JP5245164B2 - Microreactor and method for manufacturing microreactor - Google Patents

Description

  The present invention relates to a microreactor and a method for producing a microreactor.

  Conventionally, it has a flow path (micro flow path, micro channel) with a width of several [μm] to several hundreds [μm] through which a sample fluid (micro fluid) passes. About chemical reaction equipment and chemical analysis systems such as Lab-On-a-Chip (Laboratory on a Chip) and μTAS (Micro Total Analysis System) that perform measurements, so-called microreactors (microchannel reactors, microfluidic devices) Technology is known. The microreactor can perform reaction and measurement using a small amount of sample, and can save resources, save energy, increase efficiency, reduce costs, etc., when using hazardous substances and hazardous substances. Safety is also considered high. For this reason, the microreactor is useful in various fields such as analytical chemistry, synthetic chemistry, medical treatment, and environmental measurement, and research and development are actively performed.

  In addition, the space inside the microchannel increases the surface area of the inner surface per volume, so-called specific surface area, so the range in which the sample can be held is wider than when the specific surface area is small, and the efficiency of the chemical reaction is increased. Is known to be high. Here, in order to further increase the efficiency of the chemical reaction, it has been proposed to provide a structure (chemical analysis structure) for increasing the specific surface area in the microchannel. As a technique for imparting a structure for increasing the specific surface area in the microchannel, the techniques of Patent Document 1 and Non-Patent Documents 1 and 2 below are conventionally known.

  Japanese Patent Application Laid-Open No. 2008-284433 as Patent Document 1 describes a technique for a microreactor in which a mesoporous silica thin film having a film thickness of 200 [nm] or less is immobilized on the inner surface of a hollow microchannel. . That is, Patent Document 1 describes a technology that uses a silica thin film having a regular mesopore structure, easily supports a catalyst that is usually difficult to support, and improves the efficiency of chemical reactions. In Patent Document 1, first, the precursor solution of the silica thin film is caused to flow and permeate into capillary glass in which the hollow microchannel is formed by a syringe. Next, excess precursor solution is removed from the hollow microchannel by blowing nitrogen gas. Then, the capillary glass was dried at 70 ° C. for 8 hours and then sintered at 440 ° C. for 4 hours. As a result, the silica thin film was fixed on the inner surface of the hollow microchannel, and the mesoscopic thin film was ordered. A pore structure is formed and the microreactor is fabricated.

Non-Patent Document 1 describes a technique regarding a microchip (microreactor) in which carbon nanotubes (CNTs) are vertically aligned in a microchannel. In Non-Patent Document 1, a flat and wide microchannel (microchannel) is formed on a silicon substrate, and then a chemical vapor deposition method (chemical vapor deposition method, chemical vapor deposition method, CVD :) using xylene and ferrocene as raw materials. After the vertically aligned multi-walled carbon nanotubes are selectively formed in the microchannel by chemical vapor deposition, the microchip is manufactured by adhering heat resistant glass.
That is, Non-Patent Document 1 describes a technique of directly producing carbon nanotubes by the chemical vapor deposition method on a silicon substrate on which a flat and wide micro-channel that becomes the bottom surface of a microchannel is produced.

Furthermore, Non-Patent Document 2 describes a technique for directly producing carbon nanotubes in the microchannel by the chemical vapor deposition method, as in Non-Patent Document 1. In Non-Patent Document 2, first, soda-lime glass having a length of 15 [mm], a width of 140 [μm], and a depth of 20 [μm], 25 [μm], 30 [μm] and 35 [μm]. The microchannel manufactured is prepared, and a thin film of Fe—Si catalyst is deposited and fixed on the bottom surface. And after inject | pouring methane in the said microchannel, the microwave of 500 [W] is irradiated and the carbon nanotube is created. In Non-Patent Document 2, when carbon nanotubes are formed on a flat substrate by the above-described method of performing chemical vapor deposition by irradiating microwaves to methane, the length L _f [μm] of the carbon nanotubes is In contrast to the growth time t [min] that is proportional to the power of 1.5 (L _f = k ₁ × t ^1.5 ), when carbon nanotubes are created in the microchannel, carbon nanotubes It is described that the length L _c [μm] of the crystal grew in proportion to the 0.5th power of the creation time t [min] (L _c = k ₂ × t ^0.5 ).

  The carbon nanotubes described in Non-Patent Documents 1 and 2 are tubular substances having a diameter of several [nm] to several tens [nm] and a length of several [μm] to several [mm]. In addition, by the chemical vapor deposition method described in Non-Patent Documents 1 and 2, the carbon nanotubes are spaced from each other by several tens [nm] to several hundreds [nm], and the length as a representative dimension is several tens [μm]. It is also possible to create such that

JP 2008-284433 A (Abstract, “0007” to “0030”, FIGS. 1 to 5)

Hiroki Sato, “Catalytic Function of Oriented Carbon Nanotubes Grown in a Microchip”, “online”, May 31, 2006, Nissan Science Foundation, “March 19, 2009 search”, Internet <URL : Http://www.nissan-zaidan.or.jp/membership/2004/05_seika/0009.pdf> Hao-Hsuan Wu and two others, “Growth of carbon nanotubes in the microchannels of glass substrates”, Diamond and Related Materials 17 (Diamond & Related Materials 17), (USA), Elsevier, 2008, p. 1462-1466 Shigeo Maruyama and 3 others, “Low-temperature and high-purity production of single-walled carbon nanotubes by alcohol CCVD method”, “online”, February 4, 2003, University of Tokyo, “March 30, 2009 search”, Internet <URL : Http://www.photon.tu-tokyo.ac.jp/~maruyama/papers/02/Miyauchi_JSME.pdf> "PDMS specification-PDMS microfluidic chip manufacturing service Fluidware Technologies", "online", April 2007, Fluidware Technologies, Inc., "April 1, 2009 search", Internet <URL: http: // www.fluidware-technologies.com/chip/hard-pdms/hard-pdms-index.htm> “Wako Bio Window No. 29”, “online”, May 2001, Wako Pure Chemical Industries, Ltd., “April 7, 2009 search”, Internet <URL: http://www.wako-chem.co .jp / siyaku / journal / biowin / pdf / bio29.pdf> “Micro TAS Adhesive Device [USHIO Inc.]”, “online”, March 2007, USHIO ELECTRIC CO., LTD., “April 1, 2009 search”, Internet <URL: http://www.ushio.co .jp / jp / products / list / bio_mems / bio_mems_02.html>

(Problems of conventional technology)
In the technique of Patent Document 1, when preparing a silica thin film having a regular mesopore structure, each step of introducing a precursor solution, removing excess, drying and sintering is required. There was a problem that the production process of the reactor increased and the production cost increased.
Moreover, in the technique of the said patent document 1, the said process to sinter is required and it is necessary to heat the inside of the said microchannel at high temperature. Similarly, in the techniques of Non-Patent Documents 1 and 2, it is necessary to heat the inside of the microchannel at a high temperature in order to produce the carbon nanotubes by the chemical vapor deposition method.
That is, the techniques of Patent Document 1 and Non-Patent Documents 1 and 2 have a problem that the inside of the microchannel must be heated at a high temperature in order to give the microchannel a structure that increases the specific surface area. It was.

Further, in the techniques of Non-Patent Documents 1 and 2, when the carbon nanotubes are directly formed in the narrow microchannel, it is difficult to grow the carbon nanotubes longer than when synthesized on a flat silicon substrate. As described in (1), since it grows only to about 1 [μm] at a practical production time and is difficult to be oriented perpendicular to the substrate, the representative dimension is about several tens [μm]. There was a problem that it was difficult to grow it.
That is, the techniques of Non-Patent Documents 1 and 2 have a problem that the carbon nanotubes cannot be sufficiently grown in the microchannel, and it is difficult to increase the specific surface area of the microchannel.

  In view of the above-described circumstances, the present invention has a technical problem of increasing the specific surface area of a microchannel.

In order to solve the technical problem, a method of manufacturing a microreactor according to claim 1 comprises:
A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate;
The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. And a tube transfer step of transferring the carbon nanotubes on the tube generation surface to the groove,
In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
With
A method for producing a microreactor, wherein the specific surface area in the flow path is increased by the carbon nanotubes ,
further,
A carbon nanotube in which a plurality of carbon nanotubes transferred to the groove are brought into contact with a liquid communicating between the plurality of carbon nanotubes, and the liquid is vaporized to bundle the plurality of carbon nanotubes. Tube bundle creation process to create a bundle,
It is provided with.

  In order to solve the technical problem, the method for producing a microreactor according to the invention of claim 2 comprises:
  A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate;
  The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. And a tube transfer step of transferring the carbon nanotubes on the tube generation surface to the groove,
  In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
  With
  The specific surface area in the channel is increased by the carbon nanotube.
  A method of manufacturing a microreactor characterized by comprising:
  In the tube generating step, a hole of a mask corresponding to the convex portion is fitted into a convex portion of the transfer substrate formed according to the groove, and the mask is mounted on the transfer substrate, so that the tube is generated. In a state where the outer surface of the mask is disposed along the outer surface of the convex portion as a surface, the mask that is detachable from the transfer substrate after the carbon nanotubes are generated on each outer surface. Remove and leave the carbon nanotubes only on the outer surface of the convex part,
  In the tube transfer step, the carbon nanotubes on the outer surface of the convex portion are transferred to the groove.
  It is characterized by that.

  In order to solve the technical problem, the method for producing a microreactor according to the invention of claim 3 comprises:
  A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate by an alcohol-catalyzed CVD method;
  The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. The carbon nanotubes on the tube generation surface are inserted into the grooves without breaking the orientation of the carbon nanotubes by piercing the tip of the carbon nanotubes on the transfer surface side. Tube transfer process to transfer,
  In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
  With
  The specific surface area in the channel is increased by the carbon nanotube.
  It is characterized by that.

In order to solve the technical problem, the microreactor of the invention according to claim 4 comprises:
A transfer surface on which a groove is formed, and the carbon nanotube transferred to the groove with the tube generation surface of the transfer substrate on which the carbon nanotube is generated on the tube generation surface facing the transfer surface. A substrate to be transferred,
A closing substrate that has a closing surface and is bonded to the transfer substrate and closes the opening side of the groove in a state where the transfer surface and the closing surface are opposed to each other;
A flow path as a space surrounded by the carbon nanotube, the groove, and the blocking surface;
A bundle of carbon nanotubes in which the tip ends of a plurality of the carbon nanotubes whose base ends are supported on the common transferred surface;
It is provided with.

The invention according to claim 5 is the microreactor according to claim 4 ,
The transferred surface composed of polydimethylsiloxane,
It is provided with.

According to the first to fourth aspects of the present invention, since carbon nanotubes generated on the tube generation surface are transferred to the groove, carbon grown sufficiently long compared to the case where carbon nanotubes are directly generated in the flow path. Nanotubes can be arranged in the flow path, and the specific surface area in the flow path can be increased.

According to the first and fourth aspects of the present invention, when the gap between the carbon nanotube bundles can be used as a reaction field for a chemical reaction, the efficiency of the chemical reaction in the channel can be improved.
According to the first and fourth aspects of the present invention, the groove formed by the adsorbing member is adsorbed by the carbon nanotubes on the tube generation surface. Nanotubes can be easily transferred. Further, according to the first and fourth aspects of the present invention, the transfer surface can be adhered to the closing surface so that the transfer surface and the closing surface can be brought into close contact with each other, and the transfer surface is not constituted by the adsorption member. Compared to the case, the resin substrate and the closed substrate can be easily joined, and the flow path can be easily formed.

According to the second aspect of the present invention, carbon nanotubes corresponding to grooves having an arbitrary shape can be generated, and the carbon nanotubes on the outer surface of the convex portion can be transferred to the grooves. As a result, for example, even when the groove is formed with a width on the order of micrometers, the carbon nanotubes can be transferred into the groove with a width on the order of micrometers, and the degree of freedom of the shape of the flow path can be increased. In addition, carbon nanotubes that have grown sufficiently long on the outer surface of the convex portion can be placed in the flow channel with a width of the order of micrometers, so that the carbon nanotubes can be grown sufficiently long in the microchannel with a width of the order of micrometers. The specific surface area in the flow path can be increased as compared with the case where there is not.
According to the third aspect of the present invention, it is possible to reduce the collapse of the orientation during the transfer of the carbon nanotubes as compared with the case where the configuration of the present invention is not provided.

According to the invention described in claim 5 , polydimethylsiloxane can be molded with a mold to produce a resin substrate, and the groove can be easily processed. Further, according to the invention described in claim 5 , the polydimethylsiloxane has high elasticity, self-adsorption property, viscosity (fluidity), and the groove is not constituted by the polydimethylsiloxane, The carbon nanotube can be easily transferred to the groove.

FIG. 1 is an overall explanatory view of a microreactor according to Embodiment 1 of the present invention. 2 is an enlarged explanatory view of the main part of the microreactor of Example 1 of the present invention, FIG. 2A is an explanatory view of the resin substrate of Example 1, and FIG. 2B is an explanatory view of the glass plate of Example 1. 2C is an enlarged explanatory view of a section taken along the line IIC-IIC in FIG. 1, and is an explanatory view of the carbon nanotube bundle of Example 1. FIG. FIG. 3 is an explanatory diagram of a tube generation process according to the first embodiment of the present invention, and is an explanatory diagram of a chemical vapor deposition apparatus. 4A and 4B are explanatory views of the tube transfer process according to the first embodiment of the present invention, FIG. 4A is a perspective explanatory view when a resin substrate is formed using a mold, and FIG. 4B is a perspective view of the groove of the resin substrate and the silicon substrate. FIG. 4C is a sectional view taken along the line IVC-IVC in FIG. 4B, and FIG. 4D is a plan view of the groove of the resin substrate and the flatness of the silicon substrate from the state of FIG. 4C. FIG. 4E is an explanatory view of a state in which the groove of the resin substrate and the flat surface of the silicon substrate are opposed to each other from the state of FIG. 4D from the state of FIG. 4D. 5A and 5B are explanatory views of a microchannel forming process according to the first embodiment of the present invention, FIG. 5A is a perspective explanatory view of the state of FIG. 4E corresponding to FIG. 4B, and FIG. 5B is a perspective view of the silicon substrate from the state of FIG. FIG. 5C is a perspective explanatory view of a state in which the closed surface of the glass plate is made to face and approach the adsorption surface of the resin substrate instead of the flat surface, FIG. 5C is a sectional view taken along the line VC-VC of FIG. 5B, and FIG. It is explanatory drawing of the state which the resin substrate and the glass plate joined from the state of 5C. FIG. 6 is an explanatory view of the tube bundle creating process of the first embodiment of the present invention, FIG. 6A is an explanatory view of a state where a syringe needle is inserted into one through hole from the state of FIG. 5D, and FIG. FIG. 6C is an explanatory diagram of a state in which ethanol is injected into the microchannel from the state of 6A, and FIG. 6C is an explanatory diagram of a state in which ethanol is vaporized by injecting air from the state of FIG. 6B into the microchannel. 7A and 7B are explanatory views when the mask is mounted on the silicon substrate having a convex portion in the tube generation process of the first embodiment, FIG. 7A is an explanatory diagram of a state where the mask is mounted on the silicon substrate, and FIG. 7C is an explanatory view of a mask, FIG. 7D is an explanatory view of a state where carbon nanotubes are generated from the state of FIG. 7A, and FIG. 7E is a state where the mask is removed from the state of FIG. 7C It is explanatory drawing of a state. FIG. 8 is an operation explanatory view of Example 1 of the present invention, and is an enlarged explanatory view when carbon nanotubes before and after transfer are observed with a scanning electron microscope. FIG. 8A is a view before transfer on a flat surface of a silicon substrate. FIG. 8B is an explanatory view of the carbon nanotube after transfer into the groove of the resin substrate. FIG. 9 is an experimental result of Experimental Examples 1 and 2, and is an enlarged explanatory diagram when the tip of the aggregated carbon nanotube bundle is observed with a scanning electron microscope. FIG. 9A is a liquid contact range and a non-contact range. FIG. 9B is an explanatory diagram showing a state in which the tips of carbon nanotubes having a typical dimension of Experimental Example 1 of 18.5 [μm] are aggregated, and FIG. It is explanatory drawing of the state which the front-end | tip part of the carbon nanotube of 5 [micrometers] aggregated. FIG. 10 shows the experimental results of Experimental Example 1 and Experimental Example 2, and is an explanatory diagram of a graph in which the horizontal axis represents the representative dimension [μm] of the carbon nanotube and the vertical axis represents the aggregated width [μm] of the carbon nanotube. . FIG. 11 shows the experimental results of Experimental Example 1 and Experimental Example 2, and is an explanatory diagram of a graph in which the horizontal axis represents the representative dimension [μm] of the carbon nanotubes and the vertical axis represents the aggregation interval [μm] of the carbon nanotubes. is there. FIG. 12 is an experimental result of Experimental Example 3, and is an enlarged explanatory diagram when the tip of the carbon nanotube in the microchannel is observed with a scanning electron microscope. FIG. 12A is a graph of carbon before ethanol injection in the tube bundle forming step. 12B is an explanatory view showing the state of the tip of the nanotube, FIG. 12B is an explanatory view showing the state of the tip of the carbon nanotube after ethanol injection from the state of FIG. 12A, and FIG. 12C is the state of the carbon nanotube after ethanol evaporation from the state of FIG. FIG. 12D is an explanatory view showing the state of the tip of the carbon nanotube after ethanol re-injection from the state of FIG. 12C. FIG. 13 is an explanatory view of the process of vaporizing ethanol in the microchannel, FIG. 13A is an explanatory view of a state where air is injected from the state of FIG. 6B and ethanol is removed, and FIG. 13B is an ethanol state from the state of FIG. FIG. 13C is an enlarged explanatory view of the ethanol droplet of FIG. 13B, and FIG. 13D is an illustration of the ethanol from the state of FIG. 13C. It is explanatory drawing of the state to which the droplet of this shrunk | reduced. FIG. 14 is an explanatory diagram of the experimental devices of Experimental Examples 4 and 5, and Comparative Example 1, FIG. 14A is an overall explanatory diagram of the experimental device, FIG. 14B is an explanatory diagram of the microreactor of Experimental Example 4, and FIG. 14D is an explanatory diagram of the microreactor of Comparative Example 1. FIG. FIG. 15 shows the experimental results of Experimental Examples 4 and 5 and Comparative Example 1, and is an explanatory diagram of a graph with time [sec] on the horizontal axis and fluorescence intensity of resorufin on the vertical axis.

Next, specific examples of embodiments of the present invention (hereinafter referred to as examples) will be described with reference to the drawings, but the present invention is not limited to the following examples.
In the following description using the drawings, illustrations other than members necessary for the description are omitted as appropriate for easy understanding.

FIG. 1 is an overall explanatory view of a microreactor according to Embodiment 1 of the present invention.
2 is an enlarged explanatory view of the main part of the microreactor of Example 1 of the present invention, FIG. 2A is an explanatory view of the resin substrate of Example 1, and FIG. 2B is an explanatory view of the glass plate of Example 1. 2C is an enlarged explanatory view of a section taken along the line IIC-IIC in FIG. 1, and is an explanatory view of the carbon nanotube bundle of Example 1. FIG.
1 and 2, a microreactor (microreaction apparatus) 1 according to a first embodiment of the present invention includes a resin substrate 2 as an example of a substrate to be transferred and a glass plate 3 as an example of a closing substrate.

The resin substrate 2 of Example 1 includes a suction surface 2a as an example of a transfer surface and an outer surface 2b opposite to the suction surface 2a. A groove 2c having a depth on the order of micrometers is formed on the suction surface 2a of the first embodiment. Further, at both ends of the groove 2c, through holes 2d and 2d penetrating the surfaces 2a and 2b are formed.
In FIG. 2C, a plurality of carbon nanotubes 4 supported in a state where the base end portion is pierced into the bottom surface of the groove 2c are arranged inside the groove 2c. Moreover, in Example 1, the front-end | tip part of the said adjacent carbon nanotube 4 is bundled by the opening side of the said groove | channel 2c, and the several carbon nanotube bundle 6 which is a bundle for every adjacent said carbon nanotube 4 is formed. ing.

In addition, the said groove | channel 2c of Example 1 is preset so that the vertical width and horizontal width of the said bottom face may be 10 [mm] * 10 [mm], and a depth may be 60 [micrometers]. Furthermore, in Example 1, the average value of the length of each carbon nanotube 4, that is, the so-called representative dimension is preset to be about 28 [μm].
Moreover, the said glass plate 3 of Example 1 has the obstruction | occlusion surface 3a facing the said adsorption surface 2a.
In the microreactor 1 of Example 1, the adsorption surface 2a and the blocking surface 3a are joined, and the resin substrate 2 and the glass plate 3 are joined. In the microreactor 1, the opening side of the groove 2c is closed by the closing surface 3a, and a microchannel (microchannel) as a space surrounded by the carbon nanotube bundle 6, the groove 2c, and the closing surface 3a. (Channel, microchannel, channel) 7 is formed.

(About the manufacturing method of the microreactor of Example 1)
Next, the flow of each process of the manufacturing method of the said microreactor 1 of Example 1 is demonstrated below.
(About the tube production process of Example 1)
FIG. 3 is an explanatory diagram of a tube generation process according to the first embodiment of the present invention, and is an explanatory diagram of a chemical vapor deposition apparatus.
In FIG. 3, the carbon nanotubes 4 of Example 1 are generated by a chemical vapor deposition apparatus 11 as an example of a tube generation apparatus.
The chemical vapor deposition apparatus 11 of Example 1 has a heating chamber 14 surrounded by a support base 12 that supports a sample and an outer peripheral wall 13 that covers the upper side of the support base 12. Further, an upper end portion of the heating chamber 14 extends through the support base 12 into the heating chamber 14 and a lower end portion outside the heating chamber 14 is connected to a power source 16. As an example, heater support portions 17 and 17 are supported by the support base 12. A flat plate-like heater 18 as an example of a heating member is supported on the upper ends of the heater support portions 17 and 17.

On the heater 18 of the first embodiment, a silicon substrate (silicon substrate with oxide film, Si / SiO ₂ substrate) 19 as an example of a transfer substrate is supported. The silicon substrate 19 according to the first embodiment includes a flat surface (upper surface) 19 a as an example of a tube generation surface, and a heated surface (lower surface) 19 b opposite to the flat surface 19 a that contacts the heater 18. On the flat surface 19a, a catalyst 21 composed of iron (Fe) as a main component and other catalyst auxiliary agents is formed by physical vapor deposition.
In addition, the said silicon substrate 19 of Example 1 is preset so that a vertical width and a horizontal width may be 8 [mm] x 8 [mm].
Further, below the heater 18, a sample container 22 in which ethanol as a sample is stored is supported by the support 12.
Further, the heating chamber 14 of Example 1 includes a vacuum pump (rotary pump) 23 for exhausting (evacuating) gas (reactive gas, active gas) in the heating chamber 14, and the heating chamber 14. A nitrogen tank 24 for injecting nitrogen gas (inert gas) into the inside is connected.

  In FIG. 3, in the tube generation process of Example 1, first, the heating chamber 14 is evacuated by the vacuum pump 23, and the heating chamber 14 is filled with nitrogen gas by the nitrogen tank 24. The inside of the chamber 14 is purged. Next, the sample storage container 22 in which ethanol is stored is caused to enter the heating chamber 14 filled with nitrogen gas. Next, the heater 18 is heated to about 700 ° C., and the silicon substrate 19 and the catalyst 21 are heated. As a result, the iron (Fe) of the catalyst 21 is heated to form fine particles, and the ethanol stored in the sample storage container 22 is vaporized by the heat of the heater 18. Then, the ethanol as a vaporized carbon source fills the heating chamber 14, collides with the fine particles of iron (Fe), and carbon atoms are dissolved (incorporated) into the iron (Fe). The carbon nanotubes 4 are deposited.

That is, in the tube generation step of Example 1, the ethanol is dissolved in the iron (Fe) by heating the heater 18 to generate the carbon nanotubes 4 on the flat surface 19a.
In the tube generation step of Example 1, the carbon nanotubes 4 can be grown until iron (Fe) of the catalyst 21 is deactivated. Therefore, it was confirmed that the representative dimension of the carbon nanotube 4 can be grown to about 28 [μm] in about 10 [min], for example, according to the life of the catalyst 21.
In addition, the said tube production | generation process of Example 1 is described in the nonpatent literature 3 etc., for example as what is called alcohol CCVD (alcohol catalytic CVD, Alcohol Catalytic Chemical Vapor Deposition) method, and is well-known.

(About the tube transfer process of Example 1)
FIG. 4 is an explanatory view of the tube transfer process of the first embodiment of the present invention, FIG. 4A is a perspective explanatory view when a resin substrate is created using a mold, and FIG. FIG. 4C is a sectional view taken along the line IVC-IVC in FIG. 4B, and FIG. 4D is a plan view of the groove of the resin substrate and the flatness of the silicon substrate from the state of FIG. 4C. FIG. 4E is an explanatory view of a state in which the groove of the resin substrate and the flat surface of the silicon substrate are opposed to each other from the state of FIG. 4D from the state of FIG. 4D.
4A, the resin substrate 2 of Example 1 can be manufactured by pouring a resin into a mold (mold) 26, for example. In the central portion of the mold 26 of Example 1, the vertical width and the horizontal width are set in advance to 10 [mm] × 10 [mm] and the height is set to 60 [μm] corresponding to the groove 2c. A protrusion 26a is formed.

In Example 1, polydimethylsiloxane (PDMS), which is an example of an adsorbing member, is used as the resin to be poured, similarly to a conventionally known microreactor.
In FIG. 4A, in Example 1, first, the mold 26 into which the liquid polydimethylsiloxane was poured was heated at 60 ° C. for 60 [min] to cure the polydimethylsiloxane. Next, the resin substrate 2 is manufactured by peeling the polydimethylsiloxane from the mold 26 and opening the through holes 2d and 2d.

  4B to 4E, in the tube transfer process of Example 1, first, the groove 2c of the adsorption surface 2a of the resin substrate 2 and the flat surface 19a of the silicon substrate 19 are opposed to each other, as shown in FIG. The state shown in FIG. 4C is set. Next, from the state shown in FIGS. 4B and 4C, the groove 2c and the flat surface 19a are brought close to each other, and the carbon nanotube 4 on the flat surface 19a is sandwiched between the groove 2c and the flat surface 19a. The state shown in FIG. 4D is set. As a result, the tip of the carbon nanotube 4 on the flat surface 19a is stuck into the bottom surface of the groove 2c.

Here, it is known that the thermosetting polydimethylsiloxane used as silicon rubber (silicone resin) has high elasticity, self-adsorption property, viscosity (fluidity), etc. (for example, non-patent Reference 4 etc.). Therefore, when the front end of the carbon nanotube 4 on the flat surface 19a is pushed into the bottom surface of the groove 2c, the front end is pierced into the bottom, and the elasticity of the polydimethylsiloxane causes the front end of the front end. It is considered that the stabbed area is clamped and clamped, or the bottom surface pushed away by the tip portion flows and returns to be attached to the tip portion and adsorbed.
When the groove 2c and the flat surface 19a are separated from the state shown in FIG. 4D, the carbon nanotubes 4 pierced into the groove 2c are separated from the flat surface 19a as shown in FIG. 4E. .
That is, in the tube transfer process of Example 1, the grooves 2c and the flat surface 19a are brought close to each other, and the carbon nanotubes 4 on the flat surface 19a are pressed against the grooves 2c, whereby the carbon nanotubes 4 are Transfer from the flat surface 19a to the groove 2c.

(About the microchannel formation process of Example 1)
5A and 5B are explanatory views of a microchannel forming process according to the first embodiment of the present invention, FIG. 5A is a perspective explanatory view of the state of FIG. 4E corresponding to FIG. 4B, and FIG. 5B is a perspective view of the silicon substrate from the state of FIG. FIG. 5C is a perspective explanatory view of a state in which the closed surface of the glass plate is made to face and approach the adsorption surface of the resin substrate instead of the flat surface, FIG. 5C is a sectional view taken along the line VC-VC of FIG. 5B, and FIG. It is explanatory drawing of the state which the resin substrate and the glass plate joined from the state of 5C.
Further, in FIG. 5, in the microchannel forming process (flow path forming process) of Example 1, first, the carbon nanotubes 4 are transferred from the state shown in FIG. 5A to the closed surface 3a of the glass plate 3. It is made to oppose to the adsorption surface 2a of the resin substrate 2, and it is set as the state shown to FIG. 5B and FIG. 5C.

5B and 5C, the suction surface 2a and the closing surface 3a are brought close to each other, the resin substrate 2 and the glass plate 3 are brought into close contact with each other, and the state shown in FIG. 5D is obtained. To do. As a result, the lower side, which is the opening side of the groove 2c, is blocked by the adsorption surface 2a and the blocking surface 3a, and the microchannel 7 surrounded by the carbon nanotube 4, the groove 2c, and the blocking surface 3a. Is formed.
That is, in the microchannel forming step of the first embodiment, the microchannel 7 is formed by closing the opening of the groove 2c with the suction surface 2a and the closing surface 3a.

(Regarding the tube bundle creation step of Example 1)
FIG. 6 is an explanatory view of the tube bundle creating process of the first embodiment of the present invention, FIG. 6A is an explanatory view of a state where a syringe needle is inserted into one through hole from the state of FIG. 5D, and FIG. FIG. 6C is an explanatory diagram of a state in which ethanol is injected into the microchannel from the state of 6A, and FIG. 6C is an explanatory diagram of a state in which ethanol is vaporized by injecting air from the state of FIG. 6B into the microchannel.
5 and FIG. 6, in the tube bundle creation step of Example 1, first, from the state shown in FIG. 5D, as shown in FIG. 6A, the needle of the syringe (syringe) 27 containing ethanol is Is inserted into the through hole 2d. Next, from the state shown in FIG. 6A, ethanol in the syringe 27 is injected (injected) into the microchannel 7, and the microchannel 7 is filled with the ethanol as shown in FIG. 6B. The ethanol is infiltrated between the carbon nanotubes 4.

6B, after the air is re-contained in the syringe 27, the air in the syringe 27 is injected (injected) into the microchannel 7, and the ethanol in the microchannel 7 is injected. Then, the air is pushed out from the other through-hole 2d and removed, and then the air is continuously injected. As a result, as shown in FIG. 6C, the ethanol remaining in the microchannel 7 is dried and vaporized, and the tips of the plurality of adjacent carbon nanotubes 4 aggregate to form a plurality of the A carbon nanotube bundle 6 is created.
That is, in the tube bundle forming step of Example 1, the carbon nanotube bundle 6 is formed by bringing ethanol into contact with the carbon nanotubes 4 in the microchannel 7 and then injecting air to vaporize the ethanol. To do.

(Operation of Example 1)
In the microreactor 1 of Example 1 having the above-described configuration, a plurality of the carbon nanotubes 4 are arranged in the microchannel 7 as shown in FIGS. Therefore, the microreactor 1 of Example 1 can increase the specific surface area in the microchannel 7 as compared with the case where the carbon nanotubes 4 are not disposed in the microchannel 7.
Further, in the method of manufacturing the microreactor 1 of Example 1, as shown in FIGS. 3 and 4, after the carbon nanotubes 4 are formed on the flat surface 19a of the silicon substrate 19 by the alcohol CCVD method, the flat surface is formed. The carbon nanotubes 4 are transferred from 19 a to the grooves 2 c of the resin substrate 2. Then, as shown in FIG. 5, the blocking surface 3a of the glass plate 3b is joined to the adsorption surface 2b of the resin substrate 2 to which the carbon nanotubes 4 have been transferred to form the microchannel 7.

  As a result, in the manufacturing method of the microreactor 1 of Example 1, the carbon nanotubes 4 are arranged in the microchannel 7 without heating the resin substrate 2 and the glass plate 3 constituting the microchannel 7 at a high temperature. Can do. Therefore, the microreactor 1 of Example 1 can avoid heating the inside of the microchannel 7 at a high temperature in order to give the microchannel 7 a structure that increases the specific surface area. Compared with the technique described in 2, it is possible to select an optimal material for the resin substrate 2 and the glass plate 3 in order to configure the microchannel 7 without considering heat resistance and the like.

In addition, the said resin substrate 2 of Example 1 is comprised by the polydimethylsiloxane. For this reason, in the microreactor 1 of Example 1, the resin substrate 2 and the glass plate 3 can be brought into close contact with each other. That is, in the microreactor 1 of Example 1, the substrates are bonded to each other as compared with the microchip described in Non-Patent Document 1 that is formed by bonding the silicon substrate 19 on which the carbon nanotubes 4 are generated and the glass plate 3. It is easy. 4A, since the resin substrate 2 of Example 1 can be produced by pouring polydimethylsiloxane into the mold 26, the resin substrate 2 can be formed into an arbitrary shape according to the mold 26. For example, the groove 2c can be formed with a width on the order of micrometers.
In this case, since the carbon nanotube 4 is transferred from the flat surface 19a to the groove 2c, if the carbon nanotube 4 is generated on the flat surface 19a according to the shape of the groove 2c, the groove having an arbitrary shape is formed. The carbon nanotube 4 can be transferred to 2c.

7A and 7B are explanatory views when the mask is mounted on the silicon substrate having a convex portion in the tube generation process of the first embodiment, FIG. 7A is an explanatory diagram of a state where the mask is mounted on the silicon substrate, and FIG. 7C is an explanatory view of a mask, FIG. 7D is an explanatory view of a state where carbon nanotubes are generated from the state of FIG. 7A, and FIG. 7E is a state where the mask is removed from the state of FIG. 7C It is explanatory drawing of a state.
For example, when the groove 2c is not formed in the millimeter order square shown in FIGS. 1 and 2A or the like but formed in a Y shape with a micrometer order width shown in FIG. Consider a case where a convex portion 19c corresponding to a Y-shape 2c is formed (see FIG. 7B) and a mask 29 (see FIG. 7C) having a hole 28 corresponding to the convex portion 19c is attached. In this case, the hole 28 is fitted into the convex portion 19c, and the outer surface 29a of the mask 29 is arranged along the outer surface (tube generation surface) 19d of the convex portion 19c. It is formed similarly to the surface 19a (see FIG. 7A).

Further, from the state shown in FIG. 7A, after the carbon nanotubes 4 are generated on the outer surfaces 19d and 29a (see FIG. 7D), the mask 29 is removed from the silicon substrate 19 to remove the protrusions 19c. The carbon nanotubes 4 remain only on the surface 19d (see FIG. 7E).
That is, by using the mask 29 corresponding to the shape of the groove 2c, the carbon nanotube 4 corresponding to the groove 2c having an arbitrary shape can be generated, and the carbon nanotube on the outer surface 19d of the convex portion 19c can be generated. 4 can be transferred to the groove 2c. It has been confirmed by preliminary experiments that the carbon nanotubes 4 having an arbitrary shape can be generated using the mask 29.

For this reason, in the microreactor 1 of Example 1, for example, even when the groove 2c has a width on the order of micrometers and is formed in a straight line connecting the through holes 2d and 2d, The carbon nanotubes 4 can be transferred into the narrow linear groove 2c.
As a result, the microreactor 1 of Example 1 has a higher degree of freedom in the shape of the microchannel 7 than the microchip described in Non-Patent Document 1 that directly uses the carbon nanotubes 4 grown on the flat surface 19a. can do. Further, in the microreactor 1 of Example 1, the carbon nanotubes 4 grown sufficiently long on the flat surface 19a can be arranged in the narrow microchannel 7, and the carbon nanotubes grow sufficiently long in the narrow microchannel. Compared with the technique described in Non-Patent Document 2, which cannot be performed, the specific surface area in the microchannel 7 can be increased.

FIG. 8 is an operation explanatory view of Example 1 of the present invention, and is an enlarged explanatory view when carbon nanotubes before and after transfer are observed with a scanning electron microscope. FIG. 8A is a view before transfer on a flat surface of a silicon substrate. FIG. 8B is an explanatory view of the carbon nanotube after transfer into the groove of the resin substrate.
Moreover, in Example 1, the carbon nanotubes 4 on the flat surface 19a of the silicon substrate 19 are inserted into the grooves 2c of the resin substrate 2 made of polydimethylsiloxane by the tube transfer process (see FIGS. 4B to 4E). It was confirmed that more than 30% was transferred. At this time, when the carbon nanotubes 4 were observed with a scanning electron microscope (SEM) before and after the transfer, as shown in FIGS. 8A and 8B, the carbon nanotubes 4 were observed before and after the transfer. It was confirmed that the substrates 2 and 19 were oriented perpendicularly, that is, kept perpendicular.

Therefore, the microreactor 1 of Example 1 has the flatness compared to the techniques described in Non-Patent Documents 1 and 2 in which the carbon nanotubes are not easily oriented vertically as a result of growing the carbon nanotubes in a narrow microchannel. Carbon nanotubes 4 that are vertically oriented on the surface 19 a can be arranged in the microchannel 7.
Further, in Example 1, as shown in FIG. 6, the tube bundle for producing the carbon nanotube bundle 6 by bringing ethanol into contact with the carbon nanotubes 4 in the microchannel 7 and then vaporizing the ethanol. A creation process is performed.

(Experimental example)
Here, in order to evaluate the carbon nanotube bundle 6 produced by the tube bundle producing step (see FIG. 6) of Example 1, the following Experimental Examples 1 and 2 were prepared.
(Experimental example 1)
In Experimental Example 1, first, the carbon nanotubes 4 were placed on the flat surface 19a by the tube generation process of Example 1 (see FIG. 3) with representative dimensions of 8 [μm] and 18.5 [μm]. , 28 [μm]. Next, 2 [μL] of ethanol was dropped on each of the three types of carbon nanotubes 4. Then, the ethanol is vaporized, and the aggregated width d1 [μm] (refer to FIGS. 2C and 6C) which is an average value of the widths of the aggregated tip portions of the plurality of carbon nanotube bundles 6 produced, and the plurality of carbons The aggregation distance d2 [μm] (see FIGS. 2C and 6C), which is the average value of the distance between the aggregated tips of the nanotube bundle 6, was measured.

(Experimental example 2)
In Experimental Example 2, first, as in Experimental Example 1, the carbon nanotubes 4 were placed on the flat surface 19a with representative dimensions of 8 [μm], 18.5 [μm], and 28 [μm]. Generated to be. Next, the carbon nanotubes 4 were hydrophilized by irradiating the carbon nanotubes 4 with argon plasma at an acceleration voltage of 500 [V] for 5 [min]. The argon plasma is an argon gas ionized by an acceleration voltage to be in a plasma state (see, for example, Japanese Patent Application Laid-Open Nos. 2006-111504 and 2001-133439). In addition, it has been confirmed by preliminary experiments that when the argon plasma is irradiated before the liquid is dropped, the liquid is more easily penetrated between the carbon nanotubes 4 than when the plasma is not irradiated.
Next, pure water was dropped into each of the three types of carbon nanotubes 4 by 1 [μL], and the pure water was permeated between the carbon nanotubes 4. Then, the pure water was vaporized, and the aggregation width d1 [μm] and the aggregation interval d2 [μm] of the plurality of carbon nanotube bundles 6 were measured.

(Experimental results of Experimental Examples 1 and 2)
FIG. 9 is an experimental result of Experimental Examples 1 and 2, and is an enlarged explanatory diagram when the tip of the aggregated carbon nanotube bundle is observed with a scanning electron microscope. FIG. 9A is a liquid contact range and a non-contact range. FIG. 9B is an explanatory diagram showing a state in which the tips of carbon nanotubes having a typical dimension of Experimental Example 1 of 18.5 [μm] are aggregated, and FIG. It is explanatory drawing of the state which the front-end | tip part of the carbon nanotube of 5 [micrometers] aggregated.
FIG. 10 shows the experimental results of Experimental Example 1 and Experimental Example 2, and is an explanatory diagram of a graph in which the horizontal axis represents the representative dimension [μm] of the carbon nanotube and the vertical axis represents the aggregated width [μm] of the carbon nanotube. .
FIG. 11 shows the experimental results of Experimental Example 1 and Experimental Example 2, and is an explanatory diagram of a graph in which the horizontal axis represents the representative dimension [μm] of the carbon nanotubes and the vertical axis represents the aggregation interval [μm] of the carbon nanotubes. is there.

As shown in FIG. 9A, in Experimental Examples 1 and 2, the boundary between the contact range A1 where each liquid (ethanol, pure water) was dropped and contacted and the non-contact range A2 which did not contact (see the broken line in FIG. 9A) ) Can be confirmed. Further, as shown in FIGS. 9B and 9C, in Experimental Examples 1 and 2, the contact range A1 of each liquid (ethanol, pure water) has a plurality of carbon nanotubes formed by agglomeration of the tips of the carbon nanotubes 4. It can be confirmed that the bundle 6 has been created (see white portions in FIGS. 9B and 9C).
Further, as shown in FIGS. 10 and 11, when the representative dimensions of the carbon nanotube 4 of Experimental Example 1 are 8 [μm], 18.5 [μm], and 28 [μm], the aggregation width d1 is , About 5 [μm], about 8 [μm], and about 10 [μm], and the aggregation interval d2 is about 12 [μm], about 26 [μm], and about 45 [μm].
Further, when the representative dimensions of the carbon nanotubes 4 of Experimental Example 2 are 8 [μm], 18.5 [μm], and 28 [μm], the aggregation width d1 is about 5 [μm] and about 11 [ μm] and about 15 [μm], and it can be seen that the aggregation interval d2 is about 8 [μm], about 28 [μm], and about 50 [μm].

  Therefore, in Experimental Examples 1 and 2, it was confirmed that the aggregation width d1 [μm] and the aggregation interval d2 [μm] increase as the representative dimension of the carbon nanotube 4 becomes longer. In Experimental Examples 1 and 2, the aggregation width d1 is about 5 [μm] to about 15 [μm] and the aggregation interval d2 is about 8 by dropping and vaporizing the liquids (ethanol, pure water). It was confirmed that a plurality of carbon nanotube bundles 6 having a size of [μm] to about 50 [μm] could be created.

Also, whether the carbon nanotubes 4 transferred to the resin substrate 2 in the tube bundle creating step of Example 1 are aggregated at the tip portions to produce the carbon nanotube bundle 6 as in Experimental Examples 1 and 2. In order to confirm whether or not, the following Experimental Example 3 was prepared.
(Experimental example 3)
In Experimental Example 3, first, the tube generation step (see FIG. 3), the tube transfer step (see FIGS. 4B to 4E), the microchannel formation step (see FIG. 5), and the tube bundle creation step (see FIG. 6). ) To produce the microreactor 1 of Example 1. Next, ethanol was again injected into the microchannel 7 of the prepared microreactor 1 by the syringe 27, and the microchannel 7 was filled with the ethanol.

(Experimental result of Experimental Example 3)
FIG. 12 is an experimental result of Experimental Example 3, and is an enlarged explanatory diagram when the tip of the carbon nanotube in the microchannel is observed with a scanning electron microscope. FIG. 12A is a graph of carbon before ethanol injection in the tube bundle forming step. 12B is an explanatory diagram showing the state of the tip of the nanotube, FIG. 12B is an explanatory diagram showing the state of the tip of the carbon nanotube after ethanol injection from the state of FIG. 12A, and FIG. 12C is the state of the carbon nanotube after ethanol vaporization from the state of FIG. FIG. 12D is an explanatory view showing the state of the tip of the carbon nanotube after ethanol re-injection from the state of FIG. 12C.

  As shown in FIG. 12, in Experimental Example 3, in the tube bundle creation step, the carbon nanotubes in the microchannel 7 are placed between before ethanol injection (see FIG. 6A) and after ethanol injection (see FIG. 6B). It can be seen that the tip of 4 does not change (see FIGS. 12A and 12B). Further, it can be seen that the tips of the carbon nanotubes 4 aggregated between the time after ethanol injection and the time after ethanol vaporization (see FIG. 6C), and a plurality of carbon nanotube bundles 6 were formed (see FIGS. 12B and 12C). ). Furthermore, it can be seen that the tip of the carbon nanotube bundle 6 does not change between the time after ethanol vaporization and the time after ethanol reinjection (see FIGS. 12C and 12D).

  Therefore, in Experimental Example 3, it was confirmed that the carbon nanotube bundle 6 could be created for the carbon nanotubes 4 after being transferred to the grooves 2c of the resin substrate 2. In addition, it was confirmed that the carbon nanotube bundles 6 were formed by aggregation of the tips due to the vaporization of ethanol in contact with the carbon nanotubes 4 before aggregation. Furthermore, even if the carbon nanotube bundle 6 after aggregation is re-contacted with ethanol, the carbon nanotube bundle 6 does not return to the original vertically aligned carbon nanotube 4, that is, does not return to the state before aggregation, It was confirmed that the state after aggregation was maintained.

(About the factor which the front-end | tip part of the carbon nanotube 4 aggregates)
Note that the tips of the carbon nanotubes 4 are aggregated because of the frictional force between the carbon nanotubes 4 and the substrates 2, 19, the fluid drag of the carbon nanotubes 4, and the intermolecular force between the carbon nanotubes 4 (fans). This is thought to be due to the fact that the surface tension of the ethanol, such as Delwars force and van der Waals. From the experimental results of Experimental Example 3, it is considered that among these forces, the surface tension, which is a force that greatly changes with the vaporization of ethanol, strongly influences the occurrence of the aggregation.

FIG. 13 is an explanatory view of the process of vaporizing ethanol in the microchannel, FIG. 13A is an explanatory view of a state where air is injected from the state of FIG. 6B and ethanol is removed, and FIG. 13B is an ethanol state from the state of FIG. FIG. 13C is an enlarged explanatory view of the ethanol droplet of FIG. 13B, and FIG. 13D is an illustration of the ethanol from the state of FIG. 13C. It is explanatory drawing of the state to which the droplet of this shrunk.
That is, when air is injected by the syringe 27 from the state shown in FIGS. 6B and 12B, ethanol filled in the microchannel 7 is pushed out, and the state shown in FIG. 13A is obtained. At this time, as the ethanol vaporizes, the amount of liquid ethanol decreases, and the island-shaped droplets (carbons) scattered on the front ends of the carbon nanotubes 4 arranged uniformly in a planar shape. It becomes a liquid that communicates between the tips of the nanotubes), and the state shown in FIG. 13B is obtained.

From this state, when ethanol further vaporizes and the droplets become smaller, as shown in FIGS. 13C and 13D, the carbon nanotubes 4 are pulled by the droplets that are getting smaller due to the surface tension of the droplets. Inclined to. And when the water droplet-shaped ethanol which contacted the front-end | tip part of a carbon nanotube finally vaporizes, it will be considered that the carbon nanotube bundle 6 will be in the state created according to the position of each scattered dot. As the representative dimension of the carbon nanotube 4 becomes longer, the aggregation width d1 [μm] and the aggregation interval d2 [μm] increase because the surface tension is a force acting per unit length. This is considered to be because the surface tension increased as the carbon nanotubes 4 became longer.
Further, since the intermolecular force between the carbon nanotubes 4 increases as the carbon nanotubes 4 approach each other, the intermolecular force between the front end portions increases when the front end portions of the carbon nanotubes 4 aggregate. Become. For this reason, even if the aggregated carbon nanotube bundle 6 re-contacts with ethanol, the intermolecular force acting on the tip of the carbon nanotube bundle 6 acts as a force for aggregating the bundle of the tip of the carbon nanotube 4. It is considered that the state after aggregation is maintained without returning to the state before aggregation.

FIG. 14 is an explanatory diagram of the experimental devices of Experimental Examples 4 and 5, and Comparative Example 1, FIG. 14A is an overall explanatory diagram of the experimental device, FIG. 14B is an explanatory diagram of the microreactor of Experimental Example 4, and FIG. 14D is an explanatory diagram of the microreactor of Comparative Example 1. FIG.
Furthermore, in order to evaluate the microreactor 1 having the carbon nanotube bundle 6 produced by the tube bundle production process of Example 1, the following Experimental Examples 4 and 5 and Comparative Example 1 were prepared.
(Experimental example 4)
In Experimental Example 4, as in Experimental Example 3, the microreactor 1 (see FIG. 14B) of Example 1 was created by the tube generation process, the tube transfer process, the microchannel formation process, and the tube bundle creation process. did.

(Experimental example 5)
In Experimental Example 5, the microreactor 1 in which the tip of the carbon nanotube 4 is not aggregated by the tube generation process, the tube transfer process, and the microchannel formation process as compared with the microreactor 1 of Experimental Example 4 is used. '(See Fig. 14C) was created.
(Comparative Example 1)
Further, in Comparative Example 1, the microreactor 1 ″ (in which the carbon nanotubes 4 are not transferred into the microchannel 7 is compared with the microreactors 1 and 1 ′ in Experimental Examples 4 and 5 by the microchannel formation step. 14D) was created.

(Experimental conditions of Experimental Examples 4 and 5 and Comparative Example 1)
In Experimental Examples 4 and 5 and Comparative Example 1, first, as shown in FIGS. 14B to 14D, on the inner surface of each microchannel 7, 7 ′, 7 ″ of each microreactor 1, 1 ′, 1 ″, An HRP (horseradish peroxidase) 31 as an example of a catalyst and an example of an enzyme is attached (adsorbed) in advance. Next, as shown in FIG. 14A, Amplex (registered trademark) Red reagent as an example of the first sample is introduced into each of the microchannels 7 to 7 ″ by the syringe 27 (see, for example, Non-Patent Document 5) ) And hydrogen peroxide water (H ₂ O ₂ ) as an example of the second sample to cause a chemical reaction to generate resorufin as an example of a reaction product and an example of a fluorescent substance 14A, the resorufin in each of the microchannels 7 to 7 ″ is excited by irradiating an argon laser 32 from the outside, and the fluorescence of the resorufin is photographed by a CCD camera 33 and the CCD is used. A change in fluorescence intensity of the photographed resorufin was measured by a personal computer (electronic computer, fluorescence intensity measuring device) 34 connected to the camera 33.

(Experimental results of Experimental Examples 4 and 5 and Comparative Example 1)
FIG. 15 shows the experimental results of Experimental Examples 4 and 5 and Comparative Example 1, and is an explanatory diagram of a graph with time [sec] on the horizontal axis and fluorescence intensity of resorufin on the vertical axis.
As shown in FIG. 15, in Experimental Example 4, the maximum fluorescence intensity, which is the maximum value of the fluorescence intensity of the resorufin, is 2382, and the time until the maximum fluorescence intensity is shown is measured in the microchannel 7. It can be seen that it was 7.8 [sec] after the injection. In Experimental Example 5, the maximum fluorescence intensity is 1044, and the time until the maximum fluorescence intensity is shown is 14.2 [sec] after each sample is injected into the microchannel 7 ′. I understand that there was. Furthermore, in Comparative Example 1, the maximum fluorescence intensity is 1455, and the time until the maximum fluorescence intensity is shown is 27.7 [sec] after the samples are injected into the microchannel 7 ″. I understand that there was.

As a result, it can be seen that the maximum fluorescence intensity is the largest in Experimental Example 4, the second largest in Comparative Example 1, and the smallest in Experimental Example 5. It can also be seen that the time until the maximum fluorescence intensity is shown is the shortest in Experimental Example 4, the second shortest in Experimental Example 5, and the longest in Comparative Example 1. That is, it can be seen that the microreactor 1 of Experimental Example 4 caused the resorufin to chemically react more efficiently than the microreactors 1 ′ and 1 ″ of Experimental Example 5 and Comparative Example 1.
Here, the microreactor 1 of Experimental Example 4 caused the most efficient chemical reaction of resorufin, as shown in FIG. 14B, in the region between the tip portions of the plurality of carbon nanotube bundles 6. 31) is attached, and it is considered that each of the samples can enter the region. That is, in the microreactor 1 of Experimental Example 4, the catalyst (31) and each sample are more than the aggregation interval d2 [μm] (see FIGS. 2C and 6C) between the tips of the plurality of carbon nanotube bundles 6. It is thought that the molecular diameter (molecular diameter) was small.

Therefore, the microreactor 1 of the experimental example 4 is different from the microreactors 1 ′ and 1 ″ of the experimental example 5 and the comparative example 1 of the microchannel (7 to 7 ″) used as a reaction field for chemical reaction. It is considered that resorufin was most efficiently chemically reacted because the surface area of the inner surface was the largest.
Note that the maximum fluorescence intensity of the microreactor 1 ′ of Experimental Example 5 was smaller than that of Microreactors 1 and 1 ″ of Experimental Example 4 and Comparative Example 1, as shown in FIG. 14C. It is considered that the catalyst (31), each sample, or both could not enter between the carbon nanotubes 4 due to the relationship between the molecular diameter and the gap between the carbon nanotubes 4. In relation to the catalyst (31) and the type of each sample, it is considered that the entire surface of the carbon nanotube 4 could not be used as a reaction field for a chemical reaction.

That is, in the microreactor 1 ′ of Experimental Example 5, in the chemical reaction of resorufin, the depth of the microchannel 7 ′ is simply reduced by the representative dimension of the carbon nanotube 4, that is, the microchannel 7 It can be considered that the depth of ′ is constituted by 60−28 = 32 [μm].
For this reason, the microreactor 1 ′ of Experimental Example 5 has a shallower depth of the microchannel (7 ′, 7 ″) than the microreactor 1 ″ of Comparative Example 1 (32 [μm] <60 [ μm]), the range in which each sample can diffuse, that is, the diffusion distance of each sample is shortened. Therefore, in Experimental Example 5, it is considered that the chemical reaction converged faster than Comparative Example 1.

Further, the microreactor 1 ′ of Experimental Example 5 is not used for the reaction between the carbon nanotubes 4 compared to the microreactor 1 ″ of Comparative Example 1, so that the effective microchannel (7 ′ , 7 ″). As a result, it can be considered that the maximum fluorescence intensity of the microreactor 1 ′ of Experimental Example 5 was lower than that of the microreactor 1 ″ of Comparative Example 1.
As a result, it is considered that the microreactor 1 ′ of Experimental Example 5 was unsuitable for producing resorufin by chemically reacting Amplex Red reagent and hydrogen peroxide in the presence of HRP (31). In other words, when a sample having a molecular diameter that can enter between the carbon nanotubes 4 is used, the microreactor 1 ′ of Example 5 has the same effect as the microreactor 1 of Example 4. Can be expected.

From these experimental results, the microreactor 1 of Example 1 can transfer the carbon nanotubes 4 to the grooves 2 c of the resin substrate 2, and can increase the specific surface area of the microchannel 7. Further, the carbon nanotube bundles 6 can be formed by aggregating the tip portions of the transferred carbon nanotubes 4, and the carbon nanotube bundles 6 can be formed according to the representative dimensions of the carbon nanotubes 4, the contact range of liquid (ethanol, pure water, etc.), and the like. The aggregation width d1 and the aggregation interval d2 can be adjusted. For this reason, the microreactor 1 of Example 1 can adjust the surface area of the inner surface of the microchannel 7 used as a reaction field for a chemical reaction.
As a result, the microreactor 1 of Example 1 executes the chemical reaction in the microchannel 7 more efficiently than the microreactor 1 ″ of the comparative example 1 in which the carbon nanotube 4 is not present in the microchannel 7. be able to.

(Example of change)
As mentioned above, although the Example of this invention was explained in full detail, this invention is not limited to the said Example, A various change is performed within the range of the summary of this invention described in the claim. It is possible. Modification examples (H01) to (H07) of the present invention are exemplified below.
(H01) In the embodiment, in the tube generation step (see FIG. 3), the flat surface of the silicon substrate 19 is formed by the alcohol CCVD method using ethanol as a raw material by using the chemical vapor deposition apparatus 11 (see FIG. 3). Although the carbon nanotubes 4 are generated in 19a, the carbon nanotubes 4 can be generated by any method in which the carbon nanotubes 4 are vertically aligned on the flat surface 19a. For example, the CVD method using xylene and ferrozene of Non-Patent Document 1 as raw materials, the CVD method of irradiating microwaves to methane of Non-Patent Document 2, a nickel-cobalt (Ni-Co), etc. Laser ablation where a YAG (yttrium, aluminum, garnet) laser is applied to graphite (C) mixed with a metal catalyst, evaporated, sent to an electric furnace at about 1200 ° C. in an argon (Ar) stream, and attached to the wall of the electric furnace. It is also possible to generate the carbon nanotubes 4 on the flat surface 19a by using a method.

(H02) In the embodiment, in the tube generation step (see FIG. 3), the representative dimension of the carbon nanotube 4 is set to 28 [μm]. However, the present invention is not limited to this, and the depth of the microchannel 7 ( For example, the length can be changed to an arbitrary length within a range of 60 [μm]. In this case, for example, when the representative dimension is longer than 28 [μm], the aggregation width d1 [μm] of the carbon nanotube bundle 6 is made larger than about 15 [μm] in the tube bundle creating step, It can be expected that the aggregation interval d2 can be made larger than about 50 [μm].
(H03) In the embodiment, when the resin substrate 2 is formed with the mold 26 (see FIG. 4A) in the tube transfer step (see FIG. 4), the groove 2c of the resin substrate 2 is a protrusion corresponding to the groove 2c. Although the resin substrate 2 formed by heating 26a is cut out and the through holes 2d and 2d are formed by hollowing out the resin substrate 2, the present invention is not limited to this. For example, the through holes 2d and 2d are also similar to the groove 2c. It is also possible to provide the projections corresponding to the through holes 2d and 2d. In the above-described embodiment, one groove 2c and two through holes 2d and 2d are formed in the resin substrate 2. However, the number of grooves and through holes is not limited to this. For example, one through hole 2d Can be omitted, or two or more grooves or three or more through holes can be formed. Furthermore, the shape, position, size, range, and the like of the groove and the through hole can be arbitrarily changed.

(H04) In the above embodiment, the resin substrate 2 is made of the polydimethylsiloxane in the tube transfer step (see FIG. 4) (see FIG. 4A), but is not limited to this. For example, the silicon substrate 19 It is also possible to use other adsorbing members having a higher adsorptivity of the carbon nanotubes 4 than the oxide film. Moreover, it is preferable to produce the microreactor 1 having high transparency using the resin substrate 2 and the glass plate 3 made of transparent polydimethylsiloxane, but is not limited to this, and using a material that is not transparent, It is also possible to produce colored microreactors. Moreover, in the said Example, although the said resin substrate 2 whole was comprised with the said polydimethylsiloxane, it is not limited to this, For example, the said resin substrate 2 whole is comprised with materials other than the said polydimethylsiloxane, and the said adsorption | suction It is also possible to coat only the surface 2a with the polydimethylsiloxane.

(H05) In the embodiment, in the tube transfer step (see FIG. 4), the length / width / depth of the microchannel 7 is 10 [mm] × 10 [mm] × 60 [μm]. However, the present invention is not limited to this, and it is possible to form microchannels having an arbitrary length, width, and depth. The width of the microchannel 7 is configured in the so-called millimeter order, but is not limited to this. For example, the microchannel having a width in the centimeter order to the micrometer order is used by using the mask 29. It is also possible to form. In this case, if the carbon nanotubes 4 are generated according to the shape of the grooves 2c, the carbon nanotubes 4 can be transferred to the grooves 2c having an arbitrary shape.

(H06) In the embodiment, in the microchannel formation step (see FIG. 5), the resin substrate 2 and the glass plate 3 are kept in close contact due to the self-adsorption property of the polydimethylsiloxane. However, the present invention is not limited to this. For example, the adhesion range of each of the substrates 2 and 3 can be instantaneously bonded by vacuum ultraviolet (VUV). An apparatus for instantaneously bonding the substrates 2 and 3 by irradiating with vacuum ultraviolet rays is described in, for example, Non-Patent Document 6 and is well known.
(H07) In the above embodiment, the tube bundle creating step (see FIG. 6) is performed after the microchannel forming step (see FIG. 5). However, the present invention is not limited to this. For example, the tube transfer step (see FIG. 4) and the microchannel forming step (see FIG. 5). In addition, it is preferable to create the carbon nanotube bundle 6 by the tube bundle creating step, but the present invention is not limited to this, and the tube bundle creating step is omitted and the carbon nanotubes 4 are kept in the vertical orientation. It is also possible to keep it.

1 ... Microreactor,
2 ... Substrate to be transferred,
2a ... transferred surface, adsorbing member, polydimethylsiloxane,
2c ... groove,
3 ... Blocking substrate,
3a: obstruction surface,
4 ... carbon nanotube,
6 ... bundle of carbon nanotubes,
7 ... channel,
19 ... transfer substrate,
19a ... Tube generating surface,
19c ... convex part,
19d ... the outer surface of the convex part,
28 ... hole,
29 ... mask,
29a ... The outer surface of the mask.

Claims (5)

A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate;
The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. And a tube transfer step of transferring the carbon nanotubes on the tube generation surface to the groove,
In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
With
A method for producing a microreactor, wherein the specific surface area in the flow path is increased by the carbon nanotubes,
further,
A carbon nanotube in which a plurality of carbon nanotubes transferred to the groove are brought into contact with a liquid communicating between the plurality of carbon nanotubes, and the liquid is vaporized to bundle the plurality of carbon nanotubes. Tube bundle creation process to create a bundle,
A method for producing the microreactor, comprising: A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate;
The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. And a tube transfer step of transferring the carbon nanotubes on the tube generation surface to the groove,
In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
With
A method for producing a microreactor, wherein the specific surface area in the flow path is increased by the carbon nanotubes,
In the tube generating step, a hole of a mask corresponding to the convex portion is fitted into a convex portion of the transfer substrate formed according to the groove, and the mask is mounted on the transfer substrate, so that the tube is generated. In a state where the outer surface of the mask is disposed along the outer surface of the convex portion as a surface, the mask that is detachable from the transfer substrate after the carbon nanotubes are generated on each outer surface. Remove and leave the carbon nanotubes only on the outer surface of the convex part,
In the tube transfer step, the carbon nanotubes on the outer surface of the convex portion are transferred to the groove. A tube generation process for generating carbon nanotubes on the tube generation surface of the transfer substrate by an alcohol-catalyzed CVD method;
The transfer substrate and the transfer substrate in a state where the tube generation surface and the transfer surface are opposed to a transfer substrate having a transfer surface and a groove formed in the transfer surface. The carbon nanotubes on the tube generation surface are inserted into the grooves without breaking the orientation of the carbon nanotubes by piercing the tip of the carbon nanotubes on the transfer surface side. Tube transfer process to transfer,
In a state where the transfer surface and the closing surface are opposed to a closing substrate having a closing surface, the transfer substrate and the closing substrate are joined, and the opening side of the groove is closed, A flow path forming step for forming a flow path as a space surrounded by the carbon nanotube, the groove, and the closed surface;
With
A method of manufacturing a microreactor, wherein the specific surface area in the flow path is increased by the carbon nanotubes. A transfer surface on which a groove is formed, and the carbon nanotube transferred to the groove with the tube generation surface of the transfer substrate on which the carbon nanotube is generated on the tube generation surface facing the transfer surface. A substrate to be transferred,
A closing substrate that has a closing surface and is bonded to the transfer substrate and closes the opening side of the groove in a state where the transfer surface and the closing surface are opposed to each other;
A flow path as a space surrounded by the carbon nanotube, the groove, and the blocking surface;
A bundle of carbon nanotubes in which the tip ends of a plurality of the carbon nanotubes whose base ends are supported on the common transferred surface;
A microreactor comprising: The transferred surface composed of polydimethylsiloxane,
The microreactor according to claim 4 , comprising: