JP2007090306A - Method for manufacturing microstructure and microreactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple and easy method for forming a microstructure with a desired shape and reduced unevenness in size, in a high yield and at low cost. <P>SOLUTION: The method for manufacturing the microstructure incudes the step of supplying a first liquid including an energy ray-cured monomer and a polymerization initiator to a first flow passage, the step of supplying a second liquid to a second flow passage formed so as to encircle the first flow passage, the step of bringing the first liquid into contact with the second liquid into a laminar flow state at a point where the first flow passage and the second flow passage meet each other, and the step of irradiating the first liquid brought into contact with the second liquid with energy rays. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a microstructure and a microreactor. More specifically, the present invention relates to a method for manufacturing a microstructure having a desired shape and small size variation with good yield and at a low cost, and to easily provide such a microstructure. The present invention relates to a microreactor that can be manufactured.

  Microstructures (eg, fibers having a nanometer or micrometer diameter) have a very large specific surface area. Such a microstructure has a very large interface with a gas or a liquid while being a solid. As a result, the microstructure has a very large degree of influence of the surface characteristics on the overall characteristics. Also, for example, a fiber having a nanometer-sized diameter is caused by the fact that the diameter is smaller than the wavelength of light, the mean free path of the conductor is smaller, the magnetic domain is smaller than the magnetic domain, etc. It exhibits electronic, optical, electrical, magnetic and mechanical properties that are completely different from the bulk state of the same substance (quantum size effect) (see Non-Patent Document 1).

  Conventionally, melt spinning methods, wet spinning methods, interfacial polymerization methods, and the like are known as fiber manufacturing methods. However, with such conventional technology, it is practically impossible to stably manufacture a fiber having a nanometer size diameter.

  In particular, when manufacturing nanometer-sized to micrometer-sized fibers, a very expensive and large-sized apparatus is required. Moreover, the yield is very poor even when such an apparatus is used. In addition, the resulting fiber diameter distribution is very large, and it is virtually impossible to produce fibers having the desired shape (eg, elliptical, star, hollow cross-sectional shape). is there.

On the other hand, a liquid phase method is known as a method for forming fine particles, which is another typical example of a microstructure. As the liquid phase method, a coprecipitation method, a sol-gel method, a spray pyrolysis method (droplet-particle conversion process), and the like are known. The coprecipitation method and the sol-gel method have a problem that the production process is complicated. The spray pyrolysis method has attracted attention because it is relatively simple and can be manufactured in one step. However, in any of these methods, it is substantially difficult to form very fine (eg, nano-sized) fine particles.
"The latest technology of nanoparticle production, evaluation, application, and equipment", edited by Mitsue Koizumi, CMC Publishing JP 2004-195433 A

  The present invention has been made in order to solve the above-described conventional problems, and an object of the present invention is to provide a microstructure having a desired shape and small size variation with high yield and simple. The object is to provide a method of forming at low cost.

  The microstructure manufacturing method of the present invention includes a step of supplying a first liquid containing an energy ray-curable monomer and a polymerization initiator to a first channel; and forming the first channel so as to surround the first channel. Supplying a second liquid to the second flow path formed; and supplying the first liquid and the second liquid at a point where the first flow path and the second flow path merge. Contacting with a laminar flow; and irradiating the first liquid contacted with the second liquid with energy rays.

  In preferable embodiment, the Reynolds number of the said laminar flow is 0.1-200.

  In a preferred embodiment, the flow rate of the first liquid is smaller than the flow rate of the second liquid.

  In a preferred embodiment, the first liquid is supplied continuously. In another embodiment, the first liquid is supplied in a pulsatile manner.

  In a preferred embodiment, the first flow path has a substantially circular, elliptical, polygonal, cruciform or star cross-sectional shape.

  In a preferred embodiment, the production method forms microparticles, rods or fibers.

  Another method of manufacturing a microstructure according to the present invention includes a step of supplying a first liquid to a first flow path; and energy in a second flow path formed so as to surround the first flow path. Supplying a second liquid containing a linear curable monomer and a polymerization initiator; formed so as to surround a merged flow channel formed by the merge of the first flow channel and the second flow channel. Supplying a third liquid to the third flow path; and laminating the first liquid and the second liquid at a point where the first flow path and the second flow path meet. A step of contacting in a flow state; the second liquid at a point where the merged channel formed by the first channel and the second channel merged and the third channel merged; Contacting the third liquid in a laminar flow state; irradiating the second liquid contacted with the third liquid with energy rays.

  Another method of manufacturing a microstructure according to the present invention includes a step of supplying a first liquid to a first flow path; and energy in a second flow path formed so as to surround the first flow path. Supplying a second liquid containing a linear curable monomer and a polymerization initiator; supplying a third liquid to a third flow path formed so as to surround the second flow path; Contacting the first liquid and the second liquid in a laminar flow state at a point where the first flow path and the second flow path meet; the second flow path and the second flow path; A step of bringing the second liquid and the third liquid into contact in a laminar flow state at a point where the three flow paths meet; an energy ray being applied to the second liquid in contact with the third liquid Irradiating.

  In another aspect of the invention, a microreactor is provided. The microreactor of the present invention includes a first flow path to which a first liquid is supplied, a second flow path to which a second liquid is supplied, the first flow path, and the second flow path. Comprising a converging flow path formed by three-dimensionally converging, and a curing means for curing the first liquid and / or the second liquid, the first flow At least a part of the passage having the outlet as an end is surrounded by the second flow path.

  In a preferred embodiment, in the microreactor of the present invention, at least a part of the merging channel transmits ultraviolet light, and the curing means is ultraviolet light irradiation means.

  In a preferred embodiment, the microreactor of the present invention is provided with a light shielding means for preventing the first flow path and / or the second flow path from being irradiated with ultraviolet light.

  In a preferred embodiment, the microreactor of the present invention includes a plurality of second liquid supply ports to the second flow path.

  In a preferred embodiment, in the microreactor of the present invention, the inner diameter of the outlet of the first flow path is 0.05 to 0.8 mm.

  In a preferred embodiment, the microreactor of the present invention has an inner diameter of a cross section including the outlet of the first channel in the second channel (the inner diameter of the outlet of the first channel +0.2). ) Mm or more and (inner diameter of the outlet of the first flow path +1.6) mm or less.

  In a preferred embodiment, the microreactor of the present invention is provided with pulse generating means for causing the first liquid to flow in a pulsating manner in the first flow path.

  In a preferred embodiment, the pulse generating means vibrates the diaphragm portion with an actuator using a part of the first flow path as a diaphragm portion.

  In a preferred embodiment, the microreactor of the present invention includes a flow rate control means for varying the flow rate of the first liquid in the first flow channel and the flow rate of the second liquid in the second flow channel. Is provided.

The microreactor of the present invention includes a first flow path to which a first liquid is supplied, a second flow path to which a second liquid is supplied, and a third flow path to which a third liquid is supplied. The first merging channel formed by three-dimensionally joining the first channel and the second channel, the first merging channel and the third channel 3 A microreactor body having a second merge channel formed by dimensionally merging, and a curing means for curing the first liquid, the second liquid, and / or the third liquid Provided, at least a part of which the outlet of the first channel is an end is surrounded by the second channel, and at least a part of the outlet of the first merging channel is the third Surrounded by the flow path.

  In a preferred embodiment, at least a part of the second merging channel transmits ultraviolet light, and the curing means is an ultraviolet light irradiation means.

The microreactor of the present invention includes a first flow path to which a first liquid is supplied, a second flow path to which a second liquid is supplied, and a third flow path to which a third liquid is supplied. A microreactor body comprising: a first flow path, a second flow path, and a third flow path formed by three-dimensionally combining the first flow path, the second flow path, and the third flow path; A curing means for curing the second liquid and / or the third liquid, and at least a part of the first flow path having the outlet as an end is surrounded by the second flow path. At least a part of the second channel having the outlet as an end is surrounded by the third channel.

  In a preferred embodiment, at least a part of the merging channel transmits ultraviolet light, and the curing means is ultraviolet light irradiation means.

  According to the present invention, the following advantages can be obtained by contacting the reaction liquid in a laminar flow state using a microreactor: (1) Since the reaction is performed at the liquid-liquid interface, the material can be freely selected. (2) Extremely stable and precise reaction is realized in a minute space, so that the uniformity of the resulting microstructure is extremely excellent; (3) Flow path and reaction solution By changing the supply form, it is possible to form a microstructure with a desired shape; (4) it is possible to change the size of the microstructure obtained by simply controlling the flow rate; and (5 ) It is possible to manufacture a microstructure with good yield and low cost efficiently. Examples of the microstructure obtained in the present invention include nano / micro-sized microfibers, microstructures (fibers, hollow fibers, particles, irregularly shaped particles, microlots, various-shaped microcapsules, etc.). It is done.

  Hereinafter, although preferable embodiment of this invention is described, this invention is not limited to these embodiment. In the present invention, the “inner diameter” of the flow path means the internal diameter when the cross-sectional shape viewed from the flow path direction is substantially circular, and the cross-sectional shape viewed from the flow path direction is other than circular. In this case, the length corresponding to the inner diameter is meant. For example, when the cross-sectional shape is substantially square, it means the length of the diagonal inside.

A. Two-layer system FIG. 1A is a schematic view of an apparatus (microreactor) 100 that can be preferably used in a manufacturing method according to a preferred embodiment of the present invention as viewed from above, and FIG. It is sectional drawing by the -A line (namely, seeing from the flow-path direction). FIG. 2 is a perspective view of the apparatus 100. The apparatus 100 includes a microreactor body 10 and a curing means 20. The microreactor main body 10 includes a first flow path 1, a second flow path 2 formed so as to surround the first flow path 1, and the first flow path 1 and the second flow path 2. A merging channel 3 formed by merging is provided. The first flow path 1 and the second flow path 2 are partitioned by a partition wall 4 on the upstream side (right side in the illustrated example) of the confluence (that is, the upstream end of the confluence flow path 3) 3a. . The apparatus 100 includes a supply port 1 a to the first flow path 1 and supply ports 2 a and 2 a ′ to the second flow path 2.

  As a preferred embodiment, the microreactor body of the present invention has a first flow path 1 to which a first liquid is supplied and a second liquid to which a second liquid is supplied, as shown in the apparatus 100 of FIGS. 2, a merge channel 3 formed by three-dimensionally joining the first channel 1 and the second channel 2, and an outlet of the first channel 1 as an end. At least a part of this is surrounded by the second flow path 2.

The shape of each flow path 1, 2, and 3 can be suitably designed according to the objective. For example, in the embodiment as shown in FIGS. 1 and 2, the cross section along the flow path direction of the first flow path 1 is substantially linear, and along the flow path direction of the second flow path 2. The cross section is tapered, and the cross section along the flow path direction of the merge flow path 3 is substantially linear. In another embodiment, the cross section along the flow path direction of the merge flow path 3 may be substantially tapered. In yet another embodiment, the cross section of the first flow path 1 along the flow path direction is substantially tapered and may be smaller than the taper of the second flow path. Also, for example, as shown in FIG. 1, the flow path from the supply port 1a to the first flow path 1 and the flow path from the supply port 2a (2a ′) to the second flow path 2 are in the flow path direction. It is also one of the preferable forms from the viewpoint of avoiding mixing of bubbles and the like that does not have a protruding part or a corner part that becomes an obstacle along the surface.

  In the microreactor body of the present invention, the inner diameter of the outlet of the first flow path is preferably 0.05 to 0.8 mm, more preferably 0.1 to 0.8 mm, and still more preferably 0.2 to 0 mm. 0.7 mm, particularly preferably 0.2 to 0.6 mm, most preferably 0.3 to 0.5 mm. When the inner diameter of the outlet of the first channel is in the above range, the first liquid and the second liquid can be merged three-dimensionally in a laminar flow state, and a desired microstructure can be obtained. It becomes.

In the microreactor body of the present invention, an auxiliary channel that protrudes outward continuously from the first channel along the first channel may be formed at the end of the first channel 1. Good. For example, as shown in the cross-sectional view of the outlet of the first flow channel in FIG. 3, the auxiliary flow channel 5 having a quadrangular cross section that protrudes outward from the four corners of the first flow channel 1 having a quadrangular cross section. 5, 5, 5 are formed. Thus, when the auxiliary flow path is formed at the end of the first flow path, the first liquid merges with the second liquid when the first flow path merges with the second flow path. Even if it partially diffuses unstable due to the impact, a laminar flow state can be maintained satisfactorily, and the shape of the resulting microstructure can be controlled well.

  In the microreactor main body of the present invention, the inner diameter of the cross section including the outlet of the first channel in the second channel is (the inner diameter of the outlet of the first channel + 0.2) mm or more (first It is preferable that the inner diameter of the outlet of the flow path +1.6) mm or less, and more preferably, (the inner diameter of the outlet of the first flow path +0.2) mm or more, (the inner diameter of the outlet of the first flow path) +1.3) mm or less, more preferably, (the inner diameter of the outlet of the first flow path +0.3) mm or more and (the inner diameter of the outlet of the first flow path +1.0) mm or less. When the inner diameter of the cross section including the outlet of the first channel in the second channel is in the above range, the first liquid and the second liquid can be three-dimensionally merged in a laminar flow state, A desired microstructure can be obtained.

  In the microreactor body of the present invention, the inner diameter of the merging channel is preferably 0.2 to 3.0 mm, more preferably 0.3 to 2.0 mm, still more preferably 0.4 to 1.6 mm, particularly Preferably it is 0.5-1.4 mm, Most preferably, it is 0.6-1.2 mm. When the inner diameter of the outlet of the merge channel is in the above range, the first liquid and the second liquid can be merged three-dimensionally in a laminar flow state, and a desired microstructure can be obtained. .

  In the present invention, in a form in which the curing means to be described later irradiates ultraviolet light, at least a part of the merging channel transmits ultraviolet light. For example, as shown in FIG. 4, a part of the merge channel may be formed of a glass tube 3 ′ that transmits ultraviolet light. The thickness L of the merging channel (the distance from the inner wall of the merging channel to the upper surface of the microreactor body) varies depending on the material forming the merging channel, but the thickness L of the merging channel is preferably 0. 0.05 to 2 mm, more preferably 0.1 to 0.8 mm, and still more preferably 0.2 to 0.4 mm. When the thickness of the merge channel is in the above range, the ultraviolet light can be efficiently transmitted into the merge channel. As shown in FIG. 5, in the microreactor main body of the present invention, only a portion corresponding to the merge channel 3 may be formed thin. Thus, it is possible to obtain a desired microstructure by appropriately designing the material and thickness of the merging channel.

  In one embodiment, the total length of the first channel 1 is 3 to 30 mm, the total length of the second channel 2 is 3 to 30 mm, and the total length of the merge channel 3 is 10 to 60 mm. The total length of the flow path of the device 100 (the first flow path entrance to the merge flow path exit) is 30 mm to 100 mm. Here, by adjusting the total length of the merging flow path 3, it is possible to adjust the irradiation time of the ultraviolet light to be described later while maintaining the laminar flow state of the first liquid.

In the microreactor body of the present invention, the shape and position of the supply port can be appropriately designed according to the purpose. For example, as shown in FIGS. 1 and 2, the supply ports 1a, 2a and 2a ′ may all be located on the side surfaces, and as shown in FIG. The form located above may be sufficient. The microreactor of the present invention includes a plurality of second liquid supply ports to the second flow path 2 as shown in the apparatus 100 of FIGS. 1 to 3 (in FIGS. 1 to 3 and FIG. 2a ′) is preferred. More preferably, it is 2-5, and still more preferably 2-3. With such a structure, it is possible to prevent the generation of bubbles in the second flow path 2 and to realize a sufficient laminar flow.

The microreactor of the present invention includes a curing means 20 for curing a first liquid and / or a second liquid described later. A typical example of the curing means is energy beam irradiation means. Specific examples of energy rays include light (infrared light, ultraviolet light, visible light), heat, electron beam, radiation, and the like. The energy rays to be used can be appropriately selected according to the type of the reaction liquid (first liquid and second liquid). Preferably, the curing means is an ultraviolet light irradiation means. This is because it can be installed at low cost and the application range of the reaction liquid (the first liquid and the second liquid) is expanded. Moreover, it is because a reaction liquid can be hardened instantaneously. Specific examples of the ultraviolet light irradiation means include an ultra high pressure mercury lamp, a flash UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep UV lamp, a xenon lamp, a xenon flash lamp, a metal halide lamp and the like. Although the wavelength of the light source used for the ultraviolet light irradiation can be determined according to the wavelength region in which the polymerizable functional group of the ultraviolet light curable monomer described later has optical absorption, a wavelength of 210 to 436 nm is usually used. More preferably, it is 250-405 nm. Illuminance of ultraviolet light, the material for forming a confluent channel, varies by thickness is preferably 5~100mW / cm ^2, and more preferably from 10~40mW / cm ^2. The irradiation amount of ultraviolet light, the material for forming a confluent channel, varies by thickness is preferably 20~300mJ / cm ^2, and more preferably from 50~150mJ / cm ^2. The installation position of the curing means 20 is not particularly limited, but a position where the first liquid brought into contact with the second liquid can be cured is preferable. In the form in which the curing means irradiates ultraviolet light, a desired microstructure can be obtained by controlling the timing of irradiation with ultraviolet light, irradiation intensity, irradiation time, and the like.

  In the microreactor of the present invention, when the curing means irradiates ultraviolet light, as shown in FIG. 7, the first flow path and / or the second flow path is prevented from being irradiated with ultraviolet light. The light shielding means 30 may be provided. By providing such a light shielding means, it becomes possible to irradiate only the first liquid in contact with the second liquid with ultraviolet light. Examples of the light shielding means include a light shielding tape and a light shielding plate.

  For example, as shown in FIG. 8, the microreactor of the present invention may be provided with a pulse generating means 40 for causing the first liquid to flow in a pulsating manner in the first flow path 1. The position of the pulse generating means 40 may be anywhere as long as it is in the middle of the first flow path 1, and can be appropriately designed according to the purpose. By controlling the timing and time of applying the pulsed pressure, the length and shape of the obtained microstructure can be arbitrarily adjusted. When the length of the pulse is short, the length of the microstructure is shortened, and a microstructure such as a lot or fine particles can be manufactured. In a more preferred embodiment, the pulse generating means 40 uses a part of the first flow path 1 as a diaphragm part and vibrates the diaphragm part with an actuator. For example, as shown in FIG. 9, a diaphragm portion 50 formed in a part of the first flow path 1 is vibrated by an actuator 60. The frequency is preferably 1 to 30 Hz. As the actuator 70, for example, a linear actuator (PMNA-1005S) manufactured by Touzer Laboratory Co., Ltd. may be mentioned. The thin part thickness of the diaphragm part is preferably 0.05 to 0.50 mm, more preferably 0.07 to 0.40 mm, and still more preferably 0.10 to 0.30 mm. According to the stereolithography described later, a microreactor having a structure as shown in FIG. 8 can be easily produced.

  The microreactor of the present invention may include a flow rate control means for varying the flow rate of the first liquid in the first flow path 1 and the flow rate of the second liquid in the second flow path 2. . The flow rate control means is preferably provided at a location closer to the supply port side than the outlet side (upstream side). Examples of the flow rate control means include a syringe pump and a gear pump, and a syringe pump is preferable. By providing the flow rate control means, the flow rate of the first liquid in the first flow channel 1 and the flow rate of the second liquid in the second flow channel 2 can be varied. It can be arbitrarily controlled, and depending on the type of the microstructure, the degree of curing, the cured wall thickness, the hollow cross section, and the like can be arbitrarily controlled.

  The microreactor of the present invention may be produced by any method, but it is preferably produced by an optical modeling method in that it can be produced easily and accurately. The stereolithography method converts a 3D image designed with 3D CAD data into 2D slice data, and based on this data, the photocurable resin is cured layer by layer with a laser and laminated in 3D. It is a method of modeling. More specifically, a three-dimensional image designed with three-dimensional CAD data is sliced into thin layers of several layers and converted into two-dimensional slice data. Based on this two-dimensional slice data, the laser is inside the tank. The cross-sectional shape is drawn by scanning the surface of the photocurable resin. The portion irradiated with the laser is cured, and a cross-section for one layer is formed on the elevator. After that, the elevator descends one layer at a time, and several thin cross-sectional bodies are continuously laminated and three-dimensionally layered. Finally, by lifting the elevator, a three-dimensional layered model is taken out and subjected to post-processing to be completed. As an optical modeling apparatus that can be used for the optical modeling method, for example, an optical modeling apparatus (for example, SCS-1000HD) manufactured by Deemec Co., Ltd. may be used. Examples of the photocurable resin that can be used in the optical modeling method include a photocurable resin (for example, oxetane-based SCR950, etc.) manufactured by Deemec Co., Ltd. Examples of the laser include a He—Cd laser (peak wavelength = 325 nm). For example, the laser spot size is preferably φ10 to 100 μm, and more preferably φ30 to 70 μm. The thickness of one resin layer obtained by curing is preferably, for example, 10 to 50 μm, and more preferably 20 to 40 μm.

  The manufacturing method according to a preferred embodiment of the present invention includes a step of supplying a first liquid containing an energy ray-curable monomer and a polymerization initiator to the first flow path 1; a second flow to the second flow path 2; Supplying the first liquid; contacting the first liquid and the second liquid in a laminar flow state at a junction 3a of the first flow path 1 and the second flow path 2; Irradiating the first liquid contacted with two liquids with energy rays. In the present invention, by using the apparatus as described above, the first liquid and the second liquid form a laminar flow at the merge point 3a and the merge channel 3. The first liquid and the second liquid can be appropriately selected according to the purpose (details of representative examples of the first liquid and the second liquid will be described later). By bringing the first liquid and the second liquid into contact in a laminar flow state, a very stable reaction at the liquid-liquid interface becomes possible. As a result, for example, when the first liquid is continuously supplied, a very stable linear reaction solidification is realized, and a fiber having a very small diameter and extremely small variation in diameter is stable. Can be formed.

  In the present invention, since the first liquid and the second liquid are contacted in a laminar flow state, the movement / diffusion of the substance at the interface of the laminar flow can be used. It is possible to cause chemical reactions such as “polycondensation”. In the present invention, the first liquid and the second liquid are brought into contact in a laminar flow state by three-dimensionally joining the first flow path and the second flow path, so that the specific interface area is particularly high. A large three-dimensional liquid-liquid interface can be stably generated, and a microstructure having a cross-sectional shape along the interface can be stably generated in the flow path traveling direction.

  The Reynolds number of the laminar flow is preferably 0.1 to 200, more preferably 0.5 to 50, particularly preferably 1 to 20, and most preferably 1 to 8. With such a very small Reynolds number, it is possible to control the liquid width after the first liquid merges by adjusting the flow ratio of the first liquid and the second liquid. As a result, a microstructure having a desired size can be obtained very accurately. One of the great achievements of the present invention is to realize a liquid-liquid reaction in a laminar flow state having such a very small Reynolds number. In addition, by controlling the Reynolds number within the above range, even if the flow velocity of the first liquid or the second liquid in the microreactor is increased, the laminar flow state is hardly disturbed, and the three-dimensional liquid-liquid interface is not generated. It is possible to stably generate a microstructure having a cross-sectional shape along the flow path traveling direction.

  Preferably, the flow rate of the first liquid is smaller than the flow rate of the second liquid. By making the flow rate of the first liquid smaller than the flow rate of the second liquid, it is possible to form the microstructure very stably. For example, when a fiber is formed, a fiber having a very small diameter and no variation in diameter can be obtained. Furthermore, by increasing the flow rate of the second liquid, it is possible to prevent friction and blockage due to the generated microstructure in the merge channel 3. Specifically, the flow rate of the first liquid is preferably 0.05 to 1 μl / second, more preferably 0.05 to 0.83 μl / second. The flow rate of the second liquid is preferably 0.2 to 40 μl / second, more preferably 6.7 to 20 μl / second. The flow ratio of the first liquid to the second liquid is preferably 1:30 to 1: 400.

  In the present invention, by changing the shape of the flow path to which the first liquid is supplied (the first flow path 1 in FIG. 1) and the method of supplying the first liquid, any appropriate shape and A microstructure having a size can be obtained. In one embodiment, the said 1st flow path 1 has a square cross-sectional shape with an internal diameter of 1-1000 micrometers. In another embodiment, the first channel 1 has a substantially circular, elliptical, polygonal, cross-shaped or star-shaped cross-sectional shape. In still another embodiment, the first channel 1 has a multilayer structure (for example, an upper layer and a lower layer two layer structure, an upper layer, an intermediate layer, and a lower layer three layer structure) or a multiple structure (for example, FIG. 10). It may have a double structure of an inner flow path and an outer flow path as shown in a sectional view, and a triple structure of an inner flow path, an intermediate flow path, and an outer flow path). In one embodiment, the first liquid is supplied continuously (ie, substantially rectified). In another embodiment, the first liquid is supplied in a pulsatile manner. For example, when a flow path having a substantially circular cross-sectional shape is used as the first flow path 1 and the first liquid is continuously supplied, a fiber as shown in FIG. 11A is obtained. For example, when a flow path having a square cross-sectional shape is used as the first flow path 1 and the first liquid is continuously supplied, a fiber as shown in FIG. 11B is obtained. By making the first flow path shape a flat shape, a very thin flat fiber can be obtained (not shown). For example, when a flow path having a substantially circular cross-sectional shape is used as the first flow path 1 and the first liquid is supplied in a pulsating manner, fine particles as shown in FIG. 11C are obtained. By changing the flow path shape of the first liquid, fine particles as shown in FIG. 11D are obtained. By changing the pulse shape of the pulsation, a rod or a so-called skewered microstructure as shown in FIG. Further, by appropriately selecting the type of the reaction liquid (first liquid and second liquid), fine particles can be obtained even when the first liquid is continuously supplied (for example, the first liquid and the second liquid). When the first liquid is lipophilic and the second liquid is hydrophilic, the first liquid is hydrophilic and the second liquid is lipophilic).

  In the present invention, the type of the reaction liquid (first liquid and second liquid) is appropriately selected, and / or the flow rates of the first liquid and second liquid are appropriately selected (within the reactor). The contact time is appropriately selected) and / or by performing an appropriate chemical treatment or surface treatment, a hollow microstructure or a porous microstructure can be obtained.

  The 1st liquid in one embodiment of the present invention contains an energy ray hardening monomer and a polymerization initiator. Examples of the energy ray curable monomer include an ultraviolet light curable monomer and a thermopolymerizable monomer, and an ultraviolet light curable monomer is preferable. This is because the ultraviolet light curable monomer can be cured in a short time, and as a result, a microstructure having a desired size and shape can be obtained. The ultraviolet light curable monomer may be a lipophilic monomer or a hydrophilic monomer.

Examples of the lipophilic monomer include monofunctional monomers or polyfunctional monomers containing saturated hydrocarbon compounds, alicyclic compounds, and aromatic compounds; monofunctional monomers or polyfunctional monomers containing fluorine, and the like. Examples of the monofunctional monomer or polyfunctional monomer containing the saturated hydrocarbon compound, alicyclic compound, and aromatic compound include stearyl acrylate, benzyl acrylate, isobornyl acrylate (IBXA), 1,6-hexanediol diacrylate, Examples include 1,9-nonanediol diacrylate, full orange acrylate, bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate (DPHA).

  Examples of the hydrophilic monomer include trimethylolpropane triacrylate ethylene oxide adduct, trimethylolpropane triacrylate propylene oxide adduct, polyethylene oxide diacrylate compound, polypropylene oxide diacrylate compound, polyethylene oxide acrylate compound, polypropylene oxide acrylate compound, and the like. Monofunctional monomers and bifunctional and polyfunctional monomers to which ethylene oxide or propylene oxide is added; Monofunctional monomers having a hydroxyl group such as hydroxyethyl acrylate and hydroxypropyl acrylate; Monofunctional monomers having a carboxyl group such as acrylic acid; N-vinyl Other compounds such as formaldehyde, acrylic morpholine, denacol acrylate, etc. That.

  The said monomer is used individually or in combination of 2 or more types.

Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include benzoin derivatives, benzyl ketals, α-hydroxyacetophenones, α-aminoacetophenones, acylphosphine oxides, o-acyloximes and the like. Moreover, various products are marketed as a photoinitiator. Specific examples include combinations of benzophenone / amine, Michlerketone / benzophenone, thioxanthone / amine, etc. (trade names: Irgacure, Darocur, etc., manufactured by Ciba Geigy). Examples of the thermal polymerization initiator include 2,2′-azobis (isobutyronitrile), 2- (1-cyano-1-methyl) azocarboxamide, 1,1′-azobis (cyclohexane-1-carbonitrile). 2,2′-azobis (2-amidinopropane) dihydrochloride, azobis (methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile),
2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (isobutyrate), 2,2′-azobis [2- (2-imidazolin-2-yl) propane Dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] monosulfate monohydrate, anhydrous 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] disulfate, 2,2′-azobis [2- (2-imidazolin-2-yl)], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydroxyethyl] propinamido, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl)] propinamide, 2,2′-azobis (N-butyl-2-methyl) propinami And azo compounds such as 2,2′-azobis (2,4,4-trimethylpentane); peroxide compounds such as benzoyl peroxide (BPO) and the like.

  In addition to the above, the first liquid may contain additives such as a sensitizer, a dye, and a surfactant. Examples of the sensitizer include amines and thioxanthones.

  In the present invention, by incorporating another substance in the first liquid in advance, a microstructure formed by enclosing another substance in the obtained microstructure can be obtained. Examples of other substances include pigments and microorganisms.

  The second liquid in one embodiment of the present invention may be hydrophilic or oleophilic and can be appropriately selected according to the type of the first liquid used. Specific examples include liquid oils such as soybean oil, water, and aqueous solutions. The second liquid may contain an optional component such as a surfactant.

  In the present invention, the first liquid and the second liquid may be used interchangeably.

  Examples of the combination of the first liquid and the second liquid in the present invention (which is the first liquid and which is the second liquid) include, for example, a lipophilic monomer and a photopolymerization initiator. Examples thereof include a mixture and soybean oil, a mixture of a hydrophilic monomer and a photopolymerization initiator, a mixture of soybean oil and a surfactant, and the like.

B. A three-layer system diagram 12 (a) is a schematic cross-sectional view along the flow path direction of an apparatus (microreactor) 200 that can be preferably used in the manufacturing method according to a preferred embodiment of the present invention, and FIG. FIG. 12C is a cross-sectional view taken along the line BB (ie, viewed from the flow path direction), and FIG. 12C is a cross-sectional view taken along the line CC (ie, viewed from the flow path direction). The apparatus 200 includes a microreactor body 10 and a curing unit 20 for curing a first liquid, a second liquid, and / or a third liquid described later. The microreactor main body 10 includes a first flow path 1, a second flow path 2 formed so as to surround the first flow path 1, and the first flow path 1 and the second flow path 2. The first merge channel 31 formed by merging, the third channel 6 formed so as to surround the first merge channel 31, the first merge channel 31 and the third stream The path 6 is provided with a second merging channel 32 formed by merging. The first flow path 1 and the second flow path 2 are separated by a partition wall 4 on the upstream side (right side in the illustrated example) of the confluence (that is, the upstream end of the first confluence flow path 31) 31a. It has been. The first merging channel 31 and the third channel 6 are separated from each other at the merging point (that is, the upstream end of the second merging channel 32) 32a on the upstream side (right side in the illustrated example). It is partitioned by. The apparatus 200 includes a supply port 1 a to the first flow channel 1, supply ports 2 a and 2 a ′ to the second flow channel 2, and supply ports 6 a and 6 a ′ to the third flow channel 6.

  As a preferred embodiment, the microreactor body of the present invention includes a first channel 1 to which a first liquid is supplied and a second channel to which a second liquid is supplied, as shown in an apparatus 200 of FIG. The flow path 2 includes a first merge flow path 31 formed by three-dimensionally joining the first flow path 1 and the second flow path 2, and the end of the first flow path 1 is an end portion And at least a part of the second flow path 2 is surrounded. Further, the microreactor body of the present invention includes a first merging channel 31, a third channel 6 to which a third liquid is supplied, a first merging channel 31 and a third channel 6. A second merging channel 32 formed by merging three-dimensionally is provided, and at least a part of the first merging channel 31 having an outlet as an end is surrounded by the third channel 6. In the form in which the curing means 20 irradiates ultraviolet light, at least a part of the second merge channel 32 transmits ultraviolet light.

The manufacturing method according to a preferred embodiment of the present invention includes a step of supplying a first liquid to the first flow path 1; a second process that includes an energy ray-curable monomer and a polymerization initiator in the second flow path 2; A step of supplying a third liquid; a step of supplying a third liquid to the third flow path 6; and the first liquid at a confluence 31a of the first flow path 1 and the second flow path 2 A step of bringing the second liquid into contact with each other in a laminar state; a merged flow path 31 formed by the merge of the first flow path 1 and the second flow path 2 and the third flow path 6 Contacting the second liquid and the third liquid in a laminar flow state at a point 32a; and irradiating the second liquid contacted with the third liquid with energy rays. In the present invention, by using the apparatus as described above, the first liquid and the second liquid form a laminar flow at the merge point 31a and the first merge channel 31. Further, the second liquid and the third liquid form a laminar flow at the junction 32 a and the second junction channel 32.

FIG. 13A is a schematic cross-sectional view along the flow path direction of an apparatus (microreactor) 300 that can be preferably used in the manufacturing method according to a preferred embodiment of the present invention, and FIG. It is sectional drawing by the -D line (namely, seeing from the flow-path direction). The apparatus 300 includes a microreactor main body 10 and a curing unit 20 for curing a first liquid, a second liquid, and / or a third liquid described later. The microreactor body 10 is formed so as to surround the first flow path 1, the second flow path 2 formed so as to surround the first flow path 1, and the second merge flow path 2. A third flow path 6, a first flow path 1, a second flow path 2, and a third flow path 6 are provided. The first flow path 1 and the second flow path 2 are partitioned by the partition wall 4 on the upstream side (right side in the illustrated example) of the merging point (that is, the upstream end portion of the merging flow path 33) 33a. . The second flow path 2 and the third flow path 6 are partitioned by a partition wall 4 'on the upstream side (the right side in the illustrated example) 33a of the merging point (that is, the upstream end portion of the merging flow path 33). Yes. The apparatus 300 includes a supply port 1 a to the first flow channel 1, supply ports 2 a and 2 a ′ to the second flow channel 2, and supply ports 6 a and 6 a ′ to the third flow channel 6.

  As a preferred embodiment, the microreactor body of the present invention includes a first channel 1 to which a first liquid is supplied and a second channel to which a second liquid is supplied, as shown in an apparatus 300 in FIG. The flow path 2, the third flow path 6 to which the third liquid is supplied, the first flow path 1, the second flow path 2, and the third flow path 6 merge three-dimensionally. The formed flow path 33 is provided, and at least a part of the first flow path 1 with the outlet at the end is surrounded by the second flow path 2, and the outlet at the second flow path 2 is set as the end. At least a portion is surrounded by the third flow path 6. In the form in which the curing means 20 irradiates ultraviolet light, at least a part of the merging channel 33 transmits ultraviolet light.

The manufacturing method according to a preferred embodiment of the present invention includes a step of supplying a first liquid to the first flow path 1; a second process that includes an energy ray-curable monomer and a polymerization initiator in the second flow path 2; A step of supplying a second liquid; a step of supplying a third liquid to the third flow path 6; and a first liquid at a junction 33a of the first flow path 1 and the second flow path 2. And a step of bringing the second liquid and the second liquid into contact with each other in a laminar flow state; a laminar flow of the second liquid and the third liquid at a junction 33a of the second flow path 2 and the third flow path 6; And a step of irradiating the second liquid contacted with the third liquid with energy rays. In the present invention, by using the apparatus as described above, the first liquid and the second liquid form a laminar flow at the merge point 33a and the first merge channel 33. Further, the second liquid and the third liquid form a laminar flow at the junction 33 a and the second junction flow path 33.

The first liquid in one embodiment of the three-layer system of the present invention includes, for example, a precursor of SiO ₂ such as sodium silicate and methyl silicate.

The second liquid in the three-layer system is the same as the first liquid in the two-layer system described above. The third liquid in the three-layer system is the same as the second liquid in the two-layer system described above.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

  About the microreactor main body shown in FIGS. 1 and 2, a three-dimensional image designed with three-dimensional CAD data is formed into a number of thin cross-sections using an optical modeling apparatus (trade name: SCS-1000HD, manufactured by DEMEC Co., Ltd.). The slice was converted into two-dimensional slice data. A photo-curing resin (trade name: SCR950, manufactured by DEMEC Co., Ltd.) and an elevator are placed in the tank, and a laser (He-Cd laser, peak wavelength = 325 nm) is applied to the light in the tank based on the two-dimensional slice data. The surface of the curable resin was scanned to draw a cross-sectional shape. The laser spot size was φ50 μm. The portion irradiated with the laser was cured, and a cross section for one layer (thickness for one resin layer = 30 μm) was formed on the elevator. After that, the elevator descended one layer at a time, and several thin cross-sections were continuously laminated and three-dimensionally layered. Finally, by lifting the elevator, a three-dimensional layered model was taken out and post-processed to complete the microreactor shown in FIGS. The inner diameter of the outlet of the first channel is 0.42 mm (square shape with a side of 0.3 mm), and four auxiliary channels are formed at the end of the first channel to show the sectional shape of the outlet. 3 was done. The inner diameter of the cross section including the outlet of the first channel in the second channel was (the inner diameter of the outlet of the first channel + 0.9) mm.

In the microreactor body obtained above, a UV exposure machine (manufactured by Ushio Inc., peak wavelength: 365 nm) was installed as a curing means so that ultraviolet light was irradiated from above the microreactor body. The illuminance of direct light of the UV exposure machine was 24.5 mW / cm ² , and the illuminance reached inside the merged channel (thickness L: 0.3 mm) was 19.1 mW / cm ² . The amount of irradiation light was 98 mJ / cm ² . As shown in FIG. 6, until the first liquid and the second liquid contact each other, the first flow path and the second flow path to the junction are covered with a light shielding tape. As shown in FIG. 3, a quartz glass tube (outer diameter: 1.40 mm, inner diameter: 0.9 mm, length: 40 mm) was used at the end of the merged flow path.

[Preparation of the first liquid]
To 6 g of 1,6-hexanediol diacrylate (trade name: HDDA, manufactured by New Frontier), 0.3 g of a photopolymerization initiator (trade name: Irgacure 1700, manufactured by Ciba Geigy) and 0.03 g of lipophilic dye VB2620 The mixture was added dropwise and mixed using a stirrer until uniform.

  Using the microreactor produced in Example 1, the mixed solution was allowed to flow through the first flow path (inner flow path), and soybean oil was flowed into the second flow path (outer flow path). Both the mixed solution and soybean oil were continuously flowed using a syringe pump. The flow rate of the mixed solution was 0.33 μl / second, the flow rate of soybean oil was 20 μl / second, and the flow rate ratio was 1:61. The mixed solution and soybean oil were brought into contact at the junction of the microreactor body. Ultraviolet light was irradiated to the mixed solution in contact with soybean oil to obtain a microstructure.

  The obtained microstructure was a fiber-shaped UV curable resin having a square cross section (100 μm × 150 μm).

A microstructure was obtained in the same manner as in Example 2 except that a linear actuator (PMNA-1005S, manufactured by Tauzer Co., Ltd.) was used to apply a pulsed pressure to the confluence channel (thin wall portion) at 5 Hz.

  The obtained microstructure was a UV curable resin having a rectangular parallelepiped (200 μm × 250 μm × 1 mm).

[Preparation of the first liquid]
To 6 g of Denacol acrylate (trade name: DA-920, manufactured by New Frontier), 0.3 g of a photopolymerization initiator (trade name: Irgacure 1700, manufactured by Ciba Geigy) is dropped and mixed using a stirrer until uniform. did.

  Using the microreactor produced in Example 1, the above mixed solution was allowed to flow in the first flow path (inner flow path), and the surfactant (sorbitan fatty acid ester, trade name: Soybean oil in which sorbitan monolaurate (manufactured by Nacalai Tesque) was dispersed was poured. Both the mixed solution and soybean oil were continuously flowed using a syringe pump. The flow rate of the mixed solution was 0.05 μl / second, the flow rate of soybean oil was 20 μl / second, and the flow rate ratio was 1: 400. The mixed solution and soybean oil were brought into contact at the junction of the microreactor body. Ultraviolet light was irradiated to the mixed solution in contact with soybean oil to obtain a microstructure.

  The obtained microstructure was a spherical UV curable resin having a diameter of 25 μm.

  The microreactor body shown in FIG. 12 was produced in the same manner as in Example 2. The ultraviolet light irradiation conditions were the same as in Example 1.

[Preparation of second liquid]
To 6 g of 1,6-hexanediol diacrylate (trade name: HDDA, manufactured by New Frontier), 0.3 g of a photopolymerization initiator (trade name: Irgacure 1700, manufactured by Ciba Geigy) and 0.03 g of lipophilic dye VB2620 The mixture was added dropwise and mixed using a stirrer until uniform.

  Using the microreactor produced in Example 5, lipophilic methyl silicate 51 (manufactured by Colcoat Co., Ltd.) was passed through the first flow path, the above mixture was passed through the second flow path, and the third flow path was large. Soybean oil was poured. All were continuously flowed using a syringe pump. The flow rate of the lipophilic methyl silicate 51 was 0.025 μl / second, the flow rate of the mixed solution was 2.5 μl / second, and the flow rate of soybean oil was 50 μl / second. The lipophilic methyl silicate 51 and the mixed solution were brought into contact with each other at the junction of the microreactor body, and the mixed solution and soybean oil were brought into contact with each other. Ultraviolet light was irradiated to the mixed solution in contact with soybean oil to obtain a microstructure.

  The resulting microstructure was a UV curable resin encapsulating methyl silicate.

The resulting microstructure was placed in an ammonia catalyst (28 w% ammonia) and removed after 20 minutes. The encapsulated methyl silicate solidified, and a UV curable resin encapsulating SiO ₂ was obtained.

[Preparation of the first liquid]
A solution of sodium silicate dissolved in pure water (at this time, pH 14) so that SiO ₂ is 1 mol / l, an ion exchange resin (trade name: Amberlite IR120BHAG, manufactured by Organo) has a pH of 2-3. It added and stirred until it was about.

[Preparation of second liquid]
To 6 g of Denacol acrylate (trade name: DA-920, manufactured by New Frontier), 0.3 g of a photopolymerization initiator (trade name: Irgacure 1700, manufactured by Ciba Geigy) is dropped and mixed using a stirrer until uniform. did.

  Using the microreactor produced in Example 5, the sodium silicate aqueous solution was passed through the first flow path, the mixed solution was flowed through the second flow path, and pure water was flowed through the third flow path. All were continuously flowed using a syringe pump. The flow rate of the sodium silicate aqueous solution was 0.025 μl / second, the flow rate of the mixed solution was 2.5 μl / second, and the flow rate of pure water was 50 μl / second. The sodium silicate aqueous solution and the mixed solution were brought into contact with each other at the junction of the microreactor body, and the mixed solution and pure water were brought into contact with each other. Ultraviolet light was irradiated to the mixed solution in contact with pure water to obtain a microstructure.

  The obtained microstructure was a UV curable resin containing sodium silicate.

When the obtained microstructure was put in an oven at 50 ° C. and left for 1 hour and then taken out, sodium silicate was solidified, and a UV curable resin containing SiO ₂ was obtained.

  Since the production method of the present invention is very safe and highly accurate, it can be widely used in various chemical industries.

(A) is the schematic seen from the upper direction of preferable embodiment of the microreactor of this invention, (b) is sectional drawing seen from the flow-path direction of the microreactor. It is a perspective view of the microreactor in FIG. It is sectional drawing seen from the flow-path direction of another preferable embodiment of the microreactor of this invention. It is the schematic seen from the top which shows another preferable embodiment of the microreactor of this invention. It is a schematic sectional drawing which shows another preferable embodiment of the microreactor of this invention. FIG. 4 is a perspective view of another preferred embodiment of the microreactor of the present invention. It is the schematic seen from the top which shows another preferable embodiment of the microreactor of this invention. It is a schematic sectional drawing along the flow-path direction of another preferable embodiment of the microreactor of this invention. It is a schematic sectional drawing which shows preferable embodiment of the pulse generation means in the microreactor of this invention. It is sectional drawing seen from the flow-path direction in case the 1st flow path in the micro reactor of this invention has a double structure of an inner flow path and an outer flow path. It is the schematic explaining the typical example of the microstructure obtained by the manufacturing method of this invention. (A) is schematic sectional drawing along the flow-path direction of preferable embodiment of the microreactor of this invention, (b) is sectional drawing seen from the flow-path direction of the microreactor, (c) These are sectional views seen from the flow path direction of the microreactor. (A) is schematic sectional drawing along the flow-path direction of preferable embodiment of the microreactor of this invention, (b) is sectional drawing seen from the flow-path direction of the microreactor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Microreactor 10 Microreactor main body 20 Curing means 30 Light-shielding means 40 Pulse generating means 50 Diaphragm 60 Actuator 1 1st flow path 2 2nd flow path 3 Merge flow path 4 Bulkhead 5 Auxiliary flow path 1a To 1st flow path Supply port 2a Supply port to the second flow path 2a 'Supply port to the second flow path 3a Junction point

Claims (22)

Supplying a first liquid containing an energy ray-curable monomer and a polymerization initiator to the first flow path;
Supplying a second liquid to a second channel formed to surround the first channel;
Contacting the first liquid and the second liquid in a laminar flow state at a point where the first flow path and the second flow path meet;
And irradiating the first liquid contacted with the second liquid with energy rays.   The manufacturing method of Claim 1 whose Reynolds number of the said laminar flow is 0.1-200.   The manufacturing method according to claim 1, wherein a flow rate of the first liquid is smaller than a flow rate of the second liquid.   The manufacturing method according to claim 1, wherein the first liquid is continuously supplied.   The manufacturing method according to claim 1, wherein the first liquid is supplied in a pulsating manner.   The manufacturing method according to claim 1, wherein the first flow path has a substantially circular, elliptical, polygonal, cross-shaped or star-shaped cross-sectional shape.   The production method according to claim 1, wherein fine particles, rods or fibers are formed. Supplying a first liquid to the first flow path;
Supplying a second liquid containing an energy ray-curable monomer and a polymerization initiator to a second channel formed so as to surround the first channel;
Supplying a third liquid to a third channel formed so as to surround the merged channel formed by the merge of the first channel and the second channel;
Contacting the first liquid and the second liquid in a laminar flow state at a point where the first flow path and the second flow path meet;
The second liquid and the third liquid are layered at a point where the merged flow path formed by the first flow path and the second flow path merges with the third flow path. Contacting in a flow state;
Irradiating the second liquid brought into contact with the third liquid with energy rays. Supplying a first liquid to the first flow path;
Supplying a second liquid containing an energy ray-curable monomer and a polymerization initiator to a second channel formed so as to surround the first channel;
Supplying a third liquid to a third channel formed so as to surround the second channel;
Contacting the first liquid and the second liquid in a laminar flow state at a point where the first flow path and the second flow path meet;
Contacting the second liquid and the third liquid in a laminar flow state at a point where the second flow path and the third flow path meet;
Irradiating the second liquid brought into contact with the third liquid with energy rays. The first flow path to which the first liquid is supplied, the second flow path to which the second liquid is supplied, the first flow path and the second flow path are three-dimensionally merged. A microreactor body comprising a merging channel formed by
A curing means for curing the first liquid and / or the second liquid;
A microreactor, wherein at least a part of the first channel having an outlet as an end is surrounded by the second channel.   The microreactor according to claim 10, wherein at least a part of the merging channel transmits ultraviolet light, and the curing means is ultraviolet light irradiation means. 12. The microreactor according to claim 11, further comprising a light shielding means for preventing the first flow path and / or the second flow path from being irradiated with ultraviolet light.   The microreactor according to claim 10, further comprising a plurality of second liquid supply ports to the second flow path.   The microreactor according to any one of claims 10 to 13, wherein an inner diameter of the outlet of the first flow path is 0.05 to 0.8 mm.   The inner diameter of the cross section including the outlet of the first channel in the second channel is (the inner diameter of the outlet of the first channel + 0.2) mm or more (the outlet of the first channel). The microreactor according to any one of claims 10 to 14, which has an inner diameter of +1.6) mm or less.   The microreactor according to any one of claims 10 to 15, wherein pulse generating means for causing the first liquid to flow in a pulsating manner is provided in the first flow path.   17. The microreactor according to claim 16, wherein the pulse generating means uses a part of the first flow path as a diaphragm part and vibrates the diaphragm part with an actuator.   The flow rate control means for changing the flow volume of the 1st liquid in the said 1st flow path and the flow volume of the 2nd liquid in the said 2nd flow path is provided in any one of Claim 10 to 17 The microreactor as described. A first flow path to which a first liquid is supplied; a second flow path to which a second liquid is supplied; a third flow path to which a third liquid is supplied; and the first flow path. A first merging channel formed by three-dimensionally joining the path and the second channel, and a first merging channel and the third channel formed by joining three-dimensionally A microreactor body comprising a second merging flow path,
Curing means for curing the first liquid, the second liquid and / or the third liquid;
At least a part of the first flow path with the outlet as an end is surrounded by the second flow path, and at least a part of the first flow path with the outlet at the end is the third flow A microreactor surrounded by a road.   20. The microreactor according to claim 19, wherein at least a part of the second merging channel transmits ultraviolet light, and the curing means is ultraviolet light irradiation means. A first flow path to which a first liquid is supplied; a second flow path to which a second liquid is supplied; a third flow path to which a third liquid is supplied; and the first flow path. A microreactor main body comprising a merging channel formed by three-dimensionally merging the channel, the second channel, and the third channel;
Curing means for curing the first liquid, the second liquid and / or the third liquid;
At least a part of the first channel with the outlet as an end is surrounded by the second channel, and at least a part of the second channel with the outlet as an end is the third channel A microreactor surrounded by The microreactor according to claim 21, wherein at least a part of the confluence channel transmits ultraviolet light, and the curing means is an ultraviolet light irradiation means.

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