JP2009090248A - Structure having micro flow passage, its manufacturing method and microreactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure having a micro flow passage the clogging of which is restrained and to provide a method for manufacturing the structure having the micro flow passage and a microreactor the clogging of which is restrained. <P>SOLUTION: The structure having the micro flow passage is provided which has at least one connection part formed from at least two members for forming the micro flow passage and a film buried/formed at least partially in a concave part on the surface of the micro flow passage. The method for manufacturing the structure having the micro flow passage is provided and the microreactor is also provided in which a part or the whole of the micro flow passage is formed from the structure having the micro flow passage. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a microchannel structure, a method of manufacturing a microchannel structure, and a microreactor.

  In general, a microelement or device represented by a microreactor defined as “a device that uses microfabrication and performs a reaction in a microchannel having an equivalent diameter of 500 μm or less” includes, for example, a substance When applied to techniques for analysis, synthesis, extraction, and separation, there are many advantages such as small variety, variety, high efficiency, and low environmental impact, and in recent years, application to various fields is expected.

  Patent Document 1 includes a liquid introduction portion, a fine liquid passage, and a liquid discharge portion, and the liquid passage is formed by a magnetic barrier made of a strip-shaped ferromagnetic material, and has a magnetic property introduced from the introduction portion. , A microreactor configured to perform at least one of chemical reaction, mixing, extraction, and absorption in the liquid passage, and a plating solution or an etching solution to the liquid passage. Means for carrying out plating and etching by flowing is disclosed.

JP 2004-82118 A

  The problem to be solved by the present invention is to provide a microchannel structure having a microchannel in which the occurrence of clogging is suppressed.

The problem to be solved of the present invention has been solved by the following means.
<1> It has at least one connection part formed by at least two members that form a microchannel, and has a microchannel in which a coating film in which a concave portion on the inner surface of the microchannel is at least partially embedded is formed A microchannel structure characterized by that,
<2> The microchannel structure according to <1>, wherein the connection portion is a connection portion between an end portion of a tubular member forming the microchannel and one side of a pipe joint,
<3> The microchannel structure according to <1> or <2>, wherein the depth of the concave portion on the surface of the coating is 0.5 μm or less,
<4> The microchannel structure according to any one of <1> to <3>, wherein the thickness of the coating is 1.0 to 3.0 μm,
<5> The microchannel structure according to any one of <1> to <4>, wherein an inner diameter of the microchannel is 200 to 5,000 μm,
<6> The microchannel structure according to any one of <1> to <5>, wherein the coating is a coating formed of a plated metal and / or a synthetic resin material.
<7> The microchannel structure according to <6>, wherein the inner surface of the microchannel is conductive, and the coating formed of the synthetic resin material is a coating formed by electrodeposition.
<8> The microchannel structure according to <7>, wherein the coating formed by electrodeposition is a coating formed of a polyimide resin or a polyamide resin.
<9> filling a plating solution or an electrodeposition solution into at least one connection part formed by at least two members forming the microchannel and a microchannel having a conductive channel inner surface; And a method of manufacturing a microchannel structure comprising a step of forming a coating film on the inner surface of the microchannel by plating or electrodeposition, and at least partially embedding a recess in the inner surface of the microchannel ,
<10> A microreactor in which the microchannel structure according to any one of <1> to <8> forms part or all of the microchannel.

According to the invention described in <1>, it is possible to provide a microchannel structure in which clogging of the microchannel is suppressed as compared with a case where the present configuration is not provided.
Moreover, according to the invention described in <2>, a microchannel structure in which clogging is suppressed in the invention described in <1> can be provided.
In addition, according to the invention described in <3>, a microchannel structure in which occurrence of clogging is further suppressed in the invention described in <1> or <2> can be provided.
Moreover, according to the invention described in <4>, in the invention described in any one of <1> to <3>, it is possible to provide a microchannel structure in which occurrence of clogging is further suppressed. .
Moreover, according to the invention described in <5>, the microchannel structure in which occurrence of clogging is further suppressed in the invention described in any one of <1> to <4> can be provided. .
Moreover, according to the invention described in <6>, the microchannel structure in which occurrence of clogging is further suppressed in the invention described in any one of <1> to <5> can be provided. .
Moreover, according to the invention described in <7>, the microchannel structure in which occurrence of clogging is further suppressed in the invention described in <6> can be provided.
Moreover, according to the invention described in <8>, the microchannel structure in which occurrence of clogging is further suppressed in the invention described in <7> can be provided.
In addition, according to the invention described in <9>, there is provided a method for manufacturing a microchannel structure having a microchannel that is excellent in suppressing clogging compared to a case where the present configuration is not provided. be able to.
Further, according to the invention described in <10>, it is possible to provide a microreactor having a microchannel in which clogging is suppressed as compared with a case where the present configuration is not provided.

The microchannel structure according to the present embodiment has at least one connection portion formed by at least two members that form the microchannel, and a coating in which the concave portion on the inner surface of the microchannel is at least partially embedded. It has the formed micro channel.
Hereinafter, this embodiment will be described in detail.

In the present embodiment, the micro flow path is a micro flow path that allows a very small amount of liquid to flow, and refers to a micro scale flow path, but also includes a millimeter scale flow path.
The cross-sectional area of the microchannel is synonymous with 0.05 to 25 mm ² (“0.05 mm ² or more and 25 mm ² or less”. In the following, unless otherwise noted, the same applies to the description of other numerical ranges. to.) is preferably, more preferably 0.10～10Mm ^2, further preferably 0.15～5Mm ^2.
The circular equivalent inner diameter (diameter) of the microchannel calculated from the cross-sectional area of the microchannel is preferably 200 to 5,000 μm, more preferably 250 to 1,000 μm, and 300 to 500 μm. Is more preferable.
Within the above numerical range, it is easy to form a coating on the inner surface of the microchannel by plating or electrodeposition, and clogging due to the generation of bubbles is less likely to occur when liquid is introduced into the microchannel. preferable.
Further, the length of the microchannel is preferably in the range of 5 to 400 mm, more preferably in the range of 10 to 200 mm, although it depends on the shape of the microchannel to be formed.
Moreover, there is no restriction | limiting in particular about the shape of a microchannel, For example, the cross-sectional shape in a direction perpendicular | vertical with respect to a flow direction can be made into desired shapes, such as circular, an ellipse, and a polygon. The channel axis shape is not particularly limited, and may be any shape such as a straight line or a curved line. Here, the channel axis shape means an axis in the fluid flow direction in the micro channel.

The microchannel has a small size and flow velocity, and the Reynolds number of the fluid flowing through the microchannel is 2,300 or less. Therefore, in the present embodiment, the micro flow channel is not a turbulent flow but a laminar flow.
Here, the Reynolds number (Re) is represented by the following formula, and when it is 2,300 or less, the laminar flow is dominant.
Re = uL / ν (u: flow velocity, L: representative length, ν: kinematic viscosity coefficient)

Examples of the material for forming the microchannel include a conductive material and a non-conductive material.
Examples of the conductive material include alloys such as stainless steel (hereinafter, also referred to as “SUS”), and metal materials such as gold, platinum, cobalt, iron, copper, nickel, aluminum, and titanium. Of these, stainless steel is preferable. When the material of the microchannel is a conductive material such as a metal, the member that forms the microchannel can be used as an electrode. Therefore, the microchannel can be formed by electroplating or electrodeposition without performing treatment such as electroless plating. This is preferable because a film can be formed on the inner surface of the flow path.

Non-conductive materials include materials such as ceramics, glass, silicone, and resin. The material is preferably glass from the viewpoint of transparency and workability. As said glass, common things, such as soda glass, quartz glass, borosilicate glass, crystal glass, can be used, for example.
Moreover, it is also preferable to use resin from the viewpoints of low cost, transparency, moldability, impact resistance, and the like. Specific examples of the resin include polyester resin, styrene resin, acrylic resin, styrene / acrylic resin, silicone resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amide resin, amideimide resin, and butyral. Resins, urethane resins, polyethylene resins, vinyl acetate resins and the like can be mentioned. From the viewpoint of impact resistance, heat resistance, chemical resistance, transparency and the like, a resin suitable for the application can be preferably used. Further, the resin may be a mixed resin or a polymer alloy as required.

The method for forming the microchannel is not particularly limited, but a known method can be used.
The microchannel can be produced by, for example, a fine processing technique. Examples of the fine processing method include a method using LIGA technology using X-rays, a method using a resist portion as a structure by a photolithography method, a method of etching a resist opening, a micro discharge processing method, a YAG laser, There are a laser processing method using a UV laser and the like, and a mechanical micro cutting method such as an end mill using a micro tool made of a hard material such as diamond. These techniques may be used alone or in combination.

In the present embodiment, the “connecting portion” refers to a case where at least two members are connected, bonded, welded, joined, or the like (hereinafter, “connected, glued, welded, joined, etc.” is also simply referred to as “connected”). Means the closest part between the two members or the part where the surface between the two members is in contact. Examples of the microchannel structure having the microchannel having the connecting portion include the following modes, but are not limited thereto.
(1) When the end of the tubular member forming two or more micro flow paths and one side of the pipe joint are connected as shown in FIG.
(2) When a plate-like member serving as a lid of the micro-channel is connected to a plate-like member having a groove-shaped micro-channel.
(3) Like the ink jet recording head shown in FIG. 2 (Japanese Patent Laid-Open No. 2002-307676), two or more plate-like members on which microchannels are formed are connected to form a laminated body to form a micro body. When a flow path is formed.
In the above (1) to (3), since there is a limit to the processing accuracy of the members and the positioning accuracy when connecting the members, gaps and misalignment occur between the members forming the connection part, An uneven part will be formed. Further, when two or more members are bonded, a convex portion due to the protrusion of the adhesive and a concave portion due to the lack of the adhesive are formed.

Next, the “concave portion on the inner surface of the microchannel” will be described.
There are minute grooves (concave portions) formed during processing on the surface in the microchannel and concave portions formed by the concavities and convexities of the connection portion. Such a recess serves as a nucleus for generating bubbles, generating gas dissolved in the liquid introduced into the microchannel as bubbles, and further growing the bubbles (FIG. 1).
Normally, large energy exceeding a certain energy barrier is required to generate bubbles from a liquid, but bubbles that already exist absorb the gas dissolved in the surrounding liquid and expand. In case you don't need energy. In addition, when liquid is introduced into the microchannel, bubbles are likely to be generated at the corners and recesses on the inner surface of the channel, and particularly at the recesses. As shown in FIG. 3, when the bubbles 13 are generated in the flow path (particularly, the micro flow path), the flow of the liquid 14 is partially or entirely obstructed.

When a microreactor or the like is used to measure the sample volume, it is difficult to accurately measure the sample volume due to the generation of bubbles. Furthermore, when a sample is quantified or qualitatively using an optical system, scattering of light is caused by bubbles and accurate measurement cannot be performed. Further, even when a sample is quantified or qualitatively using an electrode, if bubbles are generated on the electrode, accurate measurement cannot be performed.
Usually, in the field of spectroscopic measurement, in order to prevent the generation of bubbles from the solution, pre-treatment for removing dissolved gas from the solution and suppressing the generation of bubbles such as heating and stirring of the sample and ultrasonic stirring is performed. ing. However, when using a microreactor, the sample itself is very small, and it is difficult to carry out these pretreatments for the purpose of simple and rapid measurement. It cannot be prevented.

  In order to avoid this, it is considered that the inner wall of the flow path is chemically polished (etched) (Japanese Patent Laid-Open No. 2004-82118) to reduce the depth of the recess and suppress the generation of bubbles (FIG. 4). However, this method cannot sufficiently eliminate uneven portions, particularly concave portions, at the initial stage of microchannel formation.

The microchannel structure of the present embodiment is characterized by having a microchannel with a coating formed by at least partially embedding a recess in the inner surface of the microchannel. Since the concave portion is embedded by the coating, and the concave portion on the inner surface of the microchannel serving as a bubble generation nucleus is not in contact with the liquid introduced into the microchannel, the microparticles generated by bubble generation and bubble growth in the microchannel Blockage of the flow path can be suppressed.
In particular, in the microchannel structure according to the present embodiment, when the connection portion is a connection portion between the end of the tubular member forming the microchannel and one side of the pipe joint, bubbles are generated in the microchannel. In addition, clogging of the microchannel due to bubble growth can be preferably suppressed.

Next, the film will be described.
It is preferable that the coating embeds at least partially the concave portion on the inner surface of the microchannel and embeds the entire inner surface of the microchannel. That is, it is preferable that the member forming the microchannel is not exposed in the microchannel. It is preferable that the surface of the coating formed on the inner surface of the microchannel does not have a recess that becomes a bubble generation nucleus. The recess will be specifically described below.

  The depth of the recess is preferably 0.5 μm or less, more preferably 0.3 μm or less, and even more preferably 0.1 μm or less. Here, the “depth of the recess” means the depth from the surface of the member to the bottom of the recess. When the depth of the recess is within the above numerical range, the recess is less likely to be a bubble generation nucleus, and clogging of the microchannel can be suppressed.

The width of the recess is preferably 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.1 μm or less. Here, the “width of the concave portion” means a diameter when the concave portion is obtained assuming a circular shape.
When the width of the recess is 100 μm or more, it is difficult to become a bubble generation nucleus, and even when a bubble is generated as a bubble generation nucleus, it is not possible to capture and hold the bubble. Clogging of the microchannel can be suppressed.

  The number of recesses of 0.5 μm or more is measured by a stylus scanning method, and is preferably 0 to 10 pieces / mm, more preferably 0 to 3 pieces / mm per unit measurement distance. It is preferable for it to be within the above numerical value range because bubble generation can be efficiently suppressed.

The thickness of the coating is preferably 1.0 to 3.0 μm.
When the film is formed of a synthetic resin material, the thickness is more preferably 1.5 to 2.5 μm, and further preferably 1.8 to 2.2 μm.
When the coating is formed of a plated metal, the thickness is more preferably 1.5 to 2.5 μm, and further preferably 1.8 to 2.2 μm.
It is preferable that the thickness of the coating is within the above numerical range because the concave portion on the inner surface of the microchannel can be sufficiently embedded, and the generation of bubbles in the microchannel can be suppressed.

  The film in which the concave portion on the inner surface of the microchannel is at least partially embedded is preferably a film formed of a plating metal and / or a synthetic resin material. Examples of the coating formed by plating metal include a coating formed by electroless plating and / or electroplating. Examples of the film formed of a synthetic resin material include a film formed by electrodeposition or vapor deposition polymerization.

<Electrodeposition>
In the microchannel structure, when the inner surface of the microchannel is conductive, the coating formed by the synthetic resin material is preferably a coating formed by electrodeposition.
Electrodeposition is a method in which a conductive material to be coated and a counter electrode are immersed in an electrodeposition liquid containing a resin dispersed in an aqueous medium, and a direct current is passed between both electrodes to form a coating film by an electrochemical reaction. This is a method for forming a coating (coating film) to be deposited.
As the resin contained in the electrodeposition liquid, known resins can be used and are not limited, but are excellent in heat resistance, electrical insulation, wear resistance, chemical resistance, and mechanical properties. Therefore, a polyimide resin or a polyamide resin is preferable, and a polyimide resin is more preferable.

  As a film formation method by electrodeposition, (1) after electrodeposition using an electrodeposition solution in which polyamic acid as a polyimide precursor is dissolved, the electrodeposition film of polyamic acid is heated to dehydrate and imidize to form a polyimide film. And (2) a method of forming a polyimide film using an electrodeposition solution containing polyimide. In the method (1), the polyamic acid is easily decomposed, so that the storage stability of the electrodeposition solution is poor and a heat treatment for imidization is required. In the present invention, the method (2) is preferable because the landing liquid is excellent in storage stability and does not require heating. As the polyimide resin used in (2), for example, polyimide resins described in JP-A-9-104839, JP-A-2003-327907 and the like can be used, but are not limited thereto.

The electrodeposition liquid preferably has a polyimide resin solid content concentration of 5 to 10% by weight.
Examples of the water-soluble polar solvent that dissolves the polyimide resin include N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, sulfolane, and mixtures thereof.
These water-soluble polar solvents are preferably blended in a proportion of 30 to 60% by weight with respect to the total amount of the electrodeposition solution. When it is within the range of the above numerical values, the polyimide resin does not precipitate, and a film having excellent smoothness can be obtained.

  In order to impart water solubility and / or water dispersibility to the polyimide resin, it is preferable to add a basic nitrogen-containing compound to the electrodeposition liquid as a neutralizing agent. Examples of the neutralizing agent include triethylamine, trimethylamine, tripropylamine, tributylamine, pyridine, N-ethylpiperidine, N-methylmorpholine, N, N-dimethylaminoethanol, triethanolamine, and mixtures thereof. The neutralizing agent is preferably used in an amount of 1 to 200 parts by weight per 100 parts by weight of the polyimide resin. Within the above numerical range, the polyimide resin can be stably dispersed or dissolved in the electrodeposition solution.

  In the present embodiment, the electrodeposition liquid preferably contains an oil-soluble solvent in which the polyimide resin is soluble in addition to the water-soluble polar solvent. The oil-soluble solvent means an organic solvent that is substantially insoluble or hardly soluble in water. The oil-soluble solvent is effective in that it improves the flowability of the polyimide resin deposited on the article after electrodeposition and improves the smoothness of the coating film. Examples of the oil-soluble solvent include 1-acetonaphthone, acetophenone, benzylacetone, methylacetophenone, dimethylacetophenone, propiophenone, valerophenone, anisole, methyl benzoate, benzyl benzoate, and mixtures thereof. The oil-soluble solvent is preferably blended at a ratio of 10 to 30% by weight with respect to the total amount of the electrodeposition liquid.

Examples of the polyimide dispersant include alcohol compounds, ester compounds, lactone compounds, ether compounds, ketone compounds, hydrocarbon compounds, and mixtures thereof.
Specifically, examples of the alcohol compound include benzyl alcohol, furfuryl alcohol, diacetone alcohol, methyl cellosolve, and cyclohexyl alcohol.Examples of the ester compound include methyl benzoate, isobutyl benzoate, and butyl benzoate. Examples of the lactone compound include γ-butyrolactone, examples of the ether compound include anisole, tetrahydrofuran, and dioxane. Examples of the ketone compound include cyclohexanone, Michler ketone, and butanone. Examples of the hydrocarbon compound include toluene, xylene, Decalin is mentioned.

<Method of manufacturing microchannel structure by electrodeposition>
The manufacturing method of the microchannel structure according to the present embodiment includes at least one connecting portion formed by at least two members forming the microchannel and a microchannel having a conductive channel inner surface. A step of filling an electrodeposition liquid, and a step of forming a film on the inner surface of the microchannel by electrodeposition to at least partially embed a concave portion on the inner surface of the microchannel.

The method for producing a microchannel structure of the present invention will be described below with reference to FIGS. 5 to 7 by taking as an example a process for forming a polyimide resin film by electrodeposition.
As shown in FIG. 5, an electrodeposition liquid supply port 42, an electrode (conductive) 41, an insulating electrodeposition liquid supply channel 40 having an insulating seal member 44, and 2 shown in FIG. End portions of tubular members (hereinafter also simply referred to as “SUS pipes” 11 a and 11 b) having two stainless steel (SUS) micro flow paths (diameter in the flow path of 500 μm) are connected by metal pipe joints 12. A member having a tubular microchannel (hereinafter also simply referred to as “tubular microchannel member” 10) was prepared.

The tubular microchannel member 10 was sealed and connected to the electrodeposition liquid supply channel by a seal member 44 as shown in FIG. After supplying the electrodeposition liquid 51 from the electrodeposition liquid supply port 42 and filling the electrodeposition liquid 51 in the microchannel, the tubular microchannel member is used as the anode (or cathode), and the power source is connected to the microchannel. A current was passed at a constant voltage.
The constant voltage is preferably 10 to 200V, and more preferably 50 to 150V. The time for passing the current is preferably 0.5 to 10 minutes, and more preferably 0.5 to 3 minutes. It is preferable that the end point of electrodeposition is the time when the polyimide resin coating 61 having a predetermined thickness is formed or the current value becomes less than a certain value.

As a result of passing an electric current, a polyimide resin film 61 was formed as shown in FIG. After removing the power source from the tubular microchannel member 10 and removing the electrodeposition liquid from the inside of the microchannel of the tubular microchannel member 10 and the electrodeposition liquid supply channel 40, the tubular microchannel member on which the coating 61 is formed 10 was removed from the electrodeposition liquid supply channel 40.
The tubular microchannel member 10 on which the obtained coating film is formed is preferably baked with water and air-dried, and then heated in an oven to perform baking of the polyimide coating film. The baking temperature is a temperature suitable for the solvent used. Specifically, 100 to 300 ° C is preferable, and 200 to 300 ° C is more preferable. The baking time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 1 hour. An example of the obtained microchannel structure 70 is shown in FIG.

<Electroless plating, electroplating>
As electroless plating and electroplating, known ones can be used and are not limited. Examples thereof include nickel plating, copper plating, cobalt plating, gold plating, silver plating, and palladium plating. A film composed of two or more plated metal layers may be formed. In that case, the outermost layer in the flow path is preferably gold-plated because of excellent chemical resistance.
In the case where the material forming the microchannel is non-conductive, an embodiment in which a film is formed by electrodeposition or electroplating after imparting conductivity to the inner surface of the microchannel by electroless plating or the like is also preferable. In the case of imparting conductivity to the inner surface of the microchannel by electroless plating, the thickness is preferably 0.05 to 0.5 μm, and more preferably 0.1 to 0.3 μm. Furthermore, a film may be formed that not only imparts conductivity by electroless plating but also embeds a recess in the inner surface of the microchannel.

<Method of manufacturing microchannel structure by plating>
The manufacturing method of the microchannel structure according to the present embodiment includes at least one connecting portion formed by at least two members forming the microchannel and a microchannel having a conductive channel inner surface. The method includes a step of filling a plating solution, and a step of forming a film on the inner surface of the microchannel by plating to at least partially embed a recess in the inner surface of the microchannel.
Hereinafter, the method for producing a microchannel structure according to the present invention will be described with reference to an example of a film formation process by plating. Similar to the method of manufacturing the microchannel structure by electrodeposition, an electroplating solution supply channel and a tubular microchannel member are prepared as shown in FIG. 5, and a tubular microchannel member is provided in the electroplating solution supply channel. The flow path member was hermetically connected by a seal member as shown in FIG.
After supplying the electroplating solution from the electroplating solution supply port and filling the electroplating solution in the microchannel, the tubular microchannel member is used as the anode (or cathode), the power supply is connected to the microchannel, and the constant current Shed.
The constant current is preferably 0.005 to 0.1 A / cm ² , and more preferably 0.01 to 0.03 A / cm ² . The time for passing the current is preferably 0.5 to 5 hours, and more preferably 1 to 2 hours. It is preferable that the end point of electroplating is the time when a film having a predetermined thickness is formed. An example of the obtained microchannel structure 80 is shown in FIG.

<Vapor deposition polymerization method>
A known resin material can be used for the vapor deposition polymerization method, and it is not limited, but specific examples of the resin material include polyimide resin, polyamide resin, polyurea or polyurethane resin. Among them, in the present invention, it is excellent in heat resistance, electrical insulation, abrasion resistance, chemical resistance, and also has excellent mechanical properties. Therefore, polyimide resin or polyamide resin can be preferably used, and polyimide resin is more preferable. Can be used.

<Method for producing microchannel structure by vapor deposition polymerization method>
A microchannel structure in which a polyimide resin film is formed in a microchannel by vapor deposition polymerization will be described as an example. In a vacuum chamber of 10 ⁻³ Pa, pyromellitic anhydride is heated at 180 ° C. and 4,4-diaminodiphenyl ether is heated at 160 ° C. for sublimation. After the sublimated monomer reaches the inner surface of the microchannel, the amino group and the carbonyl group react to form a polyamic acid film. Thereafter, the polyamic acid film is heated at 200 to 300 ° C. to cause a dehydration reaction to form a polyimide film. The obtained microchannel structure 90 is shown in FIG.

  The coating formed on the inner surface of the microchannel is preferably a coating formed of a plated metal and / or a synthetic resin material, and more preferably a coating of a synthetic resin material formed by electrodeposition. Electrodeposition is preferable because the viscosity of the electrodeposition liquid is low and filling into the microchannel is easy, the smoothness of the obtained coating film is excellent, and recesses can be embedded over the details in the microchannel. .

<Microreactor>
The microchannel structure can be suitably used as a microreactor part. The microreactor of the microreactor is preferably partially or entirely formed by the microchannel structure of the present embodiment. The size of the microreactor can be set appropriately according to the intended use, preferably in the range of 1 to 100 cm ^2, the range of 10 to 40 cm ² is more preferable. The thickness of the microreactor is preferably in the range of 2 to 30 mm, more preferably in the range of 3 to 15 mm.

The microreactor of the present embodiment may have a site having functions such as reaction, mixing, separation, purification, analysis, and washing depending on its application.
The microreactor of this embodiment may be provided with, for example, a fluid introduction port for introducing a fluid into the microreactor and a fluid discharge port for recovering the fluid from the microreactor as necessary.
In addition, the microreactor of the present embodiment is a combination of a plurality of devices, a device having functions such as reaction, mixing, separation, purification, and analysis, a liquid feeding device, a recovery device, and other microreactors according to the application. Etc. can be combined to suitably construct a microchemical system.

  Hereinafter, the present embodiment will be described in detail by way of examples, but the present embodiment is not limited in any way.

(Example 1)
The microchannel structure of Example 1 was produced according to the steps illustrated in FIGS. A micro-channel (diameter in the channel) formed by a metal joint and a stainless steel (SUS) pipe in the electrodeposition solution supply channel having an electrodeposition solution supply port, an electrode, and an insulating seal member shown in FIG. 500 μm) was hermetically connected by a sealing member as shown in FIG. After supplying the electrodeposition liquid from the electrodeposition liquid supply port and filling the electrodeposition liquid in the microchannel, the power source was connected to the microchannel. As a result of energizing for 1 minute at a voltage of 50 V, a polyimide resin film having a thickness of 2.0 μm was formed as shown in FIG. After removing the power source from the micro flow channel and removing the electrodeposition liquid from the micro flow channel and from the electrodeposition liquid supply flow channel, the micro flow channel with the coating formed is removed from the electrodeposition liquid supply flow channel, and 30 ° C. at 30 ° C. The polyimide coating was baked by heating for a minute. The resulting polyimide resin film had a thickness of 2 μm. A microchannel structure 70 as shown in FIG. 8 was obtained.

<Measurement of surface shape of film>
The surface shape of the coating formed on the inner surface of the microchannel of the microchannel structure obtained in Example 1 was measured with a surface profile measuring instrument Tencor P10 (manufactured by Tencor). The measurement results are shown in FIG.
As a result of the measurement, 0 concave portions having a depth of 0.5 μm or more were observed per 1 mm of the measurement distance on the polyimide coating surface. In the same manner, the measurement was performed for a recess having a depth of 0.3 μm or more and a recess having a depth of 0.1 μm or more. The results are shown in Table 1.

<Continuous liquid feeding test>
The microchannel structure of Example 1 was maintained at 50 ° C., and pure water stored by saturating oxygen at 20 ° C. was introduced at a flow rate (5 ml / h) with a syringe pump. Although liquid feeding continued for 72 hours, liquid feeding could be continued without causing clogging of the microchannel due to generation of bubbles.

(Example 2)
FIG. 9 shows an example of a microchannel structure 80 in which a concave portion on the inner surface of the microchannel is embedded by gold plating. The thickness of the obtained gold plating was 2.0 μm.
The measurement results of the surface shape of the coating and the results of the continuous liquid feeding test are shown in FIG. The unevenness on the inner surface of the flow path is relaxed compared to the case of untreated (FIG. 14), but it is not sufficient as compared with the electrodeposition of Example 1.

(Example 3)
FIG. 10 shows an example in which unevenness is buried by forming a polyimide coating on the inner surface of the flow path by vapor deposition polymerization. In a vacuum chamber of 10 ⁻³ Pa, pyromellitic anhydride was sublimated by heating at 180 ° C. and 4,4′-diaminodiphenyl ether at 160 ° C. After the evaporated monomer reaches the microchannel, the amino group and the carbonyl group react to form a polyamic acid film, which is dehydrated by heating at 250 ° C. on the inner surface of the microchannel. Reaction occurred and a polyimide film was formed. The thickness of the obtained film was 2.0 μm.
The surface roughness measurement results and the continuous liquid feeding test results are shown in FIG.
Although the clogging of the microchannel is alleviated as compared with the case where it is not treated (FIG. 14), the flatness of the coating is not sufficient. Moreover, it was difficult to form a film deep in a thin microchannel tube by this method.

(Comparative Example 1)
A microchannel was prepared in the same manner as in Example 1 except that no film was formed on the inner surface of the microchannel (FIG. 1). The surface roughness measurement results and the continuous liquid feeding test results are shown in FIG.

It is the schematic which shows an example of the conventional microchannel structure. It is the schematic which shows an example which formed the microchannel by connecting a plate-shaped member etc. and forming a laminated body. It is the schematic which shows clogging of the microchannel by bubble generation | occurrence | production. It is the schematic which shows an example of the microchannel structure after the conventional surface treatment. It is a manufacturing method of the micro channel structure of this embodiment, and is a schematic diagram showing one of the processes of forming a coat by electrodeposition. It is a manufacturing method of the micro channel structure of this embodiment, and is a schematic diagram showing one of the processes of forming a coat by electrodeposition. It is a manufacturing method of the micro channel structure of this embodiment, and is a schematic diagram showing one of the processes of forming a coat by electrodeposition. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows an example which formed the film by electrodeposition. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows an example which formed the film by gold plating. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows an example which formed the film by the vapor deposition polymerization method. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows the result of having measured the surface shape of the film formed by electrodeposition. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows the result of having measured the surface shape of the film formed by gold plating. It is the microchannel structure of this embodiment, Comprising: It is the schematic which shows the result of having measured the surface shape of the film formed by the vapor deposition polymerization method. It is the schematic which shows the result of having measured the surface shape of the microchannel inner surface of the conventional microchannel structure.

Explanation of symbols

10: Tubular microchannel member 11a, 11b: SUS tube 12: Pipe joint 13: Bubble 14: Liquid 20: Microchannel 30, 50, 60, 70, 80, 90: Microchannel structure 40: Electrodeposition solution Supply channel 41: Electrode (conductive)
42: Electrodeposition liquid supply port 44: Insulating seal member 51: Electrodeposition liquid 61: Polyimide resin film 71: Film formed by electrodeposition 81: Film formed by gold plating 91: Formed by vapor deposition polymerization method Coated film

Claims (10)

Having at least one connection formed by at least two members forming a microchannel;
A microchannel structure having a microchannel in which a coating film in which a concave portion on the inner surface of the microchannel is at least partially embedded is formed.   The microchannel structure according to claim 1, wherein the connection portion is a connection portion between an end portion of a tubular member forming the microchannel and one side of a pipe joint.   The microchannel structure according to claim 1 or 2, wherein the depth of the concave portion on the surface of the coating is 0.5 µm or less.   The thickness of the said film is 1.0-3.0 micrometers, The microchannel structure as described in any one of Claims 1-3.   The microchannel structure according to any one of claims 1 to 4, wherein an inner diameter of the microchannel is 200 to 5,000 µm.   The microchannel structure according to any one of claims 1 to 5, wherein the coating is a coating formed of a plated metal and / or a synthetic resin material.   The microchannel structure according to claim 6, wherein an inner surface of the microchannel is conductive, and the coating formed of the synthetic resin material is a coating formed by electrodeposition.   The microchannel structure according to claim 7, wherein the film formed by electrodeposition is a film formed of a polyimide resin or a polyamide resin. Filling at least one connection part formed by at least two members forming the microchannel, and a microchannel having a conductive channel inner surface with a plating solution or an electrodeposition solution; and
A method of manufacturing a microchannel structure, comprising: forming a film on the inner surface of the microchannel by plating or electrodeposition, and at least partially embedding a recess in the inner surface of the microchannel. A microreactor, wherein the microchannel structure according to any one of claims 1 to 8 forms part or all of a microchannel.

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