JPH07509188A - High-speed prototype 3D lithography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] High-speed prototyping 3D 3D lithography - The present invention is a high-speed prototyping with high precision. Concerning the field of tertiary necrolithography.

Background of the invention 3D stereolithography is a model for forming molds and testing functionality. This is a recently developed prototype technology for high-speed manufacturing of Computer-assisted design (CAD) and computers without tools Using computer-assisted manufacturing (CAM), various types of objects can be created. This is a revolutionary method of manufacturing.

U.S. Patent Nos. 4.575.330 and 4.929.402 to Hull Create a CAD file of the desired object and convert it mathematically as described in Convert to stacked sections or layers.

The first layer of the object is ethylene-coated by a polymerization initiating source, typically an ultraviolet laser. Scan over the surface of the unsaturated monomer vat. After that, on the elevator platform of the bat The actuator lowers the first layer of the model by a programmed distance. so that a new coating of polymerizable liquid covers the solidified layer. wiper The blade completes the coating thickness and then the laser Draw a new layer on top of the previous layer (repeat this step until the desired three-dimensional construct is obtained) repeat. Webbing may be included in the design if necessary to prevent object protrusions from becoming loose. may be added.

The resulting body (green body) is a partially cured construct. removed from bat After that, the green body is cured and, if necessary, papered or otherwise Smooth using this method.

The °330 patent (see Figure 4 of the '330 patent) provides that, in another embodiment, ultraviolet A layer of UV-transparent liquid that is heavier than the line-curable liquid and cannot be mixed is suspended in the vat. It teaches that , in this embodiment, the UV source is from below the vat. The UV light is irradiated through the transparent material and collects at the interface of the two liquids. °330 special Rather than submerging the object deeper into the liquid, UV curing is Draw from sexual fluids. This embodiment minimizes the amount of curable material used. It is useful for However, if the green body is not completely polymerized, it may sag. It can be deformed.

U.S. Pat. No. 5,011,635 to Murphy et al. a virtually impermeable transferable membrane, a liquid located on the membrane that can be polymerized by irradiation; three-dimensional stereolithography comprising an organic phase and an irradiation source located above the organic phase We provide equipment for This system also eliminates the need for polymerizable buffers in the equipment. The amount of liquid can be reduced. However, the presence of the membrane changes the criteria for material selection. It becomes more complicated.

U.S. Pat. No. 4,844,144 to Murphy describes three-dimensional stereolithography. Discloses a method for performing investment casting using a model manufactured by This method is used during prototyping during investment casting. Heating can weaken the pattern and cause the pattern to crack in the mold due to thermal expansion. Ethylenically unsaturated liquid mixed with an inert low thermoplastic material to prevent including using a polymer precursor fluid containing the material. Weakening of the part can lead to deformation. , and the final object becomes inaccurate.

The main problem with using 3D stereolithography for prototyping is It lacks tight dimensional tolerances.

One type of stress that causes deformation is when a material that is being converted from a liquid to a solid is already hard. Occurs when it comes into contact with and bonds with already oxidized materials. This stress causes each layer to peel away from the construct. Letting go causes winding deformation.

Another type of stress is the addition of heat, which causes the non-fully polymerized object to be annealed. (cured by panicle irradiation, or both at the same time). Na This is because, as the reaction continues, the already formed portion shrinks.

Additionally, the high temperatures required for curing in the absence of irradiation have an adverse effect on the object. hardening If the temperature is too high, the object will soften and even lose its shape.

The degree of dimensional deformation depends on the accuracy of the shape, the spatial design of the object, and the stress resistance of the object. and is determined by each part of the object. Currently, three-dimensional lithography is , advanced computer algorithms that attempt to anticipate and compensate for this shrinkage. Even if it is used, the accuracy is limited to a few tenths of an inch. Furthermore, after curing While warpage is reduced by increasing the butt hardening rate, The butt must be completely cured because of the internal stresses that occur with the subsequent deposition of layers. The rolling deformation increases significantly as the temperature increases.

An attempt to solve the problem of deformation after curing was published in U.S. Patent No. 4 by Murphy et al. ．． No. 942.001. According to this, preferably trifunctional 10-45% by weight liquid polyacrylate or polymethacrylate and 10-45% by weight 20-80% by weight resinous polymer dissolved in a mixture with %N-vinyl monomer. A vat solution containing lyacrylate or polymethacrylate is utilized. This melt When the liquid cures, it forms a lightly crosslinked, solvent-swellable polymer consisting of a heat-softening solid polymer. - provides a thin-walled component. Adding a resinous polymer to the monomer creates a polymerizable mixture The viscosity of the liquid may increase, which slows down the movement of the fluid and reduces curling deformation. Getting worse.

U.S. Pat. No. 4,945,032 to Murphy et al. Stop the irradiation at any point and then irradiate at least once during the formation of each surface layer. Repeatedly increases the strength and solvent resistance of the manufactured objects after curing. It is disclosed that deformation can be reduced. Preferably, the computer focuses Each surface layer is irradiated with ultraviolet light as a fast repeating process of laser scanning. do.

U.S. Pat. No. 4,972,006 to Murphy et al. The green body is immersed in an aqueous solution vat containing a water-soluble free radical catalyst. It is disclosed that the sinterable body can be hardened. Heat the vat for complete curing do.

Further curing can be achieved with catalysts in aqueous solution, but this technique does not alleviate the residual warpage problem that occurs in

U.S. Patent Nos. 4.999.143 and 5.059.359 to Hull et al. The issue describes, among other methods, a method of providing built-in support for objects (webs). Identify the object and use CAD to shape the surface of the solid model into a triangle (PHI GS) Rolling and deformation by dividing and getting better surface division It is disclosed that the amount can be reduced. Although this mechanical approach is useful, it Unnecessary and undesirable webs and supports are formed that must be removed.

U.S. Patent No. 5.015.424 to Sma 11ey deformation by preventing stress from being transferred from one part to another. Discloses that it can be reduced.

Design small holes or gaps at stress points in a CAD design or part By doing this, the layer parts that tend to roll up easily are separated. These gaps are It is called "Lee". Smalley is also known for bird nesting (rise and fall during production). In order to reduce unstable boundaries in the object that roughen the finished surface of the object is also used. This mechanical approach also introduces unnecessary complexity.

U.S. Patent Nos. 5.076,974 and 5.164.128 provide dimensional tolerances. Discloses a new partial construction technique called ``weave'' that improves performance. Typical The x-y cross-hatching method allows water to reach partially frozen eyes in the freezer tray. Captures liquid or semi-cured resin internally in much the same manner as it is captured in a cube. The thin-walled chambers to be captured are formed in a matrix shape that is relatively easy to ring.

As most of the liquid resin hardens in the vat, warpage after hardening is reduced and First, the surface finish is improved. Deformation after curing is due in part to less shrinkage after curing. decreases. However, the degree of cross-stripping of the beam increases and the generation of internal stress increases. As the degree of polymerization approaches 100%, the layer peels off from the structure. The resulting roll-up deformation increases significantly.

U.S. Patent No. 5.139.338, assigned to Cubital Ltd.; No. 5.157.423 describes the use of flash as a means of eliminating the associated problems after curing. Opens a method to create three-dimensional objects stereolithography using ultraviolet curing process. It shows. As with all rapid prototyping processes, solid-state or surface CAD models First, slice the roe into thin cross-sections. Then transfer the slices from your computer to the Transfer to a mask generator that acts as a photocopier. Charge a part of the surface and By “developing” the electrostatic latent image with powder, A negative image of the cross section is formed. At the same time, a thin layer of liquid photopolymer is applied to the work surface. Spread over the entire surface of the hole.

Then, place the mask plate with the negative image of the cross-sectional slice on the workbench. put it on. The shutter above both the mask and the workbench opens for 2 seconds, then It was irradiated by irradiating strong ultraviolet light from a 2 kilowatt lamp. Solidify the entire photopolymer layer at once. Areas outside the model remain liquid.

The irradiated mask is then physically polished and electrostatically discharged to release the mask from the mask plate. Remove the charge and prepare for the next negative cross-sectional image. At the same time, the forced air and Uncured polymer is removed from the workbench in combination with vacuum pressure. work The bench moves to the next station where hot wax is applied. The uncured polymer fills the cavity. next station smell and solidify the wax by applying a cooling plate.

The solidified Wa Cloth acts as a support construct and resists gravitational or contractile effects. Reduces deformation. Finally, cut the surface of the polymer/wax layer with a cutter to the desired thickness. Cut until.

This leaves the surface of the workpiece ready to receive the next polymer layer. this Repeat the process until the part is complete. Once the model is built, the support wack Clean the bath with microwave energy, hot air from a blower, and water containing solvents. Remove with agent. Each layer is fully cured so no further curing is required. Ru. Although this process can be used to form high precision parts, the stress between the layers during polymerization The part still shows some deformation due to force generation.

U.S. Pat. No. 4.752.498 and U.S. Pat. No. 4.801.477 A method for producing a stereolithography I- is described.

In this, a sufficiently rigid transparent plate or membrane is brought into contact with a liquid polymer precursor fluid. Keep the liquid in the desired shape by placing it in contact with the reaction vat, preferably to exclude air from the The volume within the vat allows for unlimited flow of fluid from around the irradiated area. There is no sealing of the plate as it varies depending on the supply. Additionally, a transparent plate to a material that leaves the irradiated polymer surface ready for further crosslinking. so that when the next layer is formed, it will adhere to the irradiated polymer surface. The above patent suggests that the solidified photopolymer can be deformed. To aid in releasing the layer without oxygen, copper or other It teaches that the compound is formed from or included in the molecule of a suppressor.

The highest precision theoretically achievable using three-dimensional stereolithography technology is diffraction limit (submicron). Manufactured by three-dimensional stereolithography Although the above techniques have been used to reduce deformation of objects that have been Not achieved yet. The mold is created using three-dimensional lithography that improves precision. There is a need to provide a method for manufacturing models that can be formed and function as desired.

High precision microelectronics with high image ratio and high construction height necessary for the production of micro and small constructs used in Micro and small constructs are typical It is generally manufactured by optical lithography, and optical lithography is The critical dimension of 0.5 μm (CD ) has been perfected to achieve. This technical description applies to batteries on silicon wafers. micro-sensors and micro-apertures by either lubrication or micro-machining. Modified to produce actuators.

High-field-of-image-ratio microconstructs can also be exposed to X-ray radiation by high quantum energy synchrotron irradiation. Manufactured using lithography. “Riga (LIGA) J process (Beraka) -ra, Microelectronic Engineering 4 (19 86) See pages 35-56 and U.S. Pat. No. 4,990,827) According to horizontal dimensions in the micrometer range and hundreds of micrometers A microconstruct is produced having a construct height of . The Riga process is schematically shown in Figure 1. . Polymers whose dissolution rate changes in liquid solvent (developer) by high-energy irradiation - The material (resist) is irradiated with intense parallel X-rays through an X-ray mask.

Teru J1 is suitable for precision deep etch X-ray lithography in thick resist layers. electron beams capable of generating highly collimated photon fluxes in the required spectral range. It is a crotron or electron storage ring. For example, 10 and 1,000 μm Patterns with thicknesses between 0. Optimal temperature between 1 and 1 nm Requires synchrotron irradiation at field wavelength. In the next step, the metal is Resist as a template in the electroforming (electroforming) process for depositing onto conductive substrates Use constructs. Then, the polymer resist is removed and the high precision metal mold is installed. supply Insert the polymer mold material into the metal mold key through the holes in the gate plate. A second plastic mold is formed by introducing the mold into the mold cavity. pre The mold is in engagement with the polymeric microconstruct, and after curing the mold resin, The plate is connected to the electrode in a second electroforming process to form a second metal microconstruct. It works. According to Riga process, image ratio up to 100 and micrometer A high precision second construct is manufactured, including a construct having a minimum horizontal dimension in the range of .

The Riga process includes microsensors, measurement devices that measure vibration and acceleration, micro For the production of optical devices and symmetrical liquid devices, as well as electrical and optical microconnectors. It is used. The main disadvantage with the Rigging process is that the fully attached metal structure Only built-in structures can be manufactured, and electronic sinks are not readily available. This requires the use of a rotron.

Guckel et al. l Conference on 5 solid-state 5 sensors and Actuators, 1991) is called Sacrificial Liga (SLIGA). We are reporting on a new process that can be done. This process is shown in FIG. Add sacrificial layer to Riga process By adding fully attached metal construction, partially attached The production of metal constructs and completely free metal constructs is facilitated. The thickness of the device It is typically larger than 10 μm and smaller than 300 μm, so it is cut out. If the stress applied to the membrane can be appropriately controlled, the self-supporting structure will undergo shape deformation. I don't. However, this process also requires the use of an electronic synchrotron, which is not readily available. Microelectronic technology that does not require the use of zero-electron synchrotrons It is advantageous to provide an apparatus and method for manufacturing high image ratio micro and small structures for It is for use.

Therefore, an object of the present invention is to create a three-dimensional solid lithography system that minimizes deformation of an object. An object of the present invention is to provide a method of manufacturing an object by graphography.

Other objects of the invention are to expand the selection of polymer precursors to include slow reacting systems and , upon solidification, the dual properties of polymer and ceramic and/or magnetic, electrical particles that form real parts with optical or optical properties. The purpose is to contain a fluid.

Still another object of the present invention is to achieve precise polymerization in a short time so that the real part can be quickly produced. The goal is to make sure that it can occur.

Still another object of the present invention is to provide high image ratio micro and An object of the present invention is to provide a process and apparatus for manufacturing small constructs.

Summary of the invention High-precision fabrication of large-scale, micro-, and small-scale constructs using 3D stereolithography A method and apparatus for manufacturing are disclosed. Objects manufactured using these methods are , with minimal stress between layers and low roll-up deformation. The object also hardens Since no post-processing is required, there is less warping.

In one embodiment, constructed using three-dimensional stereolithography under high pressure Things are manufactured. The use of high pressures results in high temperatures and/or viscosity in the reaction vat. This allows the use of synthetic polymer precursors. The pressure applied in the vat causes the solid to , magnetic particles, dielectric particles, ceramic particles, liquid crystals, liquid crystal polymers, nonlinear optics Inert polymeric or non-centrosymmetric halves, conductive particles, and conductive polymers. enables the formation of real objects (vs. prototypes) containing polymeric or non-polymeric materials. Ru. Magnetic particles, liquid crystals, liquid crystal polymers, and non-centrosymmetric halves are sensitive to magnetic or electric fields. can be properly aligned by adding .

In another embodiment, an improvement in a three-dimensional stereolithography step is provided. Ru. There, the polymer precursor fluid is moved in a differential manner along the tip. Together, the material ahead of the moving polymer region remains liquid, while the material behind the tip remains liquid. Related to stress in polymeric materials by allowing the material to solidify Deformation is minimized. Typically, the moving tip is transparent to ultraviolet light. It is a slit. Alternatively, the moving tip can open the radial opening of the iris diaphragm. It is. Then, the static liquid crystal material in front of the moving polymer region is equal to the contraction rate A stress-reduced polymer network that can flow freely at speeds of It is formed. Using this process, objects are produced by shrinkage of the material during polymerization. It may be cast in a manner that prevents cavities or hollow areas from being scratched. this method is hereinafter referred to as a "continuous polymerization" modification of three-dimensional stereolithography.

The continuous polymerization modification process of three-dimensional stereolithography can be performed at ambient pressure, high pressure or high temperature, or can be carried out at high temperature and pressure.

A two-phase vat solution containing an inert immiscible fluid below the polymer precursor fluid can be used. Ru. In another embodiment, the headspace is gas phase (or ultraviolet transparent but A multiphase system is used that is a light fluid (immiscible with the polymer precursor fluid). . There is no gas (inert or active) or intervening between the horizontal window and the reaction mixture. By using an existing fluid layer, the layer is prevented from sticking to the window. inert The fluid also prevents the polymer precursor fluid from adversely affecting the pressure application means. Ru.

Microphone demonstrating the precision of constructs manufactured using LIGA or 5LIGA technology Small and microconstructs for electronics can be constructed using the methods described herein. can be manufactured. For example, a continuously moving slit system as shown in FIGS. Selective high pressure or The polymer precursor fluid is applied to a pattern formed by a photomask at high temperatures. irradiate with a light beam. After the polymer layer with the desired pattern is formed, the actuator The elevator mechanism raises the tier (attached to the elevator platform) by a differential amount. so that unirradiated polymer fluid covers the layer. Then, the unirradiated polymer stream The body is polymerized in the desired pattern on top of the previous layer.

This process is repeated until the desired three-dimensional construct is obtained.

Once the precision plastic mold is complete, it is removed from the vat and typically Electroplating with Kkel. Then, remove the plastic mold and free A metal construct is cast.

Brief description of the drawing FIG. 1 is a cross-sectional view of an apparatus for high-pressure three-dimensional stereolithography.

Figure 2 shows the monomer/precursor pool ( FIG. 2 is an enlarged view of a local region of pool.

Figure 3 shows how an electric field or 1 is a cross-sectional view of an apparatus for high-pressure three-dimensional stereolithography, including means for applying a magnetic field; FIG. Ru.

Figure 4 shows a two-phase vat flow in which the bottom fluid is inert and the top fluid is a polymer precursor fluid. 1 is a cross-sectional view of an apparatus for high pressure three-dimensional stereolithography, including a body.

Figure 5 shows the bottom fluid being inert, the next layer being the polymer precursor fluid, and the ultraviolet Upper gas or light fluid phase that is radiolucent but immiscible with the polymer precursor fluid In a cross-sectional view of an apparatus for high-pressure three-dimensional stereolithography, including a three-phase vat fluid containing be.

Figure 6 shows a lower hydraulic fluid, polymer precursor fluid, that is inert and UV transparent. an upper gas or light fluid phase that is immiscible with the polymer precursor fluid. containing a three-phase butt fluid, a portion of which is drawn from a polymer precursor fluid. FIG. 1 is a cross-sectional view of an apparatus for pressure three-dimensional stereolithography.

Figure 7 is a cross-sectional view of a method for manufacturing micro or small constructs using LIGA technology. Ru.

Figure 8 is a cross-sectional view of a method for manufacturing micro or small constructs using 5LIGA technology. be.

FIG. 93 shows three-dimensional stereolithography in which a polymer precursor fluid is continuously polymerized. (Vl is the first valve, ■2 is the second valve) Valves, S■1 is the first solenoid valve, Sv2 is the second solenoid valve, Ql is a quick connect).

Figure 9b includes a top view of the apparatus shown in Figure 9a for introduction and removal of the desired material. Figure 3 shows a side view of the device showing a further valve boat and a wiper mechanism.

Figure 10 shows a continuous moving slit system (SMSS) for the production of three-dimensional objects. FIG. 3 is a partial cross-sectional view of the device.

Figure 11 shows an apparatus for manufacturing three-dimensional objects, including a computerized iris diaphragm (CID). FIG.

Figure 12 shows polymer precursors subjected to UV light irradiation via a continuously moving slit system. FIG. 3 is an enlarged view of a localized region of body fluid.

Figure 13 shows an object manufactured by three-dimensional stereolithography, on which it is attached. FIG. 2 is a schematic diagram of a device for efficiently removing a transparent plate from which a transparent plate is being removed. Tooru Etch the bright plate and make the etched recess into a refractor that fits the transparent plate. Filling with a flexible material with a Place the tape with the adhesive side on the transparent plate. with the non-adhesive side facing the polymer precursor fluid and the object made therefrom. Place it on a glass plate in such a way that the

FIG. 14 shows how microelectronics can be constructed using the methods disclosed herein. FIG.

' Figure 15 shows a sample fabricated using the three-dimensional stereolithography method disclosed herein. FIG. 2 is a schematic diagram of an example of a construct that can be used.

FIG. 16 can be manufactured from a mold formed by the methods described herein. FIG. 2 is a cross-sectional view of a tapered honeycomb structure.

Detailed description of the invention As used herein, the term small construct is typically less than about 10 microns in height. It refers to constructs that are no larger than about 103 microns.

As used herein, the term microconstruct is typically about 10 microns or less in height. means a small construction.

The term large scale construct refers to a construct larger than xo'' microns.

Fabricate large-scale, micro-, and small-scale constructs with high precision using 3D stereolithography A method and apparatus for manufacturing are disclosed.

As a method, one step of three-dimensional stereolithography is performed under high pressure, high temperature, or Includes continuous polymerization of polymer precursor fluids, or using combinations thereof. Ru.

■ 3D stereolithography at high pressure, high temperature, or under high pressure and high temperature. Formation of the object used Highly precise object formation using three-dimensional lithography under high pressure A method and apparatus for forming a body are disclosed. The use of high pressure in the reaction vat Allows selective use of high temperature and/or viscous polymer precursors. reaction bat The use of high temperatures in causes rapid polymerization and nearly completion during the formation of the green body. reaching a near stage. As a result, shrinkage and dimensional changes due to annealing are significantly reduced. Do a little. The high-pressure process is itself rapid, so partially polymerized starting materials, or acrylates or methacrylates or other materials that do not polymerize easily. can be forced. Therefore, high polymerization rate and selected from various chemicals The green body is produced to allow cross-linking during or after UV irradiation in the It can be done.

The use of high pressure in the reaction process also affects fillers, additives, colloidal particles, magnetic particles materials, and objects containing non-polymeric materials such as inert polymers.

The process disclosed herein comprises a permanent magnet construction (I) for horizontal spiral mound formation. EEE Transactions on Magnetics.

Vol.Mag 22(5), September 1986) and an increasing periodic magnetic field. traveling wave tube (IEEE Transactions on Magneti) complex three-dimensional magnetism such as CS, VoI Mag 25 (5), September 1989) It can be used to form air constructs.

Three-dimensional stereophosphoric graphs, such as acrylic and methacrylic esters, “- Typical ethylenically unsaturated monomers used in the manufacture of objects by Has significant vapor pressure at or near ambient temperature. Disclosed herein A closed reaction vat prevents evaporation. High pressure in the vat The use allows the monomer or precursor to be It becomes possible for the polymerization reaction to proceed at a constant high temperature. Polymerization proceeds at high temperature and pressure. go High pressure minimizes the amount of shrinkage due to monomer to polymer conversion. be controlled.

Three-dimensional stereolithography using high hydrostatic pressure, and optionally high temperature, as described herein. There is one method to improve the precision of the part formed by the fee. It is a general technology, not limited to devices. As mentioned in the Background of the Invention section , numerous devices for rapid prototyping using 3D stereolithography technology. is being developed. 3DS Systems, Inc., 5Cutival Amer ica Inc, Quadrax Laser Technologies, I nc, Light Sculping Inc, DTM Corporation ion, and others. Saw for 3D stereolithography The deformation of objects formed by any of these well-known methods and devices is hydrostatic It can be relieved by increasing the pressure. By using a pressurized gas phase, or by draining or adding an inert fluid and introducing a polymeric fluid. A system that works by increasing the level of resin at the expense of decreasing resin. may be used in this step.

FIG. 1 is a cross-sectional view of an example of an apparatus for high-precision three-dimensional stereolithography. Poly A mer precursor fluid 1o is contained in a reaction vat 12. The reaction vat is a rectangular parallelepiped It can have any shape, such as four orthogonal sides, such as in a box, or a cylinder. obtain. A bat with a cylindrical cross section may be a suitable construction for high internal pressure. Ba Means 14 for increasing the hydrostatic pressure in the vat are attached to the vat. increase pressure Examples of elevating means include pumps, HPLC or supercritical fluid extraction. Examples include compressors, hydraulic pumps, or piston-cylinder structures. but not limited to. One side of the reaction vat 12 is a window 16. A polymerization initiation source 18 moves through this. Initiation source 18 is typically an ultraviolet radiation laser. pattern in the layer of precursor fluid close to the top surface of the pool. pattern By locally photopolymerizing the pool in selected areas indicated by the laser It is formed. When the first layer is finished, the actuator mechanism 20 is moved onto the elevator platform 22. differentially lower the layer with the image of the fresh (unirradiated) precursor The fluid 10 is allowed to cover the underlying patterned layer. After that, the process is repeated, and in this way a new pattern is superimposed. Combined with a lowering platform By repeatedly using the laser at the same time, a series of images with the final part made rigid is created. A complex three-dimensional construct 24 consisting of layers is gradually formed. The unreacted fluid 10 is This part (unfired body) is discharged.

Heating can be done using coated vats, immersion coils, infrared heat lamps, or electric cartridge heaters. , including wire-wound heating tape, microwave heaters, or placing a bat in a furnace. It can be performed by standard means, but is not limited thereto.

Shrinkage of local polymerized regions within the object is minimized using this technique. It will be done. This is because when polymerization occurs, the high hydrostatic pressure within the pool forces more polymer into the pool. This is because the mer precursor fluid quickly flows into the irradiated area. empty due to contraction Further precursor fluid quickly polymerizes in the irradiated area. This is shown in Figure 2. vinegar. FIG. 2 shows a precursor fluid pool irradiated by an ultraviolet laser beam 26. FIG. 3 is an enlarged view of a local area. Shrinkage 28 is performed before additional polymer under high hydrostatic pressure. This is compensated by the rapid inflow of precursor fluid 24. Obtained green body 30 is already almost completely polymerized (and in some cases cross-linked), so it cannot be annealed. It does not shrink much during cleaning.

High-precision three-dimensional stereolithography minimizes roll-up deformation. winding up Deformation is a complex phenomenon. This is mainly due to the stress relaxation rate at the precipitation temperature. More controlled, the total residual shrinkage of the newly formed layer is fixed to the layer below it ( It is attached). The use of high temperatures ensures rapid polymerization, thereby producing new The new layer is almost completely converted to polymer. Therefore, residual shrinkage is kept to a minimum. It will be done. Furthermore, stress relaxation increases with increasing temperature and therefore during manufacturing By carefully selecting the temperature, proper relaxation can be achieved in the object.

The degree of curing that occurs in a closed vat is determined by removing the uncured material in the object using a suitable solvent. capacity by extracting the material and then comparing the weight and dimensions of the object before and after extraction. can be easily evaluated. Methyl ethyl ketone is a common solvent used for this purpose. be.

l fork The temperature within the closed, pressurized vat ranges from ambient temperature or below. The bat can withstand and induce unwanted side reactions without adversely affecting the quality of the object Any high temperature is possible unless To heat the reaction vat, it is necessary to Any means known to those skilled in the art may be used. The upper limit of the temperature used is also (1) closed The material of which the mold bat is made (e.g., is the device made of metal, stainless steel, or an alloy? The windows are thick enough to withstand thousands of pounds per square inch of pressure and temperature. (including but not limited to quartz or sapphire); (2) polyester glass; mer precursor fluid volatility (e.g., vapor pressure using monomer/polymer mixtures) (3) Standard Generally, organic decomposition (oxidative decomposition or (depolymerization) is influenced by a number of factors, including temperature. The process described in this specification Typical temperatures for temperatures range from 30 to 300°C, more typically 10°C. It is 0-300°C. Self? +J-+Jlfl! mt l-QhJ- $;W+Fj-1%fl-)/y2;/r'+-y　/+: To prevent natural convection, It is preferable to maintain a uniform temperature throughout the vat. to any system However, the optimum operating temperature can be easily determined by running the process at a temperature within this range. can be determined.

Superheated liquids may be used in this step. However, oxidative and thermally induced polymerization Care must be taken to avoid this.

pressure In closed vats, it reduces deformation of the object during manufacture or improves general quality. Any high pressure can be used as long as it improves. The pressure used in the vat is Pressure slightly higher than ambient pressure, e.g. 50-100 psi to 100°000 psi (pounds per square inch), more typically 50 or is from 100 psi to 10,000 psi. Using high pressure can cause viscous Starting materials can be used and density control with two-phase and multi-phase systems Risk of floating debris and need for web support decreases.

Monomer boiling or evaporation (these are the minimum required at constant operating temperature) The relationship between pressure and temperature determined by Toine's ceremony or open-1 shishi shi evil G kob oi or kufunwasu kufupeiro It is determined by the C1asius-C1apeyron equation. pressure and temperature for a given polymer precursor fluid by testing each Should be optimized.

For example, if the monomer is not very volatile, higher pressure and slightly higher temperature may be appropriate. can be obtained.

The transparent window shall be attached to the container by an adhesive that can withstand the desired high temperatures. do not have. Alternatively, O-rings or other materials that can withstand high temperatures can also be used to attach windows. can be used.

means of increasing pressure There are many known means for increasing the hydrostatic pressure of the fluid within the hat. This method Any of these well-known means may also be used. For example, as shown in Figure 1 Alternatively, a simple pressure pump can be connected to the device. Other examples of means of increasing pressure and Compressors, fluids, such as those used in HPLC or supercritical fluid extraction pressure pumps and piston-cylinder constructions, or sources of compressed gas; but not limited to.

1i-III P-Wc Any polymerization initiation source that can migrate through the window can be used in this method. suitable The starting source is an ultraviolet radiation laser or ultraviolet light from a mercury vapor lamp. the standard used Typically the wavelength is between 300 and 400 nm. Ultraviolet laser is quartz, saf UV-transparent windows formed from fused silica or Are known. 5chott Bk7 glass is also suitable as a UV transparent window. It is.

According to methods and conditions known to those skilled in the art, heat can also be used as a source of polymerization initiation. It can be done.

polymer precursor fluid Fast curing monomers such as acrylic esters or methacrylic esters are Ideal for use as a polymer precursor fluid. its acrylate or meth Lyric acid salts can be monomers, oligomers, or polymers, or mixtures thereof. could be. The higher the percentage of acrylate component, the faster the cure generally. numerous poly mer precursor fluids are well known and for use in three-dimensional stereolithography. are available on the market. For example, C1ba Geigy Corporation on is acrylic acid used in equipment sold by 3D Systems, Inc. o DeSoto Chemicals, In which sells salt-based fluids. c.

Also, Quadrax La5er Technologies, Inc. sells acrylate-based materials useful in the equipment it sells. du Pa Somos 2100 Photopoly sold by nt/Somos Venture Mer is a precursor fluid that contains acrylate as a subcomponent.

Another suitable material is a modified material sold by Locktite Corporation. Potting Compound 363 is an acrylic acid salt.

Ultraviolet curable resins are also described in U.S. Pat. ．． No. 001. Those skilled in the art will know of other UV curable coatings. dings, fests, and adhesives are also well known.

In prior art three-dimensional stereolithography systems, unirradiated material is newly formed. low viscosity so that it can flow freely and quickly over the surface of the polymer layer. polymer precursor fluids (such as free methacrylate or acrylate monomers) ) is required. The resulting low molecular weight dead polymer is left in the final section and is causing dimensional instability over a period of time. Due to the use of high pressure and high temperature, more viscous, preferably containing components of relatively high molecular weight, or by reaction This allows for the use of precursor fluids to form quantities of materials. - For example, before thermosetting There is a precursor fluid.

Thermoset defective works are typically highly crosslinked.

Examples include UV-curable epoxies, polyfunctional acrylates, and polyunsaturated polymers. Rimmer is an example. Substantially reduced deformation as a result of using thermoset precursor fluids A green body is obtained. The reason is that the degree of crosslinking during green body formation and precipitation is high. This is because the residual deformation after annealing is smaller.

The polymer precursor fluid is such that a solid or suitable semi-solid layer is formed upon initiation. It should cure sufficiently quickly under such conditions of use. Persons described in this specification The high pressure and selectively high temperature conditions used in the Styrene and ants could not be used due to too slow polymerization rate. This allows for the use of precursor fluids containing monomers terminated with fluorophores.

Also acrylate-terminated or unsaturated urethanes, carbonates, and epoxies It can also be used in rigid frames. An example of an unsaturated carbonate is Allyljig Recall carbonate (CR-39). Unsaturated epoxies that can be used include: Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and 1,2-epoxy-3-allylpropane. do not have.

Other monomers that can be used in high-pressure, high-temperature three-dimensional stereolithography vats Examples include N-vinyl monomers including N-vinylpyrrolidine, bisphenol-A- Bis-2-hydroxypropyl methacrylate, bisphenol-A-bis-2 -Hydroxypropyl acrylate, bisphenol-A-ethoxy diacrylate tri- or tetrafunctional acrylates or methacrylates, ethylene glycol Alkylene containing dimethacrylate and ethylene glycol diacrylate Recall diacrylate, alkylene glycol methacrylate, polyalkylene glycol diacrylate and polyalkylene glycol methacrylate, Propoxylated neopentyl glycol diacrylate, vinyl acrylate, Vinyl methacrylate, allyl acrylate, allyl methacrylate, divinyl Benzene, diallyl diglycol dicarbonate, diallyl maleate, diallyl Vinyl esthetics such as rufumarate, diallyl itaconate, and divinylmalonetona divinyl malonate, diallyl succinate, triallyl isocyanurate , bis-phenol A or ethoxylated bis-phenol A dimethacrylate or diacrylate, hexamethylene bisacrylamide or hexamethylene methylene or polymethylene bisacrylamide, including bismethacrylamide or bismethacrylamide, di(alkene) tertiary amine, trimethylolpropylene Pantriacrylate, Pentaerythritol Tetraacrylate, Divinyl ether, divinyl sulfone, diallyl phthalate, triallylmelamine, 2-i 2-incyanate ethyl methacrylate, 2-incyanate ethyl acrylate, 3-incyanate propyl acrylate, 1-methyl-2-incyanate ethyl methacrylate, and 1,1-dimethyl-2-incyanate ethyl acrylate It is related. Perfluorinated and semifluorinated derivatives of the compounds listed above are also available. is appropriate. Fluorinated monomers or polymers may also be used, e.g. in the form of non-viscous moieties. It can be used for construction.

Preformed polymers with ethylenically unsaturated groups may also be used in the precursor polymer stream. It can be used in body formation. These are acrylate-terminated novolaks, and polyurethanes, polymeric epoxies, and derived acrylates, meth Contains polycarbonates containing acrylate or other unsaturated functional groups. these Types of polymers are well known and commercially available. market available light An example of a polymerizable material is Sy, sold by Cray Valley Products. nocure product series (e.g. diacrylate derivatives of bisphenol A) 5ynocure 3101 which is and 5ynocure which is diacrylic acid aliphatic urethane ynocure 3134) and 5hell Corporation. Epon products sold (for example, all of them are bisphenol A diglycidyl ether) Epon 1001 and EpOn 828) are diacrylates of . Vinyl terminated liquid crystal polymers may also be used.

In another embodiment, the entire mixture is thickened for easier handling. Inert polymers are used as starting materials to shorten reaction times or for other reasons. may be added to the ingredients. Inert polymeric materials do not adversely affect the desired properties of the target substance. Unless otherwise specified, any polymer may be used and any amount may be used. one In general, inert polymers are polymers that do not react with other compounds in the reaction solution. be. In one embodiment, an inert polymer of hard monomer or hard material A remer is added to the polymerization solution. For example, polymer networks can be used as hard monomers. If methyl methacrylate is used in the solution, polymethyl methacrylate will polymerize. can be added to the solution. Inert materials can be used as long as they form parts with the desired properties. Any amount can be present in the polymer precursor fluid. Contains latex rubber The final material thus has a high degree of impact resistance. Typical ranges of inert materials include: 1% to 90% by weight of the polymer precursor fluid.

Non-polymeric fillers may also be added to the polymer precursor fluid. these are, CaCo, carbonates such as MgCO5, and clays including attapulgite clays. -, borates, sulfates, phosphates, celite and silica powder, etc. of diatomaceous earth, alumina, colloidal silica and zeolite solids, which Not limited. A filler is a volume that prevents a mixture from flowing no matter how much pressure is applied. may be added up to an amount. Typically 64% theoretical monotony as an upper limit for backing There is a san method.

Colloidal particles suspended by Brownian motion may be used. These are Idic gold, titanium oxide, iron oxide (magnetic), cobalt, molybdenum oxide, vana oxide Dium, nickel, alloys, transition metal-rare earth complexes, silicon dioxide, silicon nitride germanium oxide, silicon atoms, gallium arsenide, and other semiconductor particles. including.

Other inorganic particles such as sulfides and chlorides may also be used. Organic particles are Bridged beads (colloids range from the smallest to micron-sized spheres) obtain. Since most organic materials have approximately the same density, large organic particles are less likely to aggregate. It can be easily dispersed in fluids without binding.

Contains magnetic particles In another embodiment, magnetic particles may be contained in a polymer precursor solution. non-limiting An example is a magnetic material as described above containing iron oxide and a transition metal/clay compound in the form of small particles. Contains particles.

During laser irradiation, small magnetized areas, such as small motors and actuators, , the S-N poles may be aligned so that the sensor is formed, and then the resin may be cured. . Complex keys and locks can be formed using this procedure. The lock is activated by the induced current in the coil. Read the code. When the key is turned, the embedded information is read.

By 3D-stereolithography using magnetic particles in a polymer precursor liquid By controlling the electric field in the coil attached to the fabricated rod, It is possible to make dense movements. By incorporating hardened fine magnets into resin. Rods with complex information embedded by Manufactured using a method.

The rod is then connected to a variable voltage power source. Each time the current in the coil changes, the The head moves in a controlled manner.

Liquid crystal molecules (e.g. ferroelectric, cholesteric, nematic, stent methic, etc.), liquid crystal-like molecules or aggregates are aligned, and display or light Incorporated into resin for induction applications.

Nonlinear optically active compounds such as non-axisymmetric molecules and block polymers, graphs The top polymer, or copolymer, can be cured in a three-dimensionally controlled manner, and Therefore, very complex integrated light with horizontal and vertical light guiding and light modulating capabilities. Manufactures academic parts.

Figure 3 shows magnetic particles dispersed in a polymer precursor liquid by applying an electric or magnetic field. Illustration of an apparatus for high-pressure three-dimensional stereolithography, with means for performing an alignment of the It is. Ultraviolet light is applied to the polymer precursor liquid 32 containing magnetic particles or ferroelectric liquid crystals. The laser beam 34 is irradiated between the electrodes or magnets 36 and 38 and placed on the table 42. A certain object 40 is generated. Water pressure is applied by the pump 44 to the heating means 46. Therefore, the temperature increases. The upper limit of the electric field is the breakdown strength of the liquid, typically I The range is MY/cm. The upper limit of the magnetic field is the limit of available electromagnets. nuclear magnetism Large electromagnets, such as those used for resonance, produce very strong magnetic fields. magnetic The field can be oscillated in a controlled manner or reversed as desired.

Also, the magnetic fields can be crossed or rotated. The generated object has a magnetized area and a magnetic It may have an area that is not

Electric or magnetic fields can be applied horizontally and vertically.

Furthermore, particles in an object are turned off when an electric or magnetic field is turned on. They are arranged differently depending on when they are turned or reversed. be done. As is clear from the description in the specification, high-voltage three-dimensional stereolithography can contain fillers, additives, or magnetic particles in the object, so this technique is only used to manufacture actual parts, not models or prototypes. obtain. Additionally, this technology produces components that perform active functions such as motion control and light guidance. It is possible.

Two-phase butt liquid or phase butt liquid In another embodiment, the polymer precursor liquid is stored and a hydraulic fluid is used to pressurize the system. An immiscible liquid (inert liquid) is used in a high-pressure vat to act as a obtain. The inert material is typically located at the bottom of the bat, as shown in Figures 4 and 5. It is in.

The inert material is immiscible with the UV curable material and contains no uncured UV material. It has a density intermediate between that of a V-curable material and a cured UV-curable material. harden liquid , the hardened liquid (at this point a polymer) is heavier than the inert material ( become denser). The laser emits a quartz or saph crystal on a closed, pressurized container. The inert material does not need to be UV transparent as it is focused by the fire window. . Separating two liquids as disclosed in U.S. Patent No. 5.011.635 A thin film is not required in this system. If the inert material is transparent, it is shown in Figure 6. UV irradiation can be performed from the bottom of the vat as described above.

Silicones and fluoromers (fluorocarbons or fluorocarbon liquids) ) are ideal candidates for inert liquids. The density of these substances is monomer is higher than that of the polymer precursor (and the polymer that has finished polymerization (the finished polymer) ) lower than The buoyancy effect as the part descends in the inert liquid causes it to drop under gravity. to prevent parts from deforming (distorting). A non-limiting example is alkanes and PFA. Fluorine liquid is E, 1. du Pont de NeMours and Company and Mfnnesota Min Sold by ing and IarltlfaCturfJ’1g Company are doing. The silicone cone fluid contains polydimethylsiloxane oligomers and aromatic silicones. Contains loxane or aliphatic siloxane. Huls Corporate Jan manufactures all silicone fluids.

The inert liquid may be water, glycerol, glycol, alcohol, or may be a liquid fluorinated derivative.

Inert liquids perform at least three additional important functions. i.e. excess material (non-polymerized substances that adhere to the substrate) and transmit the applied high pressure. physical separation of the pump from the polymer precursor liquid. . The vat may be under increased pressure by ductwork attached to the vessel. The duct is physically separated from the polymer precursor material, thereby preventing blockage. can be prevented. When υV curable liquid is in the pump duct, even stray light will not penetrate the opening. May cause undesirable polymerization sufficient to cause blockage. Figure 4 shows an example of an apparatus for high-pressure three-dimensional stereolithography containing a two-phase liquid. It is a sectional view of a type. The polymer precursor liquid 48 is transferred to a pressurized reaction vat 52. floating on an inert solution 50 inside. Static water in a vat, typically a pump Means 54 for increasing the pressure is attached to the butt below the interface 56 of the two liquids. There is. A polymer starting source 58 is transmitted through window 6o. Typically UV light An initiation source 58, which is a laser, applies a pattern to the layer of precursor liquid proximate the top surface of the pool. Write. Once the layer is complete, the actuator mechanism 62 is placed into the inert liquid 50. The imaged polymerized layer (which is denser than the inert liquid at this point) is precipitated. Melt. The raw (unexposed) precursor solution 52 is then transferred to an interface of two liquids. Float the surface onto the imaged layer. This process is then repeated to create a new The pattern is placed on top.

A complex three-dimensional structure 64 is created by repeatedly using the laser while gradually lowering the platform. It is configured on a stand 66. In a three-dimensional structure, the last part is a series of fixed images. It is made up of layers and is immersed in an inert liquid 50. The inert liquid 50 is the unreacted liquid 48 and drain the parts (substrate).

1 to 6, polymer precursor liquid, inert liquid and inert gas, or A duct into which a lightweight liquid is added and appropriately placed as desired in a device not shown. removed.

Figure 5 shows a cross-section of the apparatus for high-pressure three-dimensional stereolithography containing a three-phase vat liquid. The three-phase vat liquid is an inert bottom liquid, the next layer is the polymer Precursor liquid 70 and UV transparent, but immiscible with the polymer precursor liquid. The upper gas phase or light liquid phase 72 is included.

Means 74 for increasing hydrostatic pressure in the vat, typically a pump, pumps the polymer precursor liquid. It is attached to the butt below the body 70. Polymer initiation source 76 passes through window 78. Reportedly. A starting source 76, typically an ultraviolet laser, is placed on the top surface of the pool. A pattern is written in a layer of adjacent precursor liquid. Once the layer is complete, the actiniator Mechanism 80 contains an imaged polymerized layer (at this point denser than the inert liquid). ) into inert liquid 68. Next, the raw (unexposed) precursor solution is A liquid 70 is suspended over the imaged layer at the interface of the two liquids. stop The process is then repeated and a new pattern is overlaid. Gradually lower the stand. A complex three-dimensional structure 82 is constructed on the table 84 by repeatedly using the laser while lowering it. to be accomplished. In a three-dimensional structure, the last part consists of successive layers of fixed Immersed in inert liquid 68. Inert liquid 68 drops unreacted liquid 70 and parts ( Drain the substrate.

Figure 6 shows a cross-section of the apparatus for high-pressure three-dimensional stereolithography containing a three-phase vat liquid. The three-phase vat liquid is inert and the lower liquid is UV transparent. , the next layer, polymer precursor liquid 90, and the polymer precursor liquid are mixed. The part contains a polymer precursor liquid, including an upper gas phase or a light liquid phase 92. being pulled up. A means of increasing hydrostatic pressure in the vat, typically a pump 94 is attached to the vat below the polymer precursor liquid 90. polymer start Source 96 is transmitted through window 98. Starting source, typically an ultraviolet laser 96 writes a pattern in the precursor liquid near the top surface of the pool on the platform 104. It's crowded. Once the layer is complete, the actiniator mechanism 100 transfers the imaged polymerized layer. lift up. The raw (unexposed) precursor liquid 90 is then divided into two liquids. At the body interface, the image is floated on the formed layer. This process is then repeated and a new pattern is placed on top. Laser while gradually raising the platform is used repeatedly to construct a complex three-dimensional structure 102 on the stand 104.

Il, using three-dimensional stereolithography involving sequential polymerization of polymer precursor fluids. Preparation of objects In functional embodiments, large-scale constructs, small-scale constructs, and microscale constructs are , prepared by three-dimensional stereolithography. with 3D stereolithography points to reduce construct distortion caused by intra- and inter-layer stresses. The remer precursor fluid is continuously polymerized. This method deals with warpage strain during the polymerization process. Reduces discomfort. Continuous polymerization modification of the three-dimensional stereolithography process can be performed at room temperature. and atmospheric pressure, room temperature and high pressure, high temperature and atmospheric pressure, or high pressure and high temperature. It can be implemented by The parameters and reaction conditions listed in Section I are , suitable for the methods disclosed in Section II, including when carried out under ambient conditions. used.

Continuous polymerization technology is described in US Pat. No. 5, filed by David S. As generally taught in No. 5.110.514 and No. 5.114.632 There is. Continuous polymerization methods reduce stress and cavities caused by material shrinkage during polymerization. Chiron, i.e. minimize the cavity. Otherwise, locked-in stress will occur. As a result, replication fidelity decreases. Stresses in locally polymerized regions of an object can be applied using this technique. minimized by using Because polymerization occurs continuously within each layer, Furthermore, the polymer precursor fluid rapidly enters the irradiated area and is produced by polymerization. This is to replenish the instantaneous capacity lost due to subsequent contraction. The flow rate is minute. Yes, but since intralaminar and interlaminar stresses are minimized or disappear, The effect is sufficient. In addition, the polymer precursor fluid has a vacancy in the irradiated area resulting from shrinkage. Polymerizes rapidly in the sinus space. This is shown in FIG. FIG. 12 shows the U Figure 2 is an enlarged view of the local area of the precursor fluid pool being irradiated by the V-mercury lamp. Ru.

Continuous polymerization processes are easily applied to either radiation or heat curing.

Radiation curing is more controllable than heat curing and generally has shorter curing times; Preferably, 1° radiation curing is carried out at a moderately high temperature to further shorten the polymerization time ( It can be.

The moving front of the polymerization initiating source, typically UV radiation, is irradiated using any suitable means. It can be accomplished. In one embodiment, a continuously moving slit system (SM SS) is used. This system uses a thin slit (typically 1 μm). ioam) irradiation causes the material in front of the moving polymer zone to become liquid the polymer precursor fluid so that the material it passes through remains solidified. Continue passing.

In other methods, the moving front surface is a radial aperture of an iris diaphragm. Mobile polymer zone The liquid state material in front of the pump flows freely and strains at a rate similar to the contraction rate. A smooth and stress-reduced polymer network is produced.

Figure 9a shows that the polymer precursor fluid is continuously polymerized (Vl is the first valve, V2 is the The second valve, Svl is the first solenoid/<lub, SV2 is the second solenoid valve Schematic side view of one apparatus for preparing objects from Ql and Q2 It is.

This example is not intended to limit the scope of the invention. Other device designs are disclosed in this application. can be easily constructed using the methods shown, all of which are within the scope of the present invention. Assume that there is.

As shown in FIG. 98, data 110 is input into computer 120. , create a CAD file for the desired object. This data 110 is mathematically It is converted into a layer side, i.e. a layer. The computer 120 controls the solenoid valve 1 60, solenoid valve 170, pulse motor 270, and electronic shutter 22 interfaces a control box 130 that controls the operation of 0; 2nd solenoid The pressure valve 170 relieves pressure from the system as needed. Inert gas is , (quick connect joint 190, through valve 150, and solenoid valve through the quick connect 170 through the through tube 155 (having the lube 160). It is supplied to the response vat 205.

An elevator 260 controlled by a pulse motor 270 is connected to the platform 215. It is. A thin layer of polymer precursor fluid 235 is passed from tube 140 through valve 145. Then, it is introduced between the platform 215 and the UV transmission window 200 in the reaction vat 205.

Valve 145 is optionally connected to computer 12 through control box 130. 0.

A power source 250 supplies power to the U cylinder 30. The power of the UV lamp is usually , ranging from a few hundred watts to a few thousand watts.

The UV light from the UV clamp 30 is reflected off the mirror 240 and passes through the electronic shutter 220. Ru. The UV light is then passed through a photomask into a thin layer of polymer precursor fluid. Continuously conveyed. The means 245 for continuously moving the light is the reflection point of the UV light from the mirror. and the photomask 210 at any suitable position. Continuously moving light Two examples of means for controlling the 11 in detail.

The photomask includes a means for continuously moving light 245 and a polymer precursor fluid 235. between the electronic shutter 220 and the transparent window 200, preferably at a position between the electronic shutter 220 and the transparent window 200. There is. Any photomask known to those skilled in the art can be used in this apparatus. −Example As US Pat. Nos. 5.157.423 and 5.139.338, Photomask where CAD slices of the body are transferred from the computer to the mask generator The system is disclosed. This photomask system produces a negative cross-sectional image of the surface. By charging the area and "developing" the electrostatic image with toner powder, the glass It operates similarly to a photocopy machine, produced on a copying plate. In other embodiments , the negative slice image is created by backlit, individually controlled liquid crystal planes. directly onto the polymer surface. Or move continuously Using the slit system, a ``dot matrix type programmable mass'' can be created. can be adopted. A photomask is a pixel reflector activated by piezoelectricity. accomplished by. This is because the target spot can be darkened/brightened ( A small deflection is sufficient for this. As continuous polymerization progresses, a slit-like mass is formed. synchronization by simultaneously switching on and off the in-line pixels. Changes will be made in due course.

In other embodiments, the microbubble technology used in inkjet printing is Used to form photomasks. A microelectrode is a liquid-filled silicone light is passed through the cylinder while the electrode is heated. moment When heated, air bubbles form at the selected site and the scattered light passes through the cylinder lens. Ru. Bubble spots correspond to dark pixels, ie, pixels that are out of focus. dark space The combination of pots and bright spots forms a photomask image.

UV light i2 is successively passed through a photomask 210 and applied onto the thin polymer precursor layer. Form a pattern of light to provide the desired shape of the polymer layer. - alternating layers are formed Then, the elevator 215 displays the image that exists on the elevator platform 215. Move the layer by a differential amount and add fresh (unexposed) precursor fluid to the bottom layer. Make sure to cover the embedded layer. Then repeat this process successfully and create a new Superimposing the patterns provides a composite three-dimensional construct consisting of a stack of fixed images. . This system integrates the concept of continuous polymerization with a three-dimensional stereolithography process. The system provides an object with minimal stress and steric distortion.

In this method, the polymer precursor fluid is deposited as a very thin layer or in an inert, immiscible layer. It can be provided as a very thin layer formed on a compatible layer. This method relies on absorption. Directly limit layer thickness and cure depth without relying solely on UV attenuation It has the advantage of The ability to form ultra-thin layers depends on the viscosity of the polymer precursor fluid. , and its propensity to spread between the transparent window and the elevator platform. This process The use of high pressures and temperatures in the process reduces the viscosity of the polymer precursor fluid. , which makes the process easier.

Using this method, objects with layers of varying physical properties can be prepared. −Example As such, the first several polymer layers are formed from a flexible, impact-resistant material; The subsequent layer is formed from a rigid thermoplastic material.

Figure 9b shows the valve flow for introducing and removing changing polymer precursor fluids. 93 and the remaining polymer precursor Figure 3 is a side view of the apparatus showing means for vacuum removing fluid from the transparent plate; child Embodiments of the apparatus prepare three-dimensional objects from layers of different polymer precursor fluids. can be used to

As shown, the control box 130 controls the desired valves (from ■1 and v3). Signal the opening of Vn) and create a layer of first polymer precursor fluid between the transparent plate and the platform. I will provide a. The IR sensor sends a signal to the control box and indicates that the desired fluid thickness is Once accomplished, close the valve. The platform is then lowered to the fluid surface and the fluid Cures in desired pattern. The platform is then moved the appropriate distance and the vacuum wiper Clear the plate and remove any residual fluid. These steps then add the second polymer precursor, and if necessary, repeat with other polymer precursor fluids. It will be done.

Figure 10 shows a system with a continuously moving slit system (SMSS) for producing three-dimensional objects. 1 is a partial cross-sectional view of an apparatus for manufacturing. As shown, the device is movable and Adjustable slit z80, pulse motor 290 to control slit movement speed , electric shutter 2201 and pulse motor 290 and other programmable components , a control box interfaced to a computer as described above in Figure 9. It has 130. Slit size depends on the type of polymer precursor fluid used. may be changed depending on the The moving speed of the UV light slit is the same as when the polymer precursor fluid is cured. The time period is usually controlled between 2 seconds and 30 seconds.

During normal running, the electronic shutter 220 is open and the slit is opened on the photomask 210. begins to move from one side to the other. When continuous curing is complete, the electronic shutter closes. Ru. As described above: - Once the alternating layers are formed, the elevator 260 The imaged layer present on the 215 is moved by a differential amount and a fresh (unexposed) (not written) so that the precursor fluid covers the underlying written layer.

Figure 11 shows that continuous polymerization is achieved using a computerized iris diaphragm (C[D). FIG. 2 is a partial cross-sectional view of an apparatus for manufacturing a three-dimensional object. The device has an iris diaphragm of 30 0. Computer-controlled rotary stage 310.1! Child shutter 220, and FIG. As shown in FIG. A control box 130 interfaces the programmable part to the combi coater. have The iris diaphragm keeps the energy per unit area constant and This is useful for smoothly controlling radiation that expands and contracts.

Rotating stage rotates the iris diaphragm if the iris diaphragm is not automated used for. First, the electronic shutter opens, then the iris diaphragm adjusts to the desired rate. Open with . When curing is complete, the electronic shutter closes. Then this process is , are repeated until a three-dimensional object is constructed.

Figure 13 shows an object formed by three-dimensional stereolithography. FIG. 2 is a schematic diagram of an apparatus for efficiently removing transparent plates from which they are attached. The transparent plate , is modified to have an uneven portion, and the recessed portion has a refractive index that matches the refractive index of the transparent plate. A flexible material with a refractive index, or filled with air.

Figure 13 shows two types of modified transparent plate surfaces: a grid surface and a dotted surface. and Other notches can also be used to modify the surface if desired. It can be done.

Tapes with an adhesive side and a non-adhesive side are designed so that the adhesive side of the tape has a modified surface of a transparent plate. The non-adhesive side of the tape is prepared from a polymer precursor fluid and a fluid placed on a glass plate so as to face the object. When the object is completed, The object is a flexible filler or air cushioning effect in a modified transparent plate. Because of its flexibility, the non-adhesive tape can be easily separated from the surface.

Examples of transparent tapes suitable for quickly separating objects from transparent plates include: E.1. Tef manufactured by DuPont NeMours and Company Examples include Ion-PEP. One side of Tef Ion-PEP film is It has a pressure sensitive adhesive and is therefore easily applied to the plate. Elasticity of flexible materials Deformation induces separation under vacuum. CHRInc is the catalog name °C” sells Tef Ion-PEP, M52, M2O, M69, and M2S. We also sell other suitable transparent polyester chives, including:

111. Preparation of microconstructs and small constructs for microelectronic applications Using one method of three-dimensional stereolithography disclosed in this application, microelectronic High definition microconstructs and small constructs suitable for applications can be prepared. These technologies Examples of specific constructs that can be formed using magnetic micromotors, shape transformers, metal curved actuators, pressure transformers, microturbines, and interengaging microcoils.

Small constructs and microconstructs for microelectronic use LIGA or 5LIGA technology High-definition plastic composites as shown in the book demonstrate the precision of constructs prepared using Once the molded part is complete, it is removed from the vat and typically nickel-plated. Electroplated. Next, the plastic molding is removed and the free metal construct is to be cast.

This technique can provide constructs with very complex shapes. 'This process is More flexible than IGA and 5LIGA technologies. Because CAD program It is easy and well automated to form photomasks using It's a good thing. Figure 9 has a half-dome, conical, and pyramidal shape and uses this technique. FIG. 2 is a diagram of the complex constructs that can be prepared using used to build this construct. As the number of layers increases, the smoothness of the surface increases. Figure 16 shows this FIG. 3 is an illustration of a tapered honeycomb shape that can be constructed using a process. Tapered C Nicum is useful in the area of bioseparations.

The molded article construction process disclosed in this application is compatible with LIGA and 5L in the following respects. It is a significant improvement over IGA technology. l) No need for X-ray irradiation; 2) No need for alignment (in SLIGA, the X-ray mask is patterned) 3) The molded article must be geometrically aligned with the sacrificial layer and the treated substrate); Construction time is significantly reduced; 4) Automatic photomask generation using CAD 6) There is no limit to the height of the structure; 7) The molded product can be It has a rough sidewall profile and can be formed from several materials in a laminate.

The invention has been described with reference to preferred embodiments. Modifications and modifications of the invention described in this application Modifications and modifications will be apparent to those skilled in the art from the foregoing detailed description of the invention. These modifications All modifications and variations are intended to be within the scope of the appended claims.

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Claims (1)

[Claims] 1. Stereolithography from polymer precursor fluids that can be cured upon exposure to a polymerization initiation source In the method of manufacturing three-dimensional objects by fission, the vat is closed to the external environment. and applying high pressure and high temperature within the vat. 2. The applied pressure ranges from slightly higher than atmospheric pressure to 100,000 m The improvement of claim 1, ranging up to psi. 3. the applied pressure is in a range between 5,000 and 8,000 psi; Improvement according to claim 1. 4. The temperature applied within the vat is in the range of 30°C to 300°C. Improvement according to claim 1. 5. The improvement of claim 1, wherein the polymer initiation source is ultraviolet light. 6. The polymer precursor fluid is a methacrylate monomer or an acrylate monomer. The improvement according to claim 1, having a viscosity greater than that of the nomer. 7. 2. The viscous polymer precursor fluid of claim 1, wherein the viscous polymer precursor fluid comprises a thermosetting fluid. improvements. 8. The modified method of claim 1, wherein the polymer precursor fluid contains an inert polymer. good. 9. The modified method of claim 1, wherein the polymer precursor fluid contains an inert polymer. good. 11. 2. The polymeric precursor fluid of claim 1, wherein the polymeric precursor fluid contains a non-polymeric inert material. Improvements to the description. 12. The non-polymeric inert materials include CaCO and MgCO, clay, and Diatomaceous earth, alumina such as borates, sulfates, phosphates, celite and silica powder , colloidal silica, and zeolite solids. Improvement described in 11. 13. 2. The polymer precursor fluid of claim 1, wherein the polymer precursor fluid contains colloidal particles. Improvement. 14. The colloidal particles are colloidal gold, titanium oxide, iron oxide (magnetic substance) , cobalt, molybdenum oxide, vanadium oxide, nickel, alloys, transition metals - rare Earth oxide complex, silicon dioxide, silicon nitrate, germanium oxide, silicon Claims selected from the group consisting of atomic groups, gallium arsenide, and other semiconductor particles Improvement described in 13. 15. 2. The polymer precursor fluid of claim 1, wherein the polymer precursor fluid contains organic crosslinked beads. improvements. 16. The improvement of claim 1, wherein the polymer precursor fluid contains magnetic particles. . 17. During the formation of the three-dimensional object, the magnetic fluid is 17. The improvement according to claim 16, wherein the are aligned. 18. The magnetic particles align to form a small motor, actuator, or sensor. 18. The improvement according to claim 17, forming a . 19. 2. The polymer precursor fluid of claim 1, wherein the polymer precursor fluid contains liquid crystals or liquid crystal agglomerates. Improvements to the description. 20. An apparatus for manufacturing objects by high-pressure three-dimensional lithography, a polymer precursor that can be transformed into a solid polymer body when exposed to a polymerization initiation source body fluids, a reaction vat containing the polymer precursor fluid through which the polymerization initiation source is permeated; a polymerization initiation source that passes through the vat; a stand on which the object is placed; actuator means for moving the object as required, and the polymer initiation source; means for continuously moving through the polymer precursor fluid; A device having. 21. 21. The apparatus of claim 20, wherein the reaction vat is closed to an external environment. . 22. 22. The vat of claim 21, further comprising means for applying pressure within the vat. Device. 23. 21. The device of claim 20, further comprising means for increasing the temperature within the vat in the vat. Place. 24. said hand continuously moving said polymerization initiation source through said polymer precursor fluid; 21. The device of claim 20, wherein the stage is an iris diaphragm. 25. said hand continuously moving said polymerization initiation source through said polymer precursor fluid; 21. The apparatus of claim 20, wherein the stage is a system of continuously moving slits. 26. The polymerization process is performed such that the polymer precursor fluid is polymerized in a desired pattern. 21. The apparatus of claim 20, further comprising a photomask for imaging the initiation source. 28. 27. The apparatus of claim 26, wherein the photomask image is piezoelectrically generated. Place. 29. 27. The photomask image according to claim 26, wherein the photomask image is generated by microbubbles. equipment.