the build region. . .<sub>4</sub>
In some embodiments of the foregoing, the apparatus further comprises a heater operatively related to the build plate and / or the liquid polymer supply, the heater is configured to heat the polymerizable liquid supplied to the build region.
In some embodiments of the foregoing, the apparatus further comprises a cooler operatively associated with the build plate configured to cool the polymerizable liquid supplied to the build region.
In some embodiments of the foregoing, the semipermeable member comprises an upper surface portion, a lower surface portion, and an edge surface portion; the building surface is in the upper surface portion; and the feed surface is on at least one of the upper surface portion, the lower surface portion, and the edge surface portion.
Some embodiments of the foregoing additionally comprise a pressure source operatively associated with the liquid polymer supply.
In some embodiments of the foregoing, the radiation source comprises a light source.
Some embodiments of the foregoing further comprise a spatial light modulation array operatively associated with the radiation source and controller and configured to carry out irradiation of the polymerizable liquid by maskless photolithography.
In some embodiments of the foregoing, the carrier comprises a plate, post, net, film, reel, or combination thereof operatively associated with at least one actuator.
In some embodiments of the foregoing, the carrier comprises a pusher, pusher, and controller configured to advance the carrier unidirectionally away from the building surface.
In some embodiments of the foregoing, the carrier has a soluble sacrificial layer thereon, and the three-dimensional object is formed in the soluble sacrificial layer.
In the 3-dimensional B9Creator ™ printer, a polydimethylsiloxane (PDMS) coating is applied to the slip build surface. The PDMS coating is said to absorb oxygen and create a lubricating thin film of non-polymerized resin through its action as a polymerization inhibitor. However, the PDMS-coated building surface is directly filled with oxygen by mechanically moving (sliding) the surface from underneath the growing object, while cleaning the non-polymerized resin from it with
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Although in some embodiments the ancillary means to provide an inhibitor such as oxygen (eg a compressor for related channels) is provided, the process still employs a layer-by-layer approach with gliding and cleaning the surface. Since the PDMS coating can be swollen by the resin, this bulging, along with these mechanical steps, can result in tearing or damage to the PDMS coating.
Non-limiting examples and specific embodiments of the present invention are explained in more detail in the drawings herein and in the specification set forth below. The description of all US patent references cited herein should be incorporated herein by reference in their entirety.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic illustration of one embodiment of a method of the present invention.
Figure 2 is a perspective view of one embodiment of an apparatus of the present invention.
Figures 3A, 3B provide side sectional views of alternate embodiments of rigid build plates for use in the present invention.
Figure 4 illustrates various alternate carriers for use in the present invention.
Figures 5A through 51 illustrate a polymerization inhibitor on a rigid build plate that helps establish an unpolymerized film on the build surface thereof.
Figures 6A through 6F illustrate the migration of an inhibitor (in this case oxygen) through a build plate from a feed surface at the back of the plate to a build surface at the front of a plate to assist to establish an uncured film on the construction surface.
Figure 7 schematically illustrates an increasing three-dimensional object advancing away from a building surface, and the space that must be filled between them before subsequent polymerization is carried out.
Figure 8 schematically illustrates an embodiment of the invention that contemplates the application of pressure to accelerate filling of the space shown in Figure 8.
Figure 9 illustrates a rod or fiber that can be produced by the methods and apparatus of the present invention.
Figure 10 is a photograph of a series of microneedles made with the η
MEXICAN INSTITUTE
DE LA MOHEDA »methods and apparatus of the present invention. The diameter of the carrier in the cftf ^ B'series StSaHEBene is approximately the same as a United States quarter (or quarter). Essentially the same carrier is used in the additional examples illustrated below.
Figure 11 is a photograph of a second series of microneedles made with the methods and apparatus of the present invention.
Figure 12 is a photograph of a ring structure that is manufactured with the methods and apparatus of the present invention. Note the extensive projection during manufacturing.
Figure 13 is a photograph of the completed ring of Figure 12.
Figure 14 is a photograph of four chess piece structures made with the methods and apparatus of the present invention.
Figure 15 is a photograph of a rectangular prism structure fabricated with the methods and apparatus of the present invention.
Figure 16 is a photograph of a spiral structure manufactured with the methods and apparatus of the present invention. Note the extensive projection during fabrication through the completed structure.
Figure 17 illustrates the effects of dye and photoinitiator on cure time.
Figure 18 is a photograph of a chess piece similar to those shown in Figure 14 above, but made with a resin dyed by the methods of the present invention.
Figure 19 schematically illustrates the fabrication of a plurality of items on the carrier, the carrier having a release layer on it.
Figure 20 schematically illustrates the release of a plurality of articles from the carrier with a release layer.
Figure 21 is a photograph of a series of prisms manufactured by the methods and apparatus of the present invention, in a release layer.
Figure 22 is a photograph of the prisms shown in Figure 21 after release.
Figure 23 is a photograph of a cylindrical confined structure produced by the methods and apparatus of the present invention.
Figure 24 is a photograph of a series similar to that of Figure 21, and produced by essentially the same methods, only comprising a polyethylene glycol polymer.
Figure 25 is a photograph of a cylindrical basket structure similar to that of Figure 23 and produced by substantially the same methods, only comprising a polyethylene glycol polymer. The part was noted for being flexible.
Figure 26 schematically illustrates one embodiment of an apparatus of the present or IMPI ^^
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W The PROPERTY νΜΜ | ΚΜΓ invention wherein one or more heaters are included to reduce I ^ W¿8¿idaa ^ ert ^ polymerizable fluid. . .<sub>t</sub> _____________ _ .....
Figure 27 schematically illustrates an embodiment of an apparatus of the present invention wherein the building region is filled with a polymerizable liquid fed through the carrier.
Figure 28 schematically illustrates an embodiment of the invention in which the outer conduits are formed to facilitate the feeding of one or multiple polymerizable liquids from the carrier to the region of construction.
Figures 29 through 31 are flow charts illustrating control systems and methods for carrying out the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is now described in more detail hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. This invention, however, can be represented in many different ways and should not be construed as limited to the embodiments set forth herein; instead, these embodiments are provided so that this description will be detailed and complete, and will fully convey the scope of the invention to those skilled in the art.
Like numbers refer to the same items throughout the description. In figures, the thickness of certain lines, layers, components, elements, or features may be exaggerated for clarity. Where used, broken lines illustrate optional features or operations unless otherwise specified.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular forms a / an, and the / la are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises or comprising when used in this specification, specify the presence of the characteristics, integers, steps, operations, component elements and / or established groups or combinations thereof, but do not exclude the presence or addition of one or more other characteristics, integers, steps, operations, elements, components, and / or groups or combinations thereof.
As used herein, the term and / or includes any and all possible combinations or one or more of the related listed items, as well as the lack of combinations when interpreted in the alternative (or).
INSTITUTO MEXICANO □ ϊ THE PROPERTY
Unless defined otherwise, all terms (including technical and scientific terms) used herein are commonly referred to as one of ordinary skill in the art to which this invention belongs. It will further be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and claims and should not be interpreted in an idealized or overly formal sense. unless expressly defined in this document. Well known designs or constructions may not be described in detail for brevity and / or clarity.
It will be understood that when an element refers to being turned on, fixed to, connected to, coupled with, making contact with etc., another element may be directly turned on to, connected to, coupled with and / or making contact with the other. element or elements involved may also be present. On the contrary, when an element is referred to as being, for example, directly in, directly attached to, directly connected to, directly coupled to or directly contacting another element, no intervening elements are present. It will also be appreciated by those skilled in the art that references to a structure or feature that is positioned adjacent to another feature may have portions that overlap or underlie the adjacent feature.
Spatially relative terms, such as under, under, under, over, over, and the like, may be used herein to facilitate description to describe a relationship of one item or feature to another item (s) or feature (s). , as illustrated in the drawings. It will be understood that the terms spatially relative are intended to encompass different orientations of the device in use or operation in addition to the orientation illustrated in the figures. For example, if the device is inverted in the figures, the elements described as below or below other elements or features can then be oriented over the other elements or features. Thus, the exemplary term below can encompass both an over and under orientation. The device can be oriented in another way (rotated 90 degrees or in other orientations) and the spatially relative descriptors used herein interpreted accordingly. Likewise, the terms up, down, vertical, horizontal, and the like are used herein for the purpose of explanation only, unless specifically indicated otherwise.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, components, regions, layers and / or sections, these elements, components, regions, layers and / or sections should not be limited by these terms. Rather, these terms are only used to distinguish one element, component, region, layer, and / or section from another element, component, region, layer, and / or section. Thus, a first element,<sub>14</sub> * · “INSTITUTO MEXICANO • t THE INDUSTRIAL FACTORY component, region, layer or section that is discussed in the present, could be called a second element, component, region, layer or section without departing from the I3V eilbefidiizuj of the present invention. The sequence of operations (or steps) is not limited to the order presented in the claims or figures unless specifically indicated otherwise.
1, Dolimerlzable Liquids
Any suitable polymerizable liquid can be used to enable the present invention. The liquid (sometimes also referred to as an ink liquid resin, or simply resin herein) may include a monomer, particularly photopolymerizable and / or free radical polymerizable monomers, and a suitable initiator such as a free radical initiator and combinations of the same. Examples include, but are not limited to, acrylics, methacrylics, acrylamides, styrenics, olefins, halogenated olefins, cyclic alkenes, maleic anhydride, alkenes, alkynes, carbon monoxide, functionalized oligomers, multifunctional good site monomers, functionalized PEGS, etc. ., including its 15 combinations. Examples of liquid resins, monomers, and initiators include but are not limited to those set forth in US Patent Nos. 8,232,043; 8,119,214; 7,935,476; 7,767,728; 7,649,029; WO 2012129968 Al; CN 102715751 A; JP 2012210408 A.
Acid-catalyzed polymerizable liquids
Although in some embodiments as shown above the polymerizable liquid comprises a free radical polymerizable liquid (in which case an inhibitor may be oxygen as described below), in other embodiments the polymerizable liquid comprises an acid catalyzed or cationically polymerized polymerizable liquid. In such embodiments, the polymerizable liquid comprises monomers containing groups suitable for acid catalysis, such as epoxide groups, vinyl ether groups, etc. Suitable monomers include olefins such as methoxyethene, 4-methoxystyrene, styrene, 2-methylprop-l-ene, 1,3-butadiene, etc .; Heterocyclic monomers (including lactones, lactams, and cyclic amines) such as oxirane, thiethane, tetrahydrofuran, oxazoline, 1,3, dioxepane, oxetan-2-one, etc., and combinations thereof. A suitable photo acid generator (PAG) (usually ionic or non-ionic) is included in the acid-catalyzed polymerizable liquid, examples of which include, but are not limited to, onium salts, sulfonium and iodonium salts, etc., such as diphenyl iodide hexafluorophosphate, diphenyl iodide hexafluoroarsenate, diphenyl iodide hexafluoroantimonate, diphenyl p-methoxyphenyl triflate, diphenyl p-toluenyl trilfate, diphenyl p-isobutylphenyl triflate, diphenyl p-tert-butylphenyl triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, etc., including mixtures of dibutylnaphthylsulfonium, etc.
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INDUSTRIAL the same. See, for example, US Patent Nos. 7,824,839; 7,550,246; 7,534,844; 6,692,891; 5,374,500; and 5,017,461; see also Photoacid Generator Seiection Guide for the etectronics industry and energy curable coatings (BASF 2010).
Hydrogels
In some embodiments suitable resins include photocurable hydrogels such as poly (ethylene glycols) (PEG) and gelatins. PEG hydrogels have been used to deliver a variety of biological products, including Growth factors; however, a major challenge faced by PEG hydrogels crosslinked by chain growth polymerizations is the potential for irreversible protein damage. Conditions to maximize release of photopolymerized PEG diacrylate hydrogel biologics can be enhanced by including affinity-binding peptide sequences in monomer resin solutions, prior to photopolymerization allowing sustained delivery. . Gelatin is a biopolymer frequently used in the food, cosmetic, pharmaceutical and photographic industries. It is obtained by thermal denaturation or chemical or physical degradation of collagen. There are three types of gelatin, including those found in animals, fish, and humans. Gelatin from cold water fish skin is considered safe for use in pharmaceutical applications. Visible or UV light can be used to entangle appropriately modified gelatin. Methods for interlocking gelatin include curative derivatives of dyes such as Rose Bengal.
Light Curable Silicone Resins
A suitable resin includes photocurable silicones. UV curing silicone rubber, such as Siltopren ™ UV Curing Silicone Rubber can be used as LOCTTTE ™ Curing Silicone adhesive sealants. Applications include optical instruments, medical and surgical equipment, outdoor lighting and fencing, electrical connectors / sensors, fiber optics, and gaskets.
Biodegradable resins
Biodegradable resins are particularly important for implantable drug delivery devices or temporary performance applications, such as biodegradable screws or stents (US Patents 7,919,162; 6,932,930). Biodegradable lactic acid and glycolic acid (PLGA) copolymers can be dissolved in PEG dimethacrylate to produce a clear resin suitable for use. Polycaprolactone and PLGA oligomers can be functionalized with acrylic or methacrylic groups to allow them to be effective resins.
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to be used.
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INSTITUTO MEXICANO DE LA PROCEDA »industrial
Photocurable polyurethanes
A particularly useful resin is photocurable polyurethane. A photopolymerizable polyurethane composition comprises (1) aliphatic diisocyanate based polyurethane, poly (hexamethylene isophthalate glycol) and optionally 1,4-butanediol; (2) a polyfunctional acrylic ester; (3) a photoinitiator; and (4) an anti-oxidant, can be formulated to provide a tough, abrasion resistant, and stain resistant material (US Patent 4,337,130). The photocurable thermoplastic polyurethane elastomers incorporate photoreactive diacetylene diols as chain extenders.
High performance resins
In some embodiments, high performance resins are used. Such high performance resins may sometimes require the use of heating to melt and / or reduce the viscosity thereof, as noted above and further discussed below. Examples of such resins include, but are not limited to, resins for those materials sometimes referred to as liquid crystalline polymers of ester, ester-imide, and ester-amide oligomers, as described in US Pat. Nos. 7,507,784; 6,939,940. Since such resins are sometimes employed as high temperature thermosetting resins, in the present invention they further comprise a suitable photoinitiator such as benzophenone, anthraquinone, and fluoroenone initiators (including derivatives thereof), to initiate irradiation crosslinking, such as was further discussed below.
Additional exemplary resins
Particularly useful resins for dental applications include EnvisionTEC's Clear Guide, EnvisionTEC's E-Denstone Material. Particularly useful resins for the hearing aid industries include EnvisionTEC's e-Shell 300 Series resin. Particularly useful resins include EnvisionTEC's HTM140IV High Temperature Molding Material for use directly with vulcanized rubber in molding / casting applications. A particularly useful material for making hard and rigid parts includes EnvisionTEC's RC31 resin. A particularly useful resin for precision casting applications includes EnvisionTEC's Easy Cast EC500.
Additional resin ingredients
Liquid resin or polymerizable material can have solid particles <sup>17</sup> IMPI Mexican institute,, DE j TO RXOPUHTAD suspended or dispersed in it. Any solid particle will be suitable, depending on the final product to be manufactured. The particles can be metallic, organic / polymeric, inorganic, or mixed materials or mixtures thereof. The particles can be non-conductive, semi-conductive, or conductive (including metallic and non-metallic or polymeric conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or non-magnetic. The particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc. The particles may comprise an active agent or detectable compound as described below, although these may also be provided dissolved or solubilized in the liquid resin as also discussed below. For example, magnetic or paramagnetic particles or nanoparticles can be used.
The liquid resin may have additional ingredients solubilized therein, including pigments , dyes, active compounds or pharmaceuticals, detectable compounds (eg fluorescent, phosphorescent, radioactive), etc., again depending on the particular purpose of the product being used. factory. Examples of such additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
Polymerization inhibitors
Polymerization inhibitors or inhibitors for use in the present invention may be in the form of a liquid or a gas. In some embodiments, gas inhibitors are preferred. The specific inhibitor will depend on the monomer to be polymerized and the polymerization reaction. For free radical polymerization monomers, the inhibitor may suitably be oxygen, which may be provided in the form of a gas such as air, an oxygen-enriched gas (optionally but in some embodiments preferably containing additional inert gases to reduce the combustibility of the themselves), or in some embodiments pure oxygen gas. In alternate embodiments, such as where the monomer is polymerized by the photoacid generator initiator, the inhibitor can be a base such as ammonia, trace amines {for example methyl amine, ethyl amine, di and trialkyl amines such as dimethyl amine, diethyl amine, trimethyl amine, triethyl amine, etc.), or carbon dioxide, including mixtures or combinations thereof.
Polymerizable liquids that carry living cells
In some embodiments, the polymerizable liquid can carry living cells as particles therein. Said polymerizable liquids are generally aqueous, and can be oxygenated, and can be considered as emulsions where living cells are the phase.<sup>18</sup>
INSTITVTt) MEXICAN different. Suitable living cells can be dicotyledonous plant cells), animal cells (eg, mammalian, avian, amphibian, reptile cells), microbial cells (eg, prokaryote, eukaryotic, protozoan, etc.), etc. The cells can be cells differentiated from or corresponding to any type of tissue (for example, blood, cartilage, bone, muscle, endocrine gland, exocrine gland, epithelial, endothelial, etc.), or they can be non-cells. differentiated such as stem cells or progenitor cells. In such embodiments the polymerizable liquid can be one that forms a hydrogel, including but not limited to those described in US Pat. Nos. 7,651,683; 7,651,682; 7,556,490; 6,602,975; 5,836,313; etc.
2. Apparatus
A non-limiting embodiment of an apparatus of the invention is shown in Figure 2. It comprises a radiation source 11 such as a digital light processor (DLP) that provides electromagnetic radiation 12 that although the reflective mirror 13 illuminates a chamber of defined construction by wall 14 and a rigid build plate 15 forms the bottom of the build chamber, which build chamber is filled with liquid resin 16. The bottom of chamber 15 is constructed of rigid build plate comprising a rigid semipermeable member as further discussed below. The upper part of the object under construction 17 is fixed to a carrier 18. The carrier is driven in the vertical direction by a linear stage 19, although alternate structures can be used as discussed below.
A liquid resin reservoir, piping, sensors and / or liquid level valves from the pumps can be included to re-supply the liquid resin pool in the build chamber (not shown for clarity) although in some embodiments it may be use a simple gravity feed. The thrusters / actuators for the carrier or linear stage, along with related wiring, can be included according to known techniques (again not shown for clarity). The thrusters / actuators, radiation source, and in some embodiments the pumps and liquid level sensors can be operatively related to a suitable controller, again in accordance with known techniques.
Building plates 15 that are used to carry out the present invention generally comprise or consist of a semi-permeable (or gas-permeable) (typically rigid or solid, stationary, and / or fixed) member, alone or in combination with one or more additional support substrates (eg, clamps and tensioning members to rigidify an otherwise flexible semipermeable material). The rigid semi-permeable member can be made of any suitable material that is optically transparent to the relevant wavelengths (or otherwise transparent to the radiation source, whether or not it is visually transparent as shown).
MSKICAN INSTITUTE
PE LA MOHEDA »is perceived by the human eye — that is, an optically transparent window may in some modalities be visually opaque), including but not limited to pornsn and mirrnpnmc glass and the rigid gas-permeable polymers used to manufacture contact lenses. rigid gas permeable. See, for example, Norman G. Gaylord, US Patent No. RE31,406; see also US Patents. Nos. 7,862,176; 7,344,731; 7,097,302; 5,349,394; 5,310,571; 5,162,469; 5,141,665; 5,070,170; 4,923,906; and 4,845,089. In some embodiments such materials are characterized as vitreous and / or amorphous and / or substantially entangled polymers that are essentially non-swellable. Preferably the rigid semipermeable member is formed of a material that does not swell when contacted with the liquid resin or material to be polymerized (ie, it is non-swellable). Suitable materials for the rigid semipermeable member include rigid amorphous fluoropolymers, such as those described in US Patent Nos. 5,308,685 and 5,051,115. For example, such fluoropolymers are particularly useful over silicones that would potentially swell when used in conjunction with organic liquid resin inks to be polymerized. For some liquid resin inks, such as more water-based monomeric systems and / or some polymeric resin ink systems that have low swelling tendencies, silicone-based window materials may be suitable. The solubility or permeability of organic liquid queen inks can be dramatically decreased by a number of known parameters including increasing the crosslinking density of the window material or increasing the molecular pitch of the liquid resin ink. In some embodiments the build plate can be formed of a film or thin sheet of material that is flexible when detached from the apparatus of the invention, but is clamped and taut when installed in the apparatus (for example, with a clamping ring) to make it rigid in the appliance. Particular materials include TEFLON AF® fluoropolymers, commercially available from DuPont. Additional materials include perfluoropolyether polymers such as those described in US Patent Nos. 8,268,446; 8,263,129; 8,158,728; and 7,435,495.
It will be appreciated that essentially all solid materials, and most of those described above, have some inherent flex even though they are not considered rigid, depending on factors such as shape and thickness and environmental factors such as pressure and the temperature to which they are subjected. Furthermore, the terms stationary or fixed with respect to the build plate is intended to mean that no mechanical interruption of the process occurs or that no mechanism or structure for mechanical interruption of the process (as in a layer-by-layer method or apparatus) is provided, even if a mechanism for build plate increment adjustment (for example, adjustment that does not lead to or causes collapse of the gradient of a polymerization zone) is provided).
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The semi-permeable member by or generates comprises a<sup>, N</sup>upper poñ! i®n, a lower surface portion, and an edge surface portion. The building surface is in the upper surface portion; and the feed surface may be one, two, or all three of the upper surface portion, the lower surface portion, and / or the edge surface portion. In the embodiment illustrated in Figure 2, the feed surface is on the lower surface portion, but alternate configurations where the feed surface is provided at one edge, and / or on the upper surface portion (near from but not separate or remote from the building surface) can be implemented with routine experience.
The semi-permeable member has, in some embodiments, a thickness of 0.01, 0.1 or 1 millimeters to 10 or 100 millimeters, or more (depending on the size of the article being manufactured, whether or not it is laminated or whether it is in contact with a plate of additional support such as glass, etc., as further discussed below.
The permeability of the semipermeable member to the polymerization inhibitor will depend on conditions such as the pressure of the atmosphere and / or the inhibitor, the choice of inhibitor, the rate or speed of manufacture, etc. In general, when the inhibitor is oxygen, the permeability of the semi-permeable member to oxygen can be 10 or 20 Barrers, up to 1000 or 2000 Barrers, or more. For example, a semi-permeable member with a permeability of 10 Barrers used with pure oxygen, or with highly enriched oxygen, the atmosphere under a pressure of 1034213.5935 Pa can perform substantially the same as a semi-permeable member with a permeability of 500 Barrers when oxygen is supplied from ambient atmosphere under atmospheric conditions.
Thus, the semi-permeable member may comprise a flexible polymer film (having any suitable thickness, for example 0.001,0.01, 0.1 or 1 millimeters to 5, 10, or 100 millimeters, or more), and the build plate it may further comprise a tension member (eg, a peripheral clamp and an operably related tension member or stretching member, as in a drum head; a plurality of peripheral clamps, etc., including combinations thereof) connected to the polymer film and to fix and rigidify the film (e.g., at least enough so that the film does not adhere to the object as it the object is advanced and resiliently or elastically recovering from there). The film has an upper surface and a lower surface, with the build surface on the upper surface and the feed surface preferably on the lower surface. In other embodiments, the semipermeable member comprises: (i) a polymeric film layer (having any suitable thickness, for example 0.001, 0.01, 0.1, or 1 millimeters to 5, 10, or 100 millimeters, or more), having a top surface placed to make
<img file="MX352425B_D0016.tif" />
<img file="MX352425B_D0017.tif" />
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MEXICAN INSTITUTE OF NOMEDAD
INDUSTRIAL X »contact with said polymerizable liquid and a bottom surface, and (i,) an optically transparent, gas-permeable support member (having any reinen, pgr Ha n.ni. oi o 1 millimeters at 10, 100, or 200 millimeters), making contact with said lower surface of the film layer. The support member has an upper surface that contacts the lower surface of the film layer, and the support member has a lower surface that can serve as the feed surface for the polymerization inhibitor. Any of the suitable materials that are semi-permeable (that are permeable to the polymerization inhibitor) can be used. For example, the polymer film or polymer film layer can, for example, be a fluoropolymer film, such as amorphous thermoplastic fluoropolymer such as TEFLON AF 1600 ™ or TEFLON AF 2400 ™ fluoropolymer films, or perfluoropolyether (PFPE), particularly interlaced PFPE film, or an interlaced silicone polymer film. The support member comprises a silicone or interlocking silicone polymer member such as a polydimethylxyloxane member, a rigid gas permeable polymer member, or a porous or microporous glass member. The films can be laminated or can be attached directly to the rigid support member without adhesive (for example, using PFPE and PDMS materials), or silane coupling agents that react with the top surface of a PDMS layer can be used to adhere to the first layer of polymer film. UV-curable, acrylate functional silicones can also be used as a tie layer between UV-curable PFPEs and rigid PDMS backing layers.
As noted above, although in some embodiments the semi-permeable member allows the inhibitor to pass through, it can simply be configured to contain a sufficient amount (or pool) of the inhibitor to continuously maintain the dead zone for a sufficient period of time, to produce the article to be manufactured without additional feeding of inhibitor during the process (whose pool can be refilled or can be recharged between production runs). The size and internal volume of the member can be configured as appropriate for the particular article to be manufactured to contain a sufficient pool of inhibitor.
When configured for placement in the apparatus, the wearer defines a building region on the building surface, within the total area of the building surface. Due to lateral launching (for example in the X and / or Y directions) it is not required in the present invention to break the adhesion between successive layers, as in the Joyce and Chen devices noted above, the area of the region Building surface within the building surface can be maximized (or conversely, the area of the building surface not focused on the building region can be minimized).
* IMPI
MEXICAN INSTITUTE
Hence, in some embodiments, the total surface area of the regioh<sup>L</sup>It will occupy at least fifty, seventy, seventy, eighty or ninety percent of the total surface area of the construction surface.
As shown in Figure 2, the various components are assembled in a support or frame assembly 5. Although the particular design of the support or frame assembly is not critical and can assume numerous configurations, in the illustrated embodiment it comprises a base 21 to which a radiation source 11 is secured or rigidly fixed, a vertical member 22 to which the linear stage is operatively related, and a horizontal table 23 to which the wall 14 is removably or securely fixed (or where the wall is placed), and with 10 the build plate rigidly fixed, either permanently or removably, to form the build chamber as described above.
As noted above, the build plate may consist of a single integral or unitary piece of a rigid semipermeable member, or it may comprise additional materials. For example, as shown in Figure 3A, a porous or microporous glass can be laminated or attached to a rigid semipermeable material. Or, as shown in Figure 3B, a semipermeable member as an upper portion may be attached to a transparent lower member having purge channels formed therein to feed gas carrying the polymerization inhibitor to the semipermeable member (through the which passes to the build surface to facilitate the formation of a non-polymerized liquid material release layer, as noted above and below). Such purge channels can extend completely or partially through the base plate: For example, the purge channels can extend partially into the base plate, but then end-to-end in the region directly underlying the build surface to avoid introduction of deformation. The specific geometries will depend on whether the feeding surface for the inhibitor in the semi-permeable member is located on the same or opposite side as the building surface, on an edge portion thereof, or a combination of several thereof. .
Any suitable radiation source (or combination of sources) can be used, depending on the particular resin employed, including electron beam and ionization radiation sources. In a preferred embodiment the radiation source is a source of actinic radiation, such as one or more light sources, and in particular one or more ultraviolet light sources. Any suitable light source can be used, such as incandescent lights, fluorescent lights, phosphorescent or luminescent lights, a laser, a light emitting diode, etc., including assemblies thereof. The light source preferably includes a patterning element operatively related to a controller, as noted above. In some embodiments, the light source or pattern-forming element comprises a
<img file="MX352425B_D0018.tif" />
<img file="MX352425B_D0019.tif" />
<sub>23</sub>
MEXICAN INSTITUTE
OS LA ntOHEIMD digital (or deformable) micromirror (DMD) with processing<sup>1</sup> of itb- ^ gfral (DLP), a spatial modulator (SLM, by ^ 'ñ-'iigliiir <sup>Qn</sup> ¡Ng ^ c) or a microelectromechanical system (MEMS) mirror array, a mask (also known as a graticule), a silhouette, or combinations thereof. See, US Patent No. 7,902,526. Preferably the light source comprises a spatial light modulation array such as a liquid crystal light valve array or DMD micromirror array (for example, with an operably related digital light processor, typically in turn under the control of a suitable controller), which is configured to carry out exposure or irradiation of the polymerizable liquid without a mask, for example, by photolithography without a mask. See, for example, US Patents. Nos. 6,312,134; 6,248,509; 6,238,852; and 5,691,541.
The alternate carriers and actuator / driver arrangements are shown in Figure 4. Numerous variations can be employed, including a pick-up spool, an XYZ pulse assembly (eg, as commonly used in an automated microscope stage), etc. In the embodiment illustrated in Figure 2, the drive assembly generally comprises a worm gear and motor, a frame and pinion and motor, a hydraulic, pneumatic or piezoelectric drive, or the like, adapted to move or advance the carrier away from building surface in vertical or Z direction only. In the alternate embodiment shown in Figure 4, a pickup spool or spool can be used, with related propellers or actuators and guides (not shown), particularly when the product being manufactured is an elongated beam or fiber (which is further discussed below). In an alternate embodiment, a pair of pickup reels with related guides, and with related propellers or actuators (not shown), can be mounted on the linear stage to provide movement in the X direction and / or the Y direction in addition to or in combination with, the movement in the Z direction provided by the linear stage 19. In still other embodiments, an XYZ pulse assembly such as that used in an automated microscope can be used in place of linear stage 19 to move or advance the carrier away from the build surface in the X, Y, and / or direction. or Z, for example, at an angle, or at changing angles, or combinations of directions in various stages. Thus advancement away from the build plate can be carried out only in the Z (or vertical) direction, or in at least the Z direction, by combining movement in the Z direction with movement in the X directions. I and. In some embodiments, there may be movement in the X and / or Y directions at the same time with the movement in the Z direction, with movement in the X and / or Y direction thus occurring during polymerization of the polymerizable liquid (ie say in contrast to the movement described in Y. Chen et al., or M. Joyce, supra, which is the movement between the previous and subsequent polymerization steps for the purpose of supplying new polymerizable liquid). In the<sup>24</sup> IMPI
INSTTTUT © MEXICANO JJ present invention such movement can be carried out by ^ profJÓÜ ^ J ^? coigT ¡mjjr burning or contamination in a particular area of the construction surface. .
Because an advantage of some embodiments of the present invention is that the size of the building surface on the semi-permeable member (i.e., the build plate or window) can be reduced due to the absence of a requirement for lateral launch. extensive as in the Joyce or Chen devices noted above, in the methods, systems and apparatus of the present invention the lateral movement (including movement in the X and / or Y direction or the combination thereof) of the wearer and object (if such lateral movement is present) is preferably not greater than, or less than, 80, 70, 60, 50, 40, 30, 20, or even 10 percent of the width (in the direction of lateral movement) of the building region.
Although in some embodiments the carrier is mounted on an elevator to advance up and away from a stationary build plate, in other embodiments the opposite arrangement can be used: That is, the carrier can be fixed and the build plate lowered to de this mode will advance the carrier away from there. Numerous different mechanical configurations will be apparent to those skilled in the art to achieve the same result, together of which the build plate is stationary in the sense that it does not require any lateral movement (X or Y) to fill the inhibitor in the itself, or no elastic build plate that must be stretched and then bounced (with related over-advancement and backing of, the carrier) needs to be employed.
Depending on the choice of material from which the carrier is made, and the choice of polymer or resin from which the article is made, the adhesion of the article to the carrier may sometimes be insufficient to retain the article in the carrier through termination. of the finished article or construction. For example, an aluminum carrier may have lower adhesion than a (polyvinyl) chloride (or PVC carrier). One solution, therefore, is to employ a carrier comprising a PVC on the surface to which the article being manufactured is polymerized. If this promotes high adhesion to conveniently separate the finished portion from the carrier, then any of a variety of techniques can be used to further secure the article to a less adhesive carrier, including but not limited to the application of an adhesive tape such as Greener Masking Tape for Basic Painting # 2025 High adhesion to further secure the item to the wearer during manufacture.
Soluble sacrificial layers
In some embodiments, a soluble sacrificial layer or release layer can be established between the carrier and the three-dimensional object, so that the sacrificial layer can subsequently be solubilized to conveniently release the three-dimensional object from the carrier an * IMPI
MSTrtUTO mexican · once manufacturing is complete. Any suitable sacrificial layer, such<sup>,</sup>^ mo * iun
<img file="MX352425B_D0020.tif" />
it can be coated or otherwise provided on the carrier can be used, and any suitable solvent (eg, polar and nonpolar organic solvents, aqueous solvents, etc. can be used). to solubilize the sacrificial release layer, although the sacrificial layer and its corresponding solvent must be chosen so that the particular material from which the three-dimensional object is formed is not unduly etched or solubilized by that solvent. The sacrificial layer can be applied to the carrier by any suitable technique, such as spraying, dip coating, painting, etc. Examples of suitable materials for the soluble sacrificial release layer (and non-limiting examples of the corresponding solvents) include but are not limited to: cyanoacrylate adhesive (acetone solvent); poly (vinylpyrrolidone) (water / or isopropyl alcohol solvent); lacquers (acetone solvent); polyvinyl alcohol, polyacrylic acid, poly (methacrylic acid), polyacrylamide, polyalkylene oxides such as polyethylene oxide, sugars and saccharides such as sucrose and dextran (all water and aqueous solvents); etc. Lower surface energy solvents are particularly preferred in some embodiments.
In some embodiments of the invention, the related actuator / driver and / or controller is configured to only advance the carrier away from the build plate (eg, it is unidirectional), as further discussed below.
In some embodiments of the invention, the related actuator / driver and / or controller is configured as a continuous thruster (as compared to a gradual thruster), as also discussed below.
3. Methods
As noted above, the present invention provides a method of forming a three-dimensional object, comprising the steps of: (a) providing a carrier and a build plate, said build plate comprises a semipermeable member, said semipermeable member comprises a build surface and a feed surface separate from said build surface, with said build surface and said carrier defining a building region therebetween, and with said feed surface in fluid contact with a polymerization inhibitor; then (simultaneously and / or sequentially) (b) filling said building region with a polymerizable liquid, said polymerizable liquid making contact with said building segment, (c) irradiating said building region through said building plate to produce a solid polymerized region in said building region, with a liquid film release layer comprised of said polymerizable liquid formed between the solid polymerized region and said building surface, the polymerization of which the liquid film is inhibited by said polymerization inhibitor; and (d)
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It is the property of advancing said carrier with said polymerized region adhered thereto away from the OCTtVsupew3lEconstruction on said stationary build plate to break up a subsequent construrion region between said polymerized region and said upper zone. In general the method includes (e) continuing and / or repeating steps (c) through (d) to produce a subsequent polymerized region adhered to a previous polymerized region until continuous or repeated deposition of the polymerized regions adhered to each other forms said three-dimensional object.
Since no mechanical release of a release layer is required, or no mechanical movement of a building surface is required to supply oxygen again, the method can be carried out in a continuous mode, although it will be appreciated that the steps The individual items noted above can be carried out sequentially, simultaneously, or a combination thereof. In fact, the speed of the steps can be varied over time depending on factors such as the density and / or the complexity of the region under manufacture.
Also, since mechanical release from a window or release layer generally requires the carrier to advance a greater distance from the build plate than is desired for the next irradiation step, which allows the window to be recoat, and then return from the carrier back closer to the build plate (for example, a two step forward one step back operation), The present invention in some embodiments allows the elimination of this backing step and allows the wearer to advance unidirectionally, or in only one direction, without intervention movement of the window to re-coat, or snap, a preformed elastic release layer.
In some embodiments, the forward step is performed sequentially in uniform increments (eg, 0.1 or 1 microns, up to 10 or 100 microns, or more) for each step or increment. In some embodiments, the advancement step is carried out sequentially in variable increments (eg, each increment ranging from 0.1 or 1 micron, up to 10 or 100 microns, or more) for each step or increment. The size of the increment, along with the speed of advance, will depend in part on factors such as temperature, pressure, structure of the article to be produced (e.g. size, density, complexity, configuration, etc.)
In other embodiments of the invention, the forward step is carried out continuously, at a uniform or variable speed.
In some modes, the rate of advance (whether carried out sequentially or continuously) is approximately 0.1 1, or 10 microns per second, up to approximately 100, 1,000, or 10,000 microns per second, again depending on factors such as temperature. , pressure, structure of the article to be produced, radiation intensity, etc.
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As further described below, in some embodiments the filling step is carried out by forcing said polymerizable liquid into said region of building the step or steps of advance can be carried out at a cumulative or average speed or speed of at least 0.1 , 1, 10, 50, 100, 500 or 1000 microns per second, or more. In general, the pressure can be whatever is sufficient to increase the speed of said step (s) of advance at least 2.4, 6, 8 or 10 times compared to the maximum speed of repetition of said steps advance in the absence of such pressure. Wherein the pressure is provided by enclosing an apparatus as described above in a pressure vessel and carrying out the process in a pressurized atmosphere (e.g. air, oxygen-enriched air, a mixture of gases, pure oxygen, etc. .) you can use a pressure of 68947.5729, 137895.1458,
206842.7187 or 275790.2916 Pa up to 1378951.4579, 2068427.187, 2757902.9159 or 3447378.6449 Pa or more. Higher pressures may be less preferred for manufacturing irregular objects compared to shorter manufacturing times due to the cost of a large high pressure vessel. In such an embodiment, both the feed surface and the polymerizable liquid can be in fluid contact with the same compressed gas (eg, one comprising 20 to 95 volume percent oxygen, the oxygen serving as the polymerization inhibitor.
On the other hand, when smaller items are manufactured, or a beam or fiber is manufactured which can be removed or removed from the pressure vessel as it is produced through a port or hole in it, then the size of the vessel Pressure can be kept smaller with respect to the size of the product being manufactured and higher pressures (if desired) can be used more easily.
As noted above, the irradiation step in some embodiments is carried out with standard irradiation. The patterned irradiation may be a fixed pattern or it may be a variable pattern created by a pattern generator (eg, a DLP) as discussed above, depending on the particular item to be manufactured.
When the patterned irradiation is a variable pattern rather than a pattern that remains constant over time, then each irradiation step can be any suitable time or duration depending on factors such as intensity of irradiation, the presence or absence of dyes in polymerizable material, growth rate, etc. Thus in some embodiments each irradiation step can be 0.001, 0.01, 0.1, 1, or 10 microseconds, up to 1, 10, or 100 minutes, or more, in duration. The interval between each irradiation step is in some embodiments preferably as short as possible, for example 0.001, 0.01, 0.1, or 1 microseconds to 0.1, 1, or 10 seconds.
In some modalities the construction surface is flat; in others the surface<sup>28</sup> , <sub>r</sub> t. μ. wmtsuo of construction is irregular such as curved in a convex or concave manner, or<sup>,</sup>'^ efí®'fJarecfe6JEz3WJas formed in it. In any case, the construction surface can be smooth or textured.
Curved and / or irregular build plates or build surfaces can be used in fiber or rod formation, to provide different materials for a single object being manufactured (i.e. different polymerizable liquids for the same build surface through of channels or trenches formed in the construction surface, each related to a separate liquid supply, etc.
Carrier feed channels for polymerizable liquid
Although the polymerizable liquid can be provided directly to the build plate from a liquid conduit and reservoir system, in some embodiments the carrier includes one or more feed channels therein. The carrier feed channels are in fluid communication with the supply of polymerizable liquid, for example a related reservoir and pump. Different carrier feed channels may be in fluid communication with the same supply and operate simultaneously with each other, or different carrier feed channels may be controlled separately from each other (for example, through the provision of a pump and / or valve for each). The separately controllable feed channels may be in fluid communication with a reservoir containing the same polymerizable liquid, or they may be in fluid communication with a reservoir containing different polymerizable liquids. Through the use of valve assemblies, different polymerizable liquids can, in some embodiments, be alternately fed through the same feed channel, if desired.
Four. Process controller and control
The methods and apparatus of the invention may include process steps and apparatus features to implement process control, including feedback control and feed-forward control, for example, to improve the speed and / or reliability of the method.
A controller to be used to carry out the present invention can be implemented as hardware circuitry, software, or a combination thereof. In one embodiment, the controller is a general-purpose computer running software that is operatively related to monitors, drives, pumps, and other components through suitable interface hardware and / or software. Suitable software for controlling a three-dimensional printing or manufacturing method and apparatus as described herein includes, but is not limited to, ReplicatorG open source 3d printing program, 3DPrint ™ controller software from
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3D systems, Slic3r, Skeinforge, KISSIicer, Repetier-Host, PrintRun, Curapetei<sub>r</sub> ) ndw5BfflBi * »us combinations.
Process parameters to monitor directly or indirectly, continuously or intermittently, during the process (for example, during one, some or all of the fill, irradiation and advance steps) include, but are not limited to, irradiation intensity, temperature of the carrier, build zone polymerizable liquid, rising product temperature, build plate temperature, pressure, feed rate, pressure, force (e.g. exerted on the build plate through the carrier and the product to be manufactured), stress (eg exerted on the carrier by the increasing product being manufactured) the thickness of the release layer, etc.
Known parameters that can be used in feedforward and / or feedback control systems include, but are not limited to, expected consumption of polymerizable liquid (e.g., of the known geometry or volume of the article to be manufactured ), degradation temperature of the polymer that is formed from the polymerizable liquid, etc.
Process conditions for control directly or indirectly, continuously or stepwise, in response to a monitored parameter and / or known parameters (for example, during any or all of the process steps noted above), include, but are not limited to a, delivery rate of the polymerizable liquid, temperature, pressure, rate or rate of advance of the carrier, intensity of irradiation, duration of irradiation (for example, for each cut), etc.
For example, the temperature of the polymerizable liquid in the build zone, or the temperature of the build plate, can be monitored, directly or indirectly with an appropriate thermocouple, non-contact temperature sensor (e.g. an infrared temperature sensor) , or other suitable temperature sensor, to determine if the temperature exceeds the degradation temperature of the polymerized product. If so, a process parameter can be adjusted via a controller to reduce the temperature in the build zone and / or build plate. Suitable process parameters for such adjustment may include: lowering the temperature with a cooler, lowering the carrier advance rate, lowering the intensity of irradiation, lowering the duration of radiation exposure, etc.
In addition, the intensity of the irradiation source (for example, an ultraviolet light source such as a mercury lamp) can be monitored with a photodetector to detect a decrease in intensity from the irradiation source (for example, through the routine degradation of it during use). If detected, a process parameter can be adjusted through a controller to accommodate the loss of intensity. Appropriate process parameters for such adjustment may include: increasing the temperature with a »IMPIAS
MST fruro mmcano heater, decrease the advance speed of the carrier, increase Ta'pSSrvsfá deSaMEO ^ ae light, etc. ,
As another example, temperature and / or pressure control to improve lead time can be achieved with heaters and coolers (individually, or in combination with each other and separately responsive to a controller), and / or with a pressure supply (eg pump, pressure vessel, valves and their combinations) and / or a pressure release mechanism such as a controllable valve (individually, or in combination with each other and separately responsive to a controller).
In some embodiments the controller is configured to maintain the polymerization zone gradient described herein (see, for example, Figure 1) throughout the manufacture of some or all of the final product. The specific configuration (eg, times, rate or speed of advance, radiation intensity, temperature, etc.) will depend on factors such as the nature of the specific polymerizable liquid and the product to be created. The configuration to maintain the gradient of the polymerization zone can be carried out empirically, by introducing a set of process parameters or instructions previously determined, or determined through a series of trial or trial and error runs; configuration can be provided through default instructions; setup can be accomplished by means of proper monitoring and feedback (as discussed above), their combinations, or in any other suitable way.
5, Manufacturing products
The three-dimensional products produced by the methods and processes of the present invention can be finished or substantially finished end products, or they can be intermediate products subject to additional manufacturing steps such as surface treatment, laser cutting, electrical discharge machining, etc. Intermediate products include products for which additional additive manufacturing, in the same apparatus or a different apparatus, can be carried out. For example, a fault or split line can be deliberately introduced into a progressive construction by interrupting, and then reintegrating, the gradient of the polymerization zone, to terminate a region of the finished product, or simply because a particular region of the product finished or construction is less fragile than others.
Numerous different products can be made by means of the methods and apparatus of the present invention, including both large-scale models and prototypes, small custom products, miniature or micro-miniature products or devices, etc. Examples include, but are not limited to, medical devices and implantable medical devices such as stents, drug delivery reservoirs, functional structures, series of
<img file="MX352425B_D0022.tif" />
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Thus, in some modalities the IJUSÍJé tfiñét Uña product has a height of 1 millimeters to 10 or 100 millimeters, or more and / or a maximum width of 0.1 or 1 millimeters to 10 or 100 millimeters, or more. In other embodiments, the product can have a height of 10 or 100 nanometers up to 10 or 100 microns, or more and / or a maximum width of 10 or 100 nanometers up to 10 or 100 microns, or more. These are examples only: The maximum size and width depend on the architecture of the particular device and the resolution of the light source and can be adjusted depending on the particular objective of the modality or item being manufactured.
In some embodiments, the product's height-to-width ratio is at least 2: 1, 10: 1, 50: 1, or 100: 1, or more, or a width-to-height ratio of 1: 1.10: 1 , 50: 1, or 100: 1, or more.
In some embodiments, the product has at least one, or a plurality of, pores or channels formed therein, as further discussed below.
The processes described herein can produce products with a variety of different properties. Therefore, in some modalities the products are rigid; in other modalities the products are flexible or elastic. In some modalities, the products are a solid; in other embodiments, the products are a gel such as a hydrogel. In some embodiments, the products have shape memory (that is, they substantially return to a previous shape after being deformed, provided they are not deformed to the point of structural failure). In some embodiments, the products are unitary (ie, they are formed from a single polymerizable liquid); In some embodiments, the products are mixed materials (that is, they are formed from two or more different polymerizable liquids). The particular properties will be determined by factors such as the choice of polymerizable liquid (s) employed.
In some embodiments, the product or made article has at least one projecting (or protrusion) feature, such as a bridging element between the two support bodies, or a cantilever element projecting from a substantially vertical support body. Due to the unidirectional and continuous nature of some embodiments of the present processes, being substantially reduces the problem of fault or split lines that form between the layers when each layer is polymerized to substantial completion and exposed a substantial interval of time. that occurs before the next pattern. In fact, in some embodiments the methods are especially advantageous for reducing, or eliminating, the number of support structures for such projections that are manufactured concurrently with the article.
The present invention is explained in more detail in the following non-limiting Examples.
<img file="MX352425B_D0023.tif" />
EXAMPLE 1
IMPI
MTtTUTO MEXICANO oe LA rtOHEDAD INDUSTRIAL
Inhibitor Transfer to Build a Surface of a Surface of.
Separate Feeding
A drop of ultraviolet (UV) curable adhesive was placed on a metal plate and covered with a 10mm thick plate of TEFLON® AF fluoropolymer (an amorphous crystalline polymer) as shown in Figure 5A. UV radiation was delivered to the adhesive from the side of the Teflon AF as shown in Figure 5B. After UV exposure the two plates were separated. It was found that no force was required to separate the two plates. Upon examination of the samples it was found that the adhesive cured only near the metal plate and that the thin film of the uncured adhesive was present on the Teflon AF fluoropolymer plate and also in the cured portion of the adhesive as shown. in Figure 5C.
Two controlled experiments were also performed where a clean glass (Figures 5D to 5F) and also a release coat treated glass (Figures 5G to 51) were used. It was confirmed that considerable force was required to separate the clean glass from the metal and the adhesive was found to remain on the glass. Less force was required to separate the treated glass, while the adhesive remained on the metal plate.
The chemical phenomenon that describes the observed behavior is oxygen inhibition of the radical polymerization reaction. In particular, Teflon AF has a very high coefficient of oxygen permeability. The constant supply of oxygen through the 10mm thick Teflon AF is sufficient to prevent a thin layer of acrylate adhesive from polymerization. The thickness of the uncured adhesive layer in the aforementioned experiment was in the order of 10 microns and can be increased or decreased by varying the amount of photoinitiator present in the adhesive.
EXAMPLE 2
Transfer of Inhibitor Through Build Plate to Build Surface
Samples 1 and 2 were prepared in a similar manner where a bead of UV curable adhesive was placed on a metal plate and covered with a 10mm thick plate of TEFLON® AF fluoropolymer as shown in Figure 6A. . Both samples were exposed to a nitrogen environment to remove any oxygen presence as shown in Figure 6B. Then both samples were brought to a standard atmosphere environment and Sample 1 was immediately exposed to UV radiation while Test 2 was
<img file="MX352425B_D0024.tif" />
IMPI
INSTITUTO MEXICANO DE LA PROPIEDAD industrial exposed to UV radiation 10 minutes after being in the atmosphere environment. Both samples were exposed to the same amount of UV radiation as shown in Figure 6C and Figure 6E. Upon examination of the samples after UV exposure it was found that the adhesive was fully cured in Sample 1 as shown in Figure 6D and only near the metal plate in Sample 2 as shown in Figure 6F. A thin film of uncured adhesive was present on the Teflon AF fluoropolymer plate and also in the cured portion of the adhesive for Sample 2. This experiment shows that the inhibitor, oxygen, was transferred through the Teflon AF plate to the adhesive. during the 10 minute period of being exposed to the ambient atmosphere.
EXAMPLE 3
Higher Manufacturing Speed: Pressure
A UV transparent and highly oxygen permeable material was used as the bottom of a chamber filled with photocurable resin in a device of the invention. During construction, the upper part of an object was attached to a support plate that moves upward at a substantially constant speed while the lower portion of the object is constantly formed just above the bottom of the chamber. The void between the bottom of the object and the bottom of the chamber is always filled with resin. As the object is formed and advanced, the resin in the vacuum is constantly replenished with supply resin contained in the chamber.
The speed of object formation depends on the resin viscosity η, atmospheric pressure P, the height of the space between the object and the bottom of the chamber h, and the linear dimension L of the bottom surface of the object. Simple calculations are performed to calculate this velocity using the theory of viscous flow between two parallel plates. The time τ required to fill the space shown in Figure 7 is given by the equation:
<img file="MX352425B_D0025.tif" />
Assuming that:
L ~ 100 mm h ~ 100 microns η - 100 cPoise P ~ 1 atm
IMPIAS,
MEXICAN INSTITUTE
DR: λ PROPIROAi.
In this illustrative embodiment, time τ is calculated for eStEfFWUn oroephi-ae 1 second, resulting in manufacturing speeds of 100 microns per second or 5 minutes per centimeter. These calculations assume that the thickness of the uncured resin is maintained at approximately 100 microns. Depending on the resin chemistry and the permeability of the base plate, this parameter can vary. If, for example, the gap is 25 microns, then the manufacturing rates at atmospheric pressure will decrease according to Equation 1 by a factor of 16. However, when increasing the ambient pressure to more than atmospheric pressure, for example By applying an external pressure in the order of 1034213.5935 Pa as shown in Figure 8, in some embodiments you can increase the manufacturing speed by a factor of 10.
When oxygen is the polymerization inhibitor, the uncured resin gap can be controlled by altering the physical environment in the enclosed chamber that contacts the feed surface. For example, an atmosphere of pure oxygen, or enriched in oxygen (for example, 95% oxygen 5% carbon dioxide) can be provided instead of compressed air, in order to increase the space resulting in an increase in the manufacturing time.
EXAMPLE 4
Rod and Fiber Manufacturing
The methods of the present invention can be used to make an elongated rod or fiber as shown in Figure 9, the rod or fiber having (for example) a width or diameter of 0.01 or 0.1 to 10 or 100 millimeters. Although a circular cross section is shown, any suitable cross section can be used, including elliptical, polygonal (triangular, square, pentagonal, hexagonal, etc.), irregular, and combinations thereof. The rod or fiber may have a plurality of elongated pores or channels formed therein (eg, 1, 10, 100, 1,000, 10,000, or 100,000 or more) of any suitable diameter (eg, 0.1 or 1 micron, up to 10 or 100 microns or more) and any suitable cross section as described above. A liquid not polymerized in the pores or channels can be removed (if desired) by any suitable technique, such as blowing, pressure, vacuum, heating, drying and combinations thereof. The length of the rod or fiber can be increased by using a take-up reel as described above, and the speed of manufacture of the rod or fiber can be increased to carry out polymerization under pressure as described above. A plurality of such rods or fibers can be constructed at the same time from a single build plate by providing a plurality of independent pickup carriers or reels. Said rods or fibers can be used for any purpose, such as using each pore or channel in it.
IMPI Mexican institute »t LA MOPIFOAO industrial
<img file="MX352425B_D0026.tif" />
as a separate channel in a microfluidic system.
EXAMPLE 5
Illustrative apparatus
An apparatus that can be used to carry out the present invention was assembled as described above, with a LOCTTTE ™ UV Curing Rod System as the ultraviolet light source, a build plate comprised of a Teflon AF 2400 film with 0.006 cm thick Biogeneral clamped in a window and tensioned to substantial rigidity with a tension ring, the optical components: from Newport Corporation, Edmund Optics, and Thorlabs, a Texas Instruments DLP LightCrafter Development Kit such as the digital projector, a THK Co., LTD ball screw linear stage that serves as an elevator for the carrier, a Parallax continuous servo Inc such as the carrier or motor lift and thruster, a Propeller microcontroller-based motion controller from Parallax Inc., a magnetic encoder-based position controller from Austria Microsystems, motion control software written in SPIN language created by Parallax, open source Slic3r 3D cutting software, and image control software written using a Qt framework and Visual C ++.
Several different example items made with this device by the methods described herein are further described below.
EXAMPLE 6
Manufacture of a Series of Microguides 700 Mieras
Using an apparatus as described in the example above, trimethylolpropane triacrylate as the polymerizable liquid, and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as a photoinitiator, the series of microneedles shown were made in Figure 10. The carrier was advanced unidirectionally by means of the ball screw at a continuous speed of 10 microns per second and successive exposures were carried out every 2 microns along the height of the construction at a duration of 0.2 seconds per exposure. The total number of successive exposures was 350 and the total build time was 70 seconds.
EXAMPLE 7
Manufacture of a Series of Microguides 2000 Mieras
The 2000 micron microneedle series shown in Figure 11 was made in a
MEXICAN INSTITUTE
OF THE CURRENCY in a similar way as described in Example 6 above, with 1000 expósl ^ bnes sbcési ^ ís during a total manufacturing time of 200 seconds. .............
It will be apparent that other series, for example with microneedles having widths of 5 to 500 microns and heights of 5 to 2000 microns or more, can be manufactured in a similar manner. Although a square cross section is shown, any suitable cross section can be used, including circular, elliptical, polygonal (triangular, rectangular, pentagonal, hexagonal, etc.), irregular, and combinations thereof. The microneedle spacing can be varied as desired, eg from 5 to 100 microns, and the microneedles or other microstructures can be arranged with respect to each other in any suitable pattern, eg, square, rectangular, hexagonal, etc.
EXAMPLE 8
Fabrication of a Ring Structure
A ring was made using the apparatus described in Example 5 above, trimethylolpropane triacrylate as the polymerizable liquid, and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as the photoinitiator. The carrier was advanced unidirectionally by means of the ball screw at a continuous speed of 20 microns per second and successive exposures were carried out every 10 microns along the height of the construction for a duration of 0.5 seconds per exposure. The total number of successive exposures was 1040 and the total build time was 520 seconds. Figure 12 shows the ring during manufacture, and Figure 13 shows the ring after manufacture. Note the absence of supports for elements extensively projected during manufacture.
EXAMPLE 9
Manufacture of a Chess Piece
The chess piece shown in Figure 14 was made using the apparatus described in the previous examples, trimethylolpropane triacrylate as the polymerizable liquid, and diphenyl oxide (2,4,6-trimethylbenzoyl) phosphine as a photoinitiator. The carrier was advanced unidirectionally by means of the ball screw at a continuous speed of 20 microns per second and successive exposures were carried out every 10 microns along the height of the construction for a duration of 0.5 seconds per exposure. The total number of successive exposures was 1070 and the total build time was 535 seconds.
INSTITUTO MEXICAN ·
OF THE PROPERTY
EXAMPLE 10 industrial
Fabrication of a Ribbed Rectangular Prism
The ribbed rectangular prism shown in Figure 15 was made using the apparatus described in the previous Examples, trimethylolpropane triacrylate as the polymerizable liquid, and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as the photoinitiator. The carrier was advanced unidirectionally by means of the worm gear at a continuous speed of 20 microns per second and successive exposures were carried out every 10 microns along the height of the construction for a duration of 0.5 seconds per exposure. The total number of successive exposures was 800 and the total build time was 400 seconds.
EXAMPLE 11
Fabrication of a Coiled or Spiral Structure
The coil or coil shown in Figure 16 was made using the apparatus that was described in the previous examples, trimethylolpropane triacrylate as the polymerizable liquid, and diphenol oxide (2,4,6-trimethylbenzo L) phosphine as the photoinitiator. The carrier was advanced unidirectionally by means of the ball screw at a continuous speed of 20 microns per second and successive exposures were carried out every 10 microns along the height of the construction for a duration of 0.5 seconds per exposure. The total number of successive exposures was 970 and the total build time was 485 seconds.
Note that this extensively cantilevered structure was manufactured free of any supporting structures.
EXAMPLE 12
Exposure Time vs. Depth of Cure
An experiment was conducted with various concentrations of amber candle dye and photoinitiator (PI) in trimethylolpropane triacrylate as the polymerizable liquid and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as the photoinitiator. The results are shown in Figure 17. The image used was a 6mm circle, which produced a disk-like part in the resin bath, when cured. The thickness of the disc varied based on the exposure time and the concentration of the photoinitiator and dye in the resin. All resin mixes would begin to cure rapidly and approach a limiting value. The optimal resin should cure in a short period of time and the limiting value should be as small as possible.
<img file="MX352425B_D0027.tif" />
IMPI ** ΤΓΠΓΓΟ MEXICAN PROPERTY
The two resins that best meet these criteria are 3% photoinity8P<sup>or</sup>£ BVy '<sup>l</sup>0.
(fine spots) and 5% photoinitiator without any dye (solid). These resins also produce the best printed parts in terms of characteristic contrast and clarity.
A chess piece made from such a dye-containing resin is shown in Figure 18.
EXAMPLE 13
Sacrificial Layers for Liberation ') Soluble in the Carrier
A shortcoming of the prior techniques is that the requirement to break the build plate adhesion, for example by sliding the build plate or by using an elastic build plate, makes it problematic to employ a release layer or soluble adhesive layer / in the carrier that can fail prematurely during the manufacturing process. The present invention facilitates the use of a release layer on the carrier during manufacture.
The surface of the carrier can be coated with a release layer, that is, a soluble sacrificial layer (e.g. cyanoacrylate adhesive), and the series of objects can be printed as shown in Figure 19. Any suitable thickness of the Release layer can be used, for example, from 100 nanometers to 1 millimeter. By dipping the carrier with the fabricated objects in an appropriate solvent (e.g. acetone for the cyanoacrylate adhesive) that selectively dissolves or solubilizes the release layer then the objects are released from the carrier as shown in Figure 20.
EXAMPLE 14
Fabricate Rectangular Prisms in a Release Layer
The series of rectangular prisms with dimensions of 200 x 200 x 1000 microns shown in Figure 21 was made using the apparatus described above, trimethylolpropane triacrylate as the polymerizable liquid, diphenyl oxide (2,4,6- trimethylbenzoyl) phosphine as the photoinitiator, and cyanoacrylate adhesive as the release layer. The carrier was advanced by means of the ball screw at a continuous speed of 10 microns per second and successive exposures were carried out every 10 microns along the height of the construction for a duration of 1 second per exposure. The total number of successive exposures was 100 and the total build time was 100 seconds. The cyanoacrylate release layer was then dissolved by acetone to produce free floating prisms as shown in Figure 22.
<sup>3</sup>9 IMPI
0 <5ΠΠΠΟΜΕΧΟΜ§ »ΕΕΙΑΨΒΠΡίίδ * ®
EXAMPLE 15 mwjKBUM
Manufacture of Cylindrical Basket Structures
The cylindrical basket structure of Figure 23 was made using the apparatus described in the previous Example, trimethylolpropane triacrylate as the polymerizable liquid, and diphenyl oxide (2,4,6-trimethylbenzoyl) phosphine as the photoinitiator. . The carrier was advanced by means of the ball screw at a continuous speed of 20 microns per second and successive exposures were carried out every 10 microns along the height of the construction at a duration of 0.5 seconds per exposure. The total number of successive exposures was 1,400 and the total build time was 700 seconds. No detachable support structure for cantilever features or projections were used.
EXAMPLE 16
Manufacture of Structures of a Hydroqel
Figure 24 and Figure 25 are photographs of string structures and basket structures, respectively, produced in a manner similar to those described above, except that they were manufactured using PEG (poly (ethylene glycol) diacrylate, average Mn 700 ) as the polymerizable liquid and 5% diphenyl oxide (2,4,6-trimethylbenzoyl) phosphine as the photoinitiator. The processing conditions were otherwise the same for the previously manufactured triacrylate parts.
EXAMPLE 17
Hydroqel-Based Parts Flexibility
The cylindrical basket structure produced in Example 23 above and shown in Figure 25 was placed manually between two glass microscope stages and pressure was applied manually until the cylindrical basket structure was deformed and substantially flattened. Manual pressure was then released, and the basket structure returned to its former substantially cylindrical shape. The flexibility, elasticity, and shape memory properties of the articles make them attractive for a variety of uses, including but not limited to stents for various biomedical applications.
<img file="MX352425B_D0028.tif" />
EXAMPLE 18
IMPI
IKTTTVTO MEXICANO M CA fft0ft £ DA0 tNfX & niAL
Manufacture of Intraluminal Stents for Toranóntirn Use
Stents are typically used as adjuncts to percutaneous transluminal balloon angioplasty procedures, in the treatment of blocked or partially blocked arteries and other blood vessels. As an example of a balloon angioplasty procedure, a guiding catheter or sheath is percutaneously introduced into the cardiovascular system of a patient through a femoral artery and advanced through the vasculature until the end is distal to the Guiding catheter is placed proximal to the injury site. A guidewire and a dilatation catheter having a balloon at the distal end are inserted through the guide catheter with the guidewire sliding into the dilatation catheter. The guidewire is first advanced out of the guide catheter into the patient's vasculature and directed through the vascular lesion. The dilation catheter is subsequently advanced over the previously advanced guidewire until the dilation balloon is properly positioned through the vascular lesion. Once in position through the lesion, the expandable balloon is inflated to a predetermined size with a radiopaque fluid at relatively high pressure to radially compress the atherosclerotic plaque of the lesion against the interior of the artery wall and into the artery wall. way to dilate the lumen of the artery. The balloon is then deflated to a small profile so that the dilation catheter can be withdrawn from the patient's vasculature and blood flow resumed through the dilated artery.
Balloon angioplasty sometimes results in short-term or long-term failure. That is, the canisters may be closed abruptly shortly after the procedure or restenosis occurs gradually over a period of months thereafter. To counteract restenosis after angioplasty, implanted intraluminal prostheses, commonly referred to as stents, are used to achieve long-term vessel patency. A stent functions as a scaffold to structurally support the vessel wall to maintain luminal patency, and is transported to a site of injury via a delivery catheter.
Types of stents can include balloon expandable stents, self-expanding spring-type stents, and thermally expandable stents. Expandable balloon stents are delivered via a dilatation catheter and are plastically deformed by an expandable member, such as an inflation balloon, from a small initial diameter to a larger expanded diameter. Self-expanding stents are formed as spring elements that are radially compressed around a delivery catheter. A compressed self-expanding stent is normally maintained in the compressed state by means of a delivery sheath. Behind the
4i IMPIAS
INSTITUTO MEXICAHL '
FROM THE supply to an injury site, the supply sheath retracts allowing<sup>T</sup>the sfeRT to expand. Thermally expandable stents are formed from Hp mAmnna Hp form gijp aiparins have the ability to expand from a small initial diameter to a second larger diameter upon application of heat to the alloy.
It may be desirable to provide localized drug treatment of a container at the site that is supported by a stent. Thus, it is sometimes desirable to use a stent both as a support for a lumen wall as well as a delivery vehicle for one or more pharmacological agents. Unfortunately, the bare metal materials typically employed in conventional stents are generally not capable of carrying and delivering pharmacological agents. Previously devised solutions to this dilemma have been to bind drug-bearing polymers to metal stents. Additionally, methods have been described wherein the metallic structure of a stent has been formed or treated to create a porous surface that improves the ability to retain applied pharmacological agents. However, these methods have generally failed to provide a quick, easy and inexpensive way of loading drugs into intraluminal prostheses, such as stents. Furthermore, only small amounts of drugs can be loaded into the thin polymeric layers.
Intraluminal prostheses, such as stents, have been developed using various polymeric materials and / or coatings of polymeric materials to overcome the limitations of conventional metal prostheses. However, it would be desirable to be able to adjust the various mechanical properties (eg, modulus, hook force, flexibility, etc.) of polymeric intraluminal prostheses. For example, for intraluminal prostheses that are used to deliver pharmacological agents, it would be desirable to be able to adjust the rate of elution of a pharmacological agent from there. As another example, it would be desirable to be able to adjust the rate of degradation and / or the nature of degradation of the polymeric material.
In accordance with the embodiments of the present example, methods of manufacturing polymeric intraluminal prostheses (eg, formed from the polymeric material to suitably include functionalized PEG, PLGA, polycaprolactone, gelatin, etc.) include annealing the polymeric material to selectively modify the crystallinity or crystalline structure thereof that is achieved by the methods described herein, including but not limited to those that are established in connection with cylindrical basket structures as described above.
Pharmacological agents placed on or within the polymeric material may include, but are not limited to, agents selected from the following categories: antineoplastics, antimitotics, anti-inflammatories, antiplatelets, anticoagulants, antifibrins, antithrombins, antiproliferatives, antibiotics, antioxidants, immunosuppressants, antiallergic substances , and their
INSTITUTO MEXICANO DE LA PROPERTY INDUSTRIAL combinations.
According to other embodiments of the present invention, the degree of SliLI elazaetho · molecular of the polymeric material of an intraluminal prosthesis can be modified by subjecting the polymeric material to treatment and / or chemical irradiation. The polymeric material can be subjected to treatment and / or chemical irradiation before, during and / or after annealing. These treatments can also act as a sterilization step.
EXAMPLE 19
Manufacture of Series of Therapeutic Microachias
Many promising new therapeutics are large biomolecules, such as peptides, proteins, antibodies, and nucleic acids. These molecules may be too large, brittle, or insoluble for delivery through traditional routes of introduction. Hypodermic injection (including intravascular, intramuscular, etc.) allows delivery of sensitive therapeutics, but induces pain, provides opportunities for accidental needle sticks, and produces sudden and biohazard waste. Furthermore, in the case of vaccine delivery, hypodermic needles do not deliver doses to the optimal location to elicit an immune response; they penetrate muscle, a region known to have a lower density of immune-sensitive cells than skin. Transdermal patches are effective in targeting drugs released over time (such as nicotine and seasickness medications), but the epidermis (specifically the stratum corneum) limits the diffusion of most drugs (> 500 Da) through the skin. Clearly, the ability to effectively transport therapeutics in the body remains a significant challenge.
Although there are limitations to traditional transdermal drug delivery, typically dependent on passive diffusion of therapeutics through the skin, this route of administration remains very promising.
Using the apparatus described in the Examples above and photopolymerizable, biocompatible and biodegradable resins (suitably functionalized PEG, PLGA, polycaprolactone, gelatin, etc.) are used in combination with therapeutics and vaccine elements (antigens, adjuvants, etc.) , to produce series of therapeutic microneedles that have essentially the same structure or appearance as shown above. Those skilled in the art will appreciate numerous different structures and architectures for such series of therapeutic microneedles that can be produced by the methods and apparatus described herein.
<img file="MX352425B_D0029.tif" />
IMPI
1NST1TUT MEXICAN
OF PROELITY
INDUSTRIAL
EXAMPLE 20
Vertical Resolution Dependence on Manufacturing Speed
During the part construction process, the controller image processing unit (IPU) in some modes constantly updates cross-sectional layer images of the part. The maximum image / update speed may vary in some modes from 1 frame per second up to 1000 frames per second, depending on the hardware.
If the desired vertical resolution is delta then during the construction process the advance dz of the part carrier during an image structure must be less than delta. If the manufacturing speed is / then dz is given by means of dz = - f
In order to achieve delta resolution, the build speed / must be less than the maximum build speed /<sub>m</sub>to<sub>X</sub> which is given by = ¥
Two chess piece parts similar to those illustrated above were made with a carrier advance speed of 250mm / hour and 500mm / hour. The maximum speed of the particular IPU frame used to make the parts was approximately 1 frame per second. The estimated resolution of these parts was 50 microns at 250mm / hour, and 100 microns at 500mm / hour.
EXAMPLE 21
Higher Manufacturing Speed: Temperature
The increased speed of manufacturing by means of pressure was described above. In addition, in the methods and apparatus that were established both generally and specifically above and below, the manufacturing speed can be increased by heating the polymerizable liquid, or the resin, to reduce the viscosity of the same, to facilitate the filling of the area. with the polymerizable liquid or the migration of the polymerizable liquid in the construction zone (with or without increased pressure). Some resins, such as high performance resins including those noted above, can be solid at room temperature and pressure, and heating can be a convenient way to liquefy them.
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IMPI Instituto Mixícano · € LA FBOPiEDAO
Heating can be accomplished by any convenient approach, such as with closed oven infrared heaters operatively related to a temperature sensor and controller, as schematically illustrated in Figure 26. Numerous additional types and configurations of heaters can be used, alone or in combination with the above and others. Resistive heaters can be used, for example, immersed in the polymerizable liquid in the build plate. Thermoelectric devices or Peltier heaters can be used, for example by contacting the build plate and / or the polymerizable liquid. The polymerizable liquid can be pre-heated, in a storage tank and / or through various feed lines. One or more temperature sensors can be used to detect ambient temperature (in the chamber), build plate temperature, carrier temperature, polymerizable liquid temperature (for example, at any point, such as on the build plate ), etc.
In some embodiments, the polymerizable liquid is heated to at least 5, 10, 20, 40, 60, 80, or 100 degrees Centigrade or higher than room temperature.
In some embodiments, the polymerizable liquid has a viscosity of at least 100, 1,000, or 10,000 centipoise, up to 1,000,000 centipoise or more at 25 degrees Centigrade and atmospheric pressure (note 1 centipoise = 1 milliPascal second). In some embodiments, such polymerizable liquids may have a viscosity when heated (eg, by the amount described above) of no more than 1,000, 100, 10, or 1 centipoise. The specific final viscosity desired to be achieved will depend on factors such as the desired manufacturing speed, the size and shape of the article being manufactured, the presence or absence of increased pressure, etc.
Viscosity can be measured by any suitable technique, for example by means of a Brookfield viscometer having a cone and plate geometry, with a cone angle of 1 degree, a diameter of 40 millimeters, operated at 60 revolutions per minute.
Coolers can optionally be included if desired to more quickly correct temperature (with heaters, or without heaters, for example, to help dissipate exothermic heat generated by rapid light curing. Again, any suitable cooler setting can be used, generally operationally related to a temperature sensor and controller as noted above. Heat exchangers, heat sinks, coolants, thermoelectric devices such as Peltier coolers (which can also serve as Peltier heaters), etc. can be used.
<img file="MX352425B_D0030.tif" />
EXAMPLE 22
IMPI
ΙΝΓΓΓΓυΤΟ M1XICANO 06 INDUSTRIAL PROPERTY
Feed Resin through Carrier and Internal Feed Channels__
As discussed in Example 3 the speed of object formation depends on the linear dimension L of the lower surface of the object, the resin viscosity η, the atmospheric pressure P, and the height of the space between the object and the bottom. camera h. The time τ required to fill the space between the object and the bottom of the chamber is:
<img file="MX352425B_D0031.tif" />
<h) P
As can be seen, a 10-fold increase in part size results in a 100-fold decrease in manufacturing speed. To eliminate such strong manufacturing speed dependence on part size, polymerizable liquid (or resin) can be fed through the part carrier and through the part as shown in Figure 27.
The pump can comprise any suitable pumping device, including but not limited to syringe pumps, gear pumps, peristaltic pumps, etc. The speed at which the pump operates is controlled by a controller and depends on the geometry of the part and the speed of manufacture.
In this approach the dependence of the manufacturing speed of the part on the linear dimension L of the lower surface of the object, the resin viscosity η, the atmospheric pressure P, and the height of the space between the object and the bottom of the chamber h is no longer limited by the above equation but is preferably controlled by the speed at which the resin pump operates, the rate of the cure reaction and the ability to mitigate heat removal from the cure reaction. The pump in this example could comprise a syringe pump, gear pump, or peristaltic pump. The operation of the pump could be included in the feedback loop that is controlled by the central processing unit where the pumping speeds depend on the geometry of the part and the desired manufacturing speed.
EXAMPLE 23 Controlling Resin Feed Rate: Advance Feed Control
During the part construction process the rate of resin consumption changes based on the cross-sectional area of the part.
resin delivery rate is described below. If the speed of construction is v and the cross section of part A varies with time, how / 1f¿7eQUu) £ esJaj ^ theQcity of ^ uH ^ of the resin can be adjusted to correspond, in whole or in part, with:
For example, during the construction process a central processing unit (CPU) that serves as a controller can calculate in real time the current cross section of the part, then calculate the delivery speed based on a rule such as the above equation and communicating the calculated speed to a resin delivery pump controller (RDPC). The RDPC can then adjust the speed of the resin supply pump based on the data received from the CPU.
Such a feedforward control system can be used alone or in combination with other feedforward or feedback control systems (eg, temperature and / or pressure control) as described above.
EXAMPLE 24
Feed Polymerizable Liquid through External Feed Ducts
In some embodiments where the polymerizable liquid is delivered through one or more channels formed in the carrier, it may be desired that some, or all, of the article being manufactured is totally solid. In such cases, separate or external feed conduits in fluid communication with one (or each) channel supplying polymerizable liquid may be manufactured at the same time adjacent to the article being manufactured (in contrast to one or more internal feed channels formed within of the item that is produced.
The polymerizable liquid can then be provided through the external feed conduit (s) to the build plate and build zone. In some multiple embodiments of such feed conduits, for example 2, 10, 100, or 1000 or more may be constructed, depending on the size of the item being manufactured. Said external feed conduits may be used in combination, at the same time or sequentially (eg alternately), with internal feed channels (ie channels formed within the article being manufactured).
<img file="MX352425B_D0032.tif" />
EXAMPLE 25
IMPI
ΙΗ3ΤΙΤΙΠΌ M8XICANO
D € THE INDUSTRIAL METHOD
Manufacture With Multiple Different Resins with Multiple Feed-nc rnnriurt-nc.
Items can be manufactured using multiple resins by feeding the different resins through the build deck, and using them to create tubes or channels to supply the resin to the correct area of the part being manufactured.
Figure 28 illustrates the method that can be used to feed resin through the build deck, is used to fabricate the resin supply channels as needed, and when necessary, feeds additional resin to fabricate the part itself. When the section is finished fabrication, the channel is cured and another channel can start feeding the next resin to continue fabricating the part.
EXAMPLE 26
Control Method and Apparatus
A method and apparatus as described above can be controlled by a software program running on a general purpose computer with suitable interface hardware between that computer and the apparatus described above. Numerous alternatives are commercially available. Non-limiting examples of a combination of the components are shown in Figures 29 to 31, where the Microcontroller is Parallax Propeller, the Scaler Motor Drive is Sparkfun EasyDriver, the LED Driver is a Luxeon Single LED Driver, the USB for Serial It is a Parallax USB to Serial converter, and the DLP System is a Texas Instruments LightCrafter system.
The foregoing is illustrative of the present invention and should not be construed as a limitation thereof. The invention is defined by the following claims, with equivalents of the claims included therein.
<img file="MX352425B_D0033.tif" />
Contents66
53 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53
123 members in 18 offices
Priority claims19
| Document | Office | Kind | Date |
|---|---|---|---|
| 201361763746 | United States of America | P | |
| 201361763746 | United States of America | P | |
| 61763746 | United States of America | – | |
| 201361865841 | United States of America | P | |
| 201361865841 | United States of America | P | |
| 61865841 | United States of America | – | |
| 201361919903 | United States of America | P | |
| 201361919903 | United States of America | P | |
| 61919903 | United States of America | – | |
| 2014015497 | United States of America | W | |
| 2014015497 | United States of America | W | |
| 61763746 | – | – | – |
| 61865841 | – | – | – |
| 61919903 | – | – | – |
| PCTUS2014015497 | – | – | – |
| US201361763746P | – | – | – |
| US201361865841P | – | – | – |
| US201361919903P | – | – | – |
| WO2014US15497 | – | – | – |
Members123
| Document | Office | Kind | |
|---|---|---|---|
| CA2898098A1 | Canada | A1 | |
| CA2898103A1 | Canada | A1 | |
| CA2898106A1 | Canada | A1 | |
| WO2014126830A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2014126834A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2014126837A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2014126830A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2014126834A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US2014361463A1 | United States of America | A1 | |
| TW201447478A | Taiwan Province of China | A | |
| WO2014126837A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US2015072293A1 | United States of America | A1 | |
| US2015097315A1 | United States of America | A1 | |
| US2015097316A1 | United States of America | A1 | |
| US2015102532A1 | United States of America | A1 | |
| KR20150117273A | Republic of Korea | A | |
| KR20150117274A | Republic of Korea | A | |
| KR20150117275A | Republic of Korea | A | |
| CN105122135A | China | A | |
| CN105122136A | China | A | |
| US9205601B2 | United States of America | B2 | |
| US9211678B2 | United States of America | B2 | |
| US9216546B2 | United States of America | B2 | |
| EP2956821A2 | European Patent Office (EPO) | A2 | |
| EP2956822A2 | European Patent Office (EPO) | A2 | |
| EP2956823A2 | European Patent Office (EPO) | A2 | |
| US2016059484A1 | United States of America | A1 | |
| US2016059486A1 | United States of America | A1 | |
| US2016059487A1 | United States of America | A1 | |
| CN105452958A | China | A | |
| JP2016509962A | Japan | A | |
| JP2016509963A | Japan | A | |
| JP2016509964A | Japan | A | |
| MX2015010374A | Mexico | A | |
| MX2015010375A | Mexico | A | |
| MX2015010376A | Mexico | A | |
| US9360757B2 | United States of America | B2 | |
| EP2956822B1 | European Patent Office (EPO) | B1 | |
| EP2956823B1 | European Patent Office (EPO) | B1 | |
| HK1215475A | Hong Kong, China | A | |
| HK1215475A1 | Hong Kong, China | A1 | |
| HK1215476A | Hong Kong, China | A | |
| HK1215476A1 | Hong Kong, China | A1 | |
| HK1215477A | Hong Kong, China | A | |
| HK1215477A1 | Hong Kong, China | A1 | |
| DK2956823T3 | Denmark | T3 | |
| HRP20161016T1 | Croatia | T1 | |
| US2016311158A1 | United States of America | A1 | |
| ES2588485T3 | Spain | T3 | |
| US9498920B2 | United States of America | B2 | |
| PL2956823T3 | Poland | T3 | |
| US2017095972A1 | United States of America | A1 | |
| EP3187938A1 | European Patent Office (EPO) | A1 | |
| BR112015017976A2 | Brazil | A2 | |
| BR112015018056A2 | Brazil | A2 | |
| BR112015018105A2 | Brazil | A2 | |
| EP3203318A1 | European Patent Office (EPO) | A1 | |
| MX350841B | Mexico | B | |
| MX352425BThis record | Mexico | B | |
| MX352989B | Mexico | B | |
| EP2956821B1 | European Patent Office (EPO) | B1 | |
| ES2667676T3 | Spain | T3 | |
| US9993974B2 | United States of America | B2 | |
| DK2956821T3 | Denmark | T3 | |
| EP2956821B8 | European Patent Office (EPO) | B8 | |
| US10016938B2 | United States of America | B2 | |
| JP6356700B2 | Japan | B2 | |
| EP3358405A1 | European Patent Office (EPO) | A1 | |
| US10093064B2 | United States of America | B2 | |
| JP6423801B2 | Japan | B2 | |
| TW201842404A | Taiwan Province of China | A | |
| US10144181B2 | United States of America | B2 | |
| US10150253B2 | United States of America | B2 | |
| TWI655498B | Taiwan Province of China | B | |
| US2019126534A1 | United States of America | A1 | |
| US2019126547A1 | United States of America | A1 | |
| US2019134888A1 | United States of America | A1 | |
| JP6522519B2 | Japan | B2 | |
| JP2019089340A | Japan | A | |
| EP2956823B2 | European Patent Office (EPO) | B2 | |
| DK2956823T4 | Denmark | T4 | |
| HRP20161016T4 | Croatia | T4 | |
| PL2956823T5 | Poland | T5 | |
| US2019374755A1 | United States of America | A1 | |
| WO2019234541A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2019389127A1 | United States of America | A1 | |
| ES2588485T5 | Spain | T5 | |
| CN105122135B | China | B | |
| CN105452958B | China | B | |
| CN105122136B | China | B | |
| US10596755B2 | United States of America | B2 | |
| US10618215B2 | United States of America | B2 | |
| US2020139617A1 | United States of America | A1 | |
| JP6700443B2 | Japan | B2 | |
| US10710305B2 | United States of America | B2 | |
| AU2019281331A1 | Australia | A1 | |
| CN112236185A | China | A | |
| IL278994A | Israel | A | |
| IL278994D0 | Israel | D0 | |
| US2021069965A1 | United States of America | A1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 352425
- Publication, DOCDB
- 352425
- Publication, EPODOC
- MX352425
- Application
- 2015010375
- Application, DOCDB
- 2015010375
- Application, EPODOC
- MX20150010375
Titles2
- Spanish
- MÉTODO Y APARATO PARA FABRICACIÓN TRIDIMENSIONAL CON ALIMENTACIÓN A TRAVÉS DE PORTADOR.
- English
- METHOD AND APPARATUS FOR THREE-DIMENSIONAL MANUFACTURING WITH FEEDING THROUGH A CARRIER.
Classification
- CPC, 30
- G03F7/0037
- B29C64/135
- B29C64/40
- B29C2033/0005
- B33Y10/00
- B33Y30/00
- B33Y50/02
- B29K2071/02
- B29K2105/0005
- B29K2105/0058
- B29K2827/12
- B29K2883/005
- B29K2995/0026
- B29K2995/0065
- B29C64/124
- B29C64/393
- B29C64/129
- B29C33/0061
- B29C35/0888
- B29C2035/0827
- G05B2219/00
- G05B2219/49016
- A61M37/0015
- A61F2/82
- A61F2240/001
- B33Y80/00
- B29K2067/00
- B29K2995/006
- B29L2031/753
- B29L2031/7534
- IPC, 6
- G03F7 26
- B29C33 58
- B29C33 62
- B33Y30 00
- B33Y50 02
- G03F7 00