JP2006321083A - Method for producing micro reactor and method for producing master mold for micro reactors or female mold - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method which can form a micro-reactor having a complex shape or a mold for its production accurately, simply, and promptly. <P>SOLUTION: In the method for producing the micro-reactor etc., cured resin layers are formed by selectively irradiating a photo-curable resin liquid with light, and a three-dimensional shape is formed by laminating the cured resin layers in turn. The present invention is particularly effective when the structure of the micro reactor etc., is a complex three-dimensional structure having an overhang part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a microreactor or a microreactor characterized in that a photocurable resin liquid is selectively irradiated with light to form a cured resin layer, and the cured resin layer is sequentially laminated to form a three-dimensional structure. This is a method for manufacturing a reactor mold.

  Fine processing is performed on the surface of a transparent substrate such as glass to form a concave-convex shape such as a groove shape, and a tubular structure is formed by capping, and a liquid or gas is allowed to flow through the tubular structure. Techniques for small devices that perform chemical reactions, physical reactions, and the like are known (Patent Documents 1 to 11). These small devices are referred to as chemical microdevices, Lab-on-chips, biochips, and the like depending on their applications. In the present application, these small devices are collectively referred to as microreactors. Microreactors are also used as chemical or biological reactors or analyzers (typically multistage synthesizers or ultra-small columns for chromatography), microelectrodes, various physical / chemical sensors, etc. Is expected.

  These microreactors typically form grooves having a width and depth of several to several hundreds of μm on the surface of a rectangular parallelepiped having a length and width of several centimeters and a thickness of about 1 mm. Has a structure in which a cover for covering is attached. Furthermore, in the case of an electrical device such as an electrode or a sensor, a thin metal layer is provided on the surface of the transparent substrate by vapor deposition or the like to provide conductivity, and not only the groove shape but also a more complicated three-dimensional structure. For example, by forming a thin piece partly floating from the surface of the substrate, a sensor for detecting strain against mechanical vibration can be obtained.

  Conventionally, microreactors form surface irregularities by cutting a transparent substrate such as glass or forming a thin layer of a cured product of a photocurable resin according to a predetermined mask pattern using a lithography technique. In addition, the lid member is separately bonded so as to cover the groove portion to form a tubular structure. In addition, when a lithography technique or the like is used, a technique for forming a structure having an overhang portion by adopting an intermediate process for providing a sacrificial layer is also known (Patent Documents 10 and 11).

  On the other hand, in the photo-curing modeling method (hereinafter referred to as “optical modeling method”), modeling is performed based on data of a cross-sectional group obtained by slicing a three-dimensional model to be modeled into a plurality of layers. Usually, light is first applied to the surface of the photocurable resin liquid in a region corresponding to the lowermost cross section. Then, the photocurable resin liquid on the liquid surface portion irradiated with light is photocured, and a cured resin layer having one cross section of the three-dimensional model is formed. Next, an uncured photocurable resin liquid is coated on the surface of the cured resin layer with a predetermined thickness. At this time, it is common to coat the cured resin layer by immersing it in a photocurable resin liquid filled in the resin tank by a predetermined thickness. In addition, a relatively small amount of a photocurable resin is applied to the entire surface by a recoater every time one cured resin layer is formed. Then, laser beam scanning is performed on the surface along a predetermined pattern, and the coat layer portion irradiated with light is cured. The cured portion is laminated and integrated with the lower cured resin layer. Thereafter, a desired three-dimensional model is formed by repeating the light irradiation and the coating of the photocurable resin liquid while switching the cross section handled in the light irradiation process to an adjacent cross section (see Patent Document 12 and Patent Document 13). The stereolithography method is a technique that can easily and quickly form a three-dimensional structure having an overhang portion based on CAD data. However, it is difficult to increase the resolution of a modeled object with conventional stereolithography methods. There is a typical resolution of several tens of μm, which is difficult to use for manufacturing a microreactor that requires higher resolution.

JP 2003-14772 A JP 2003-117409 A JP 2003-139761 A JP 2003-149252 A JP 2004-69625 A JP 2004-178319 A JP 2004-195433 A JP 2004-219199 A Japanese Patent Laying-Open No. 2005-22364 JP 2004-69733 A JP 2004-9183 A JP 56-144478 A JP-A-62-35966

  When a cutting method or a lithography method is used, these methods can be formed only in a structure that does not have an overhang portion in principle. For example, an overhang in which a plurality of flow paths intersect three-dimensionally or the like. It has been difficult to produce a microreactor or macroreactor mold (hereinafter referred to as “microreactor etc.”) having a complicated three-dimensional structure having a part. In addition, if an intermediate process for forming a sacrificial layer is employed, a process for removing the sacrificial layer after the formation of the three-dimensional structure is required. For example, the manufacturing process becomes complicated and a long time is required for manufacturing. was there.

  The present invention has been made to solve such a problem, and forms a microreactor having a complicated three-dimensional shape, particularly a three-dimensional structure having an overhang portion, with high accuracy, simply and quickly. An object of the present invention is to provide a manufacturing method that can be used.

  In the manufacturing method of the microreactor and the like according to the present invention, the cured resin layer is formed by repeatedly irradiating the photocurable resin liquid with light by repeating collective exposure in units of projection areas. The three-dimensional structure is formed by sequentially laminating. The present invention is particularly effective when the structure of a microreactor or the like is a complicated three-dimensional structure having an overhang portion.

Here, when the area of the projection region is 100 mm ² or less, a microreactor or the like can be formed with higher accuracy by using the optical modeling method according to the present invention.
Similarly, when the thickness of one layer of the cured resin layer is 10 μm or less, a microreactor or the like can be formed with higher accuracy by using the optical modeling method according to the present invention.

  The method for producing a microreactor or the like according to the present invention is suitably used when the photocurable resin liquid is cured by light reflected by a digital mirror device.

  In addition, the microreactor or the method of manufacturing the female mold for manufacturing the microreactor according to the present invention is a microreactor made of ceramics having higher strength by blending ceramic powder into the photocurable resin liquid. Female molds for manufacturing reactors and microreactors can be formed.

  According to the manufacturing method of the present invention, it is possible to provide a manufacturing method of a microreactor or the like capable of forming a microreactor or the like having a complicated three-dimensional structure with high accuracy, simply and quickly.

  Hereinafter, embodiments to which the present invention can be applied will be described. The following description is to describe the embodiment of the present invention, and the present invention is not limited to the following embodiment. For clarity of explanation, the following description is omitted and simplified as appropriate. Moreover, those skilled in the art can easily change, add, and convert each element of the following embodiments within the scope of the present invention.

Embodiment 1 of the Invention [Method for Producing Microreactor]
An example of a photo-curing modeling apparatus (hereinafter referred to as “optical modeling apparatus”) used in the method for manufacturing a microreactor according to the present invention will be described using FIG. The optical modeling apparatus 100 includes a light source 1, a digital mirror device (DMD) 2, a lens 3, a modeling table 4, a dispenser 5, a recoater 6, a control unit 7, and a storage unit 8.

The light source 1 generates a laser beam. As the light source 1, for example, a laser diode (LD) or an ultraviolet (UV) lamp that generates 405 nm laser light is used.
The digital mirror device (DMD) 2 is a device developed by Texas Instruments, and hundreds of thousands to millions of micromirrors that move independently on a CMOS semiconductor, for example, 480,000 to 1.31 million are spread. It has been. Such a micromirror can be tilted by about ± 10 degrees, for example, about ± 12 degrees about the diagonal line by an electrostatic field effect. The micromirror has a square shape in which the length of one side of the pitch of each micromirror is about 10 μm, for example, 13.68 μm. The interval between adjacent micromirrors is, for example, 1 μm. The entire DMD 2 used in the first embodiment has a square shape of 40.8 × 31.8 mm (of which the mirror portion has a square shape of 14.0 × 10.5 mm), and one side. Is composed of 786,432 micromirrors having a length of 13.68 μm. The DMD 2 reflects the laser beam emitted from the light source 1 by the individual micromirrors, and only the laser beam reflected by the micromirrors controlled by the control unit 7 at a predetermined angle passes through the condenser lens 3. 4 is irradiated to the photo-curable resin 9 on 4.
The lens 3 guides the laser beam reflected by the DMD 2 onto the photocurable resin 9 to form a projection region. The lens 3 may be a condenser lens using a convex lens or a concave lens. When a concave lens is used, a projection area larger than the actual size of DMD 2 can be obtained. The lens 3 according to the first embodiment is a condensing lens, and reduces incident light about 15 times and condenses it on the photocurable resin 9.
The modeling table 4 is a flat table on which the cured resin is sequentially deposited and placed. The modeling table 4 can be moved horizontally and vertically by a driving mechanism (not shown), that is, a moving mechanism. With this drive mechanism, stereolithography can be performed over a desired range.
The dispenser 5 accommodates the photocurable resin 10 and supplies a predetermined amount of the photocurable resin 10 to a predetermined position.
The recoater 6 includes, for example, a blade mechanism and a moving mechanism, and applies the photocurable resin 10 uniformly.

The control unit 7 controls the light source 1, DMD 2, modeling table 4, dispenser 5, and recoater 6 according to control data including exposure data. The control unit 7 can typically be configured by installing a predetermined program in a computer. A typical computer configuration includes a central processing unit (CPU) and memory. The CPU and the memory are connected to an external storage device such as a hard disk device as an auxiliary storage device via a bus. This external storage device functions as the storage unit 8 of the control unit 7. A storage medium drive device such as a flexible disk device, a hard disk device, or a CD-ROM drive that functions as the storage unit 8 is connected to a bus via various controllers. A portable storage medium such as a flexible disk is inserted into a storage medium driving apparatus such as a flexible disk apparatus. The storage medium can store a predetermined computer program for executing the present embodiment by giving instructions to the CPU in cooperation with the operating system.
The storage unit 8 stores control data including exposure data of cross-sectional groups obtained by slicing a three-dimensional model to be modeled into a plurality of layers. Based on the exposure data stored in the storage unit 8, the control unit 7 mainly controls the angle control of each micromirror in the DMD 2 and the movement of the modeling table 4 (that is, the position of the laser beam irradiation range with respect to the three-dimensional model). Execute the modeling of the three-dimensional model.

The computer program is executed by being loaded into a memory. The computer program can be compressed or divided into a plurality of parts and stored in a storage medium. In addition, user interface hardware can be provided. Examples of the user interface hardware include a pointing device for inputting such as a mouse, a keyboard, or a display for presenting visual data to the user.
As the photocurable resin 10, a resin that is cured by visible light and light outside the visible light region can be used. For example, an acrylic resin corresponding to 405 nm having a curing depth of 15 μm or more (500 mJ / cm ² ) and a viscosity of 1500 to 2500 Pa · s (25 ° C.) can be used.

Next, the optical modeling operation of the optical modeling apparatus 100 according to the first embodiment will be described. First, the uncured photocurable resin 10 is accommodated in the dispenser 5. The modeling table 4 is in the initial position. The dispenser 5 supplies the stored photocurable resin 10 on the modeling table 4 by a predetermined amount. The recoater 6 sweeps the photocurable resin 10 as it is stretched and forms a coat layer for one layer to be cured.
The laser beam emitted from the light source 1 enters the DMD 2. The DMD 2 is controlled by the control unit 7 in accordance with the exposure data stored in the storage unit 8 and adjusts the angle of the micromirror corresponding to the portion where the photocurable resin 10 is irradiated with the laser beam. Thereby, the laser beam reflected from the micromirror is irradiated onto the photocurable resin 10 via the condenser lens 3, and the laser beam reflected from the other micromirrors is not irradiated onto the photocurable resin 10. Irradiation of the laser beam to the photocurable resin 10 is performed for 0.4 seconds, for example. At this time, the projection area onto the photocurable resin 10 is, for example, about 1.3 × 1.8 mm, and can be reduced to about 0.6 × 0.9 mm. The area of the projection region is usually desirably 100 mm ² or less.
By using a concave lens for the lens 3, the projection area can be expanded to about 6 × 9 cm. If the projection area is enlarged beyond this size, the energy density of the laser beam applied to the projection area becomes low, and the photocurable resin 10 may be insufficiently cured. When forming a three-dimensional model larger than the size of the laser beam projection area, it is necessary to irradiate the entire modeling area by moving the irradiation position of the laser beam, for example, by horizontally moving the modeling table 4 by a moving mechanism. is there. Laser beam irradiation is performed one shot at each projection area. Control of laser beam irradiation to each projection area will be described in detail later.
In this way, by moving the projection area and performing irradiation of the laser beam with each projection area as a unit, that is, exposure, the photocurable resin 10 is cured, and a first cured resin layer is formed. Is done. The lamination pitch for one layer, that is, the thickness of one cured resin layer is, for example, 1 to 50 μm, preferably 2 to 10 μm, and more preferably 5 to 10 μm.

  Subsequently, a second layer of a three-dimensional model having a desired shape is simultaneously formed in the same process. Specifically, the photocurable resin 10 supplied from the dispenser 5 is applied to the outside of the cured resin layer formed as the first layer so as to be stretched beyond the three-dimensional model by the recoater 6. Then, a second cured resin layer is formed on the first cured resin layer by irradiating with a laser beam. Thereafter, the third and subsequent cured resin layers are sequentially deposited in the same manner. Then, when the deposition of the final layer is completed, the modeled object formed on the modeling table 4 is taken out. The molded article can be further cured by removing the photocurable resin liquid adhering to the surface by washing or other methods and irradiating or heating with a UV lamp or the like as necessary.

The three-dimensional structure such as a microreactor to be manufactured may be an arbitrary structure as long as it is within the resolution range of the optical modeling apparatus. The manufacturing method of the microreactor and the like of the present invention is particularly suitable for manufacturing a microreactor having a complicated three-dimensional structure having an overhang portion. Specific examples of the three-dimensional structure having an overhang portion include a tubular structure that intersects three-dimensionally, and a structure that includes a plurality of layers that are stacked at intervals in the vertical direction.
Here, “having an overhang portion” means that the overhang portion is present at least in part when viewed from the vertical direction even when the three-dimensional structure is rotated and installed in any direction. To do. In addition, the overhang portion is a portion having a structure in which the horizontal width of the upper portion is larger than the horizontal width of a certain portion. Typically, the overhang portion is in contact with the column portion and the column portion than the column portion. However, it is not limited to a linear structure, but includes a shape having a curved surface that rises in the vertical direction and protrudes in the horizontal direction, and a so-called reverse tapered shape. It is a concept. For example, the cylindrical shape is an overhang when viewed from the vertical direction with the cylindrical side in contact with the horizontal plane, but there is no overhang when viewed from the vertical direction with the bottom in contact with the horizontal plane. It is not a three-dimensional structure having an overhang portion. On the other hand, the spherical shape is a three-dimensional structure having an overhang portion. The manufacturing method of the present invention is particularly suitable for modeling a three-dimensional structure having an overhang portion. If the structure has no overhang portion when viewed from a certain direction, the overhang portion is essentially difficult to manufacture. This is because even if other manufacturing methods are used, it may be possible to form the three-dimensional structure.

  Although the photocurable resin used for this invention is not specifically limited, Usually, the photocurable resin composition which has a radically polymerizable compound and / or a cationically polymerizable compound is used suitably. In addition, a photopolymerization initiator corresponding to radical polymerization or cationic polymerization is usually added to these photocurable resin compositions.

  A three-dimensional object made of a cured product obtained by the above-mentioned stereolithography is taken out from the stereolithography apparatus, and after removing the unreacted composition (uncured) remaining on the surface and inside, it is washed as necessary. To do. Here, as the cleaning agent, alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone, etc .; aliphatics typified by terpenes Organic solvents; low viscosity thermosetting resins and photocurable resins.

Embodiment 2 of the Invention [Method for Producing Microreactor Made of Ceramic]
When it is desired to manufacture the microreactor with ceramic, ceramic powder can be blended with the photocurable resin composition. The number average particle diameter is usually 0.01 to 0.5 μm, preferably 0.02 to 0.3 μm, more preferably 0.05 to 0.2 μm, as measured by electron microscopy. It is. The particle size of the ceramic powder is measured by electron microscopy, but scanning electron microscopy is particularly preferred. The shape of the ceramic powder is not particularly limited as long as it has a granularity that can define the particle size. For example, it is not limited to a spherical shape, and may be a pulverized body or the like. The particle diameter in the case of a shape other than a spherical shape is defined by the maximum diameter in the electron microscope image.

  The material constituting the ceramic powder is not particularly limited as long as it does not substantially absorb the light having the irradiation wavelength. For example, oxides such as alumina, zirconia, titania, zinc oxide, ferrite, barium titanate, apatite, silica, carbides such as zirconium carbide and silicon carbide, nitrides such as aluminum nitride, silicon nitride, and sialon (SiAlON), or Various ceramics such as a mixture thereof can be used. Usually, as the component (A), alumina, zirconia, silica, aluminum nitride, silicon nitride, or a mixture thereof is preferably used.

  When a three-dimensional product obtained by photocuring a photocurable resin containing a ceramic powder is fired, a microreactor made of a ceramic fired body can be obtained. The firing method used here is not particularly limited, and a known method can be used.

Embodiment 3 of the Invention [Method for Producing Microreactor Mold]
Another embodiment of the present invention is a mold manufacturing method used in the manufacture of microreactors. In the first and second embodiments, the microreactor itself is modeled and manufactured by the optical modeling method. In the third embodiment, the mold used for manufacturing the microreactor is modeled and manufactured by the optical modeling method described in the first embodiment. To do. The mold is roughly classified into a female mold and a master mold, and any of them can be shaped and manufactured by the optical modeling method. The female mold is a mold for producing a microreactor by copying the shape from the mold, and the master mold is a prototype of the microreactor to be finally produced. A mold for producing a female mold.

  When manufacturing a microreactor from a female mold, for example, a silane compound having a hydrolyzable group is injected into the female mold, and a hydrolysis / condensation reaction is caused by heating, etc. A three-dimensional structure made of polysiloxane is obtained. A microreactor can be obtained by separating the three-dimensional structure from the female mold. If the structure of the female mold is complicated, the female mold may not be peeled unless the female mold is destroyed. In such a case, for example, the cured resin constituting the female mold is burned away by heat treatment at 300 ° C. for about 6 hours, or the ultrasonic treatment is performed for about 1 hour by immersing in an organic solvent such as ethanol. The female mold can be destroyed by a method such as swelling of the cured resin constituting the mold. Even if the female mold made of the photocurable resin is not broken due to peeling, the number of times that the microreactor can be manufactured is limited because the mechanical strength is inferior to that of a mold or the like. However, unlike a mold, a female mold can be obtained easily and quickly, which is effective when trial manufacture of microreactors having various shapes.

When manufacturing a microreactor from a master mold, for example, Ni electroforming is performed on the surface of the master mold, and then the master mold is peeled off to produce a female mold in which the shape of the master mold is copied. A polysiloxane microreactor can be obtained by injecting and reacting a silane compound having a hydrolyzable group in the same manner as described above by using this female mold and peeling it from the female mold.
In addition, a vacuum casting reversal type made of ordinary silicon rubber can be produced as a female type that is a copy of the shape of the master type. A microreactor such as urethane resin, acrylic resin, or ceramic slurry can be obtained by vacuum casting using the silicon rubber mold thus obtained.

It is a figure which shows schematic structure of the optical modeling apparatus concerning Embodiment 1 of invention.

Explanation of symbols

1 Light source 2 DMD
DESCRIPTION OF SYMBOLS 3 Condensing lens 4 Modeling table 5 Dispenser 6 Recoater 7 Control part 8 Memory | storage part 9 Photocurable resin 10 Photocurable resin 100 Optical modeling apparatus

Claims (14)

  By repeating collective exposure with the projection area as a unit, selectively irradiating light to the photocurable resin liquid to form a cured resin layer, and sequentially laminating the cured resin layer to form a three-dimensional structure. A method for producing a microreactor, which is characterized.   The method for manufacturing a microreactor according to claim 1, wherein the three-dimensional structure of the microreactor has an overhang portion.   The method for producing a microreactor according to claim 1, wherein the photocurable resin liquid contains ceramic powder. The method of manufacturing a microreactor according to any one of claims 1 to 3, wherein an area of the projection region is 100 mm ² or less.   The method for producing a microreactor according to any one of claims 1 to 4, wherein a thickness of one layer of the cured resin layer is 10 µm or less.   The method of manufacturing a microreactor according to any one of claims 1 to 5, wherein the photocurable resin liquid is cured by light reflected by a digital mirror device.   By repeating collective exposure with the projection area as a unit, selectively irradiating light to the photocurable resin liquid to form a cured resin layer, and sequentially laminating the cured resin layer to form a three-dimensional structure. A method for producing a microreactor mold, which is characterized.   The manufacturing method of the type | mold for microreactors of Claim 7 with which the three-dimensional structure of the said microreactor has an overhang part. 9. The method for manufacturing a microreactor mold according to claim 7, wherein the area of the projection region is 100 mm < ² > or less.   The method for manufacturing a mold for a microreactor according to any one of claims 7 to 9, wherein the thickness of one layer of the cured resin layer is 10 µm or less.   The method of manufacturing a microreactor mold according to any one of claims 7 to 10, wherein the photocurable resin liquid is cured by light reflected by a digital mirror device.   The method for producing a microreactor mold according to any one of claims 7 to 11, wherein the microreactor mold is a female mold for producing a microreactor.   The method for producing a mold for a microreactor according to claim 12, wherein the photocurable resin liquid contains a ceramic powder. The microreactor mold manufacturing method according to any one of claims 7 to 11, wherein the microreactor mold is a master mold for manufacturing a microreactor female mold.

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