JP2006255634A - Fine passage, its production method and usage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine passage enough in strength and without dissolution and elusion for an organic solvent, etc. <P>SOLUTION: The fine passage consists of a first substrate 2, ribs 3A, 3B which are obtained by calcining a glass composition, have a height of 10 μm-1 mm and are arranged on the first substrate to be spaced 100 μm -1 mm, and a second substrate 4 which is arranged on the ribs 3A, 3B as to cover an upper surface between the ribs 3A, 3B. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a microchannel provided with a rib obtained by firing a glass composition, a microchannel manufacturing method for manufacturing the microchannel rib by printing and firing, and a microchannel configured using the microchannel. Reactor related.

In recent years, a technology called nanotechnology has been used in the fields of fine chemicals, biochemicals, etc., and has made great progress. A microreactor is a general term for reaction devices having a plurality of flow channels (channels) on the micro and nano scales. This microreactor actively utilizes the scale law, and the reaction field is reduced by reducing the size. By increasing the ratio of (interface) to the ratio per volume, a rapid and efficient reaction system is created.
For example, by causing two types of liquids to flow through the same microchannel, a reaction occurs due to mass transfer at the interface. A microreactor is used as a reaction apparatus at that time. Microreactors are used not only for chemical reactions but also for mixing and separating two or more liquids by mass transfer at the interface.

When producing a microreactor, a metal, silicon, ceramics, a polymer material, or the like is used as a substrate. In addition, as a microfabrication technique for producing a micro flow path, an X-ray lithography method, a micro etching method, a micro electric discharge machining method, a laser machining method, a mechanical micro cutting method using a micro sand blast, and a micro tool are generally used. (For example, see Non-Patent Document 1).
Masami Hamada, Current Status and Prospects of Micro Machining, Journal of Precision Engineering, Japan Society for Precision Engineering, February 2002, Volume 68, Number 2, Pages 161-166

However, there are several problems with such a microfabrication technique.
For example, when a microchannel is formed by corroding a substrate by X-ray lithography or microetching, the cross section of the channel is hemispherical because the erosion extends in the lateral direction as the channel deepens. Or it becomes trapezoid, and there was a problem that the flow path as designed could not be formed.
Further, when the flow path is cut in the base material by a mechanical micro cutting method represented by a micro electric discharge machining method or the like, the smoothness of the cut surface is limited. If there is a problem with the smoothness of the flow path, there is a problem that is different from the flow path at the time of design, and bubbles that cannot be removed when flowing a liquid with high surface tension such as water. Side reaction caused by

On the other hand, a method of manufacturing a micro flow path for a microreactor by an injection molding method or a transfer molding method using a polymer material (resin) as a base material of the microreactor is known (see, for example, Patent Document 1). .
JP 2004-188862 A

In the manufacturing method of the microchannel of Patent Document 1 described above, a resin in which a gaseous substance such as carbon dioxide gas or a supercritical substance such as carbon dioxide supercritical fluid is dissolved is used for the purpose of reducing the viscosity of the resin. It has been. As the resin, polyolefin resin, polystyrene resin, polylactic acid resin, acrylic resin, polycarbonate resin, polyethylene terephthalate resin, and the like are used.
However, in this manufacturing method of the micro flow path, it is necessary to dissolve the specific substance as described above in the resin in order to reduce the viscosity, and the injection molding method or the transfer molding using the resin having the reduced viscosity. Although the micro flow path is formed by the method so as to reduce the variation in the volume of the micro flow path, it is still not sufficient. There is also concern about the elution of trace components of stabilizers and surfactants contained in the resin.

On the other hand, there is also known a method for producing a ceramic sintered body having a comb-like fine channel that uses ceramics as a base material for a microreactor and sinters an extruded product or a laminate of a plurality of green sheets. (For example, refer to Patent Document 2). Here, the ceramic raw material used is a specific silicon nitride-based powder with limited β fraction, oxygen content, average particle size, crystal form and the like.
JP 2004-202813 A

  However, in the manufacturing method of the minute (fine) flow path of Patent Document 2 described above, the sintering temperature is as high as 1650 ° C. to 1850 ° C. during pre-firing and 1850 ° C. to 1900 ° C. during sintering. Therefore, assuming that ribs are formed on an organic polymer material as a base material, in this firing temperature range, most of the organic polymer material is within a range that causes thermal decomposition even in an inert deoxygenated gas atmosphere. Yes, this method is not applicable. Furthermore, since it is made of ceramics, it is not yet sufficient although it is considered for thermal shock resistance. In addition, it is easily estimated that the adhesion strength at the metal-ceramic interface is remarkably lowered or peeled off due to the cooling after the end of firing even in the case of a base material such as a metal.

Further, a method of leaving only a portion corresponding to the rib on the surface of the glass and completely cutting the portion corresponding to the groove to make the rib is well known as a manufacturing method of a plasma display panel or the like (for example, a patent Reference 3).
JP-A-6-314542

  In the manufacturing method of the micro flow path of the above-mentioned patent document 3, since the area of the cutting part is large, the environmental load is large from the viewpoint of effective use of resources and from the viewpoint of energy. In addition, when a substrate made by this microchannel manufacturing method is used as a microreactor, since the cutting is performed by a sandblast method using fine alumina or diamond, smoothness is a problem as in the above case. It has become. An etching method is effective for correcting the smoothness, but it is necessary to use hydrogen fluoride or the like. Furthermore, the environmental load increases, and at the same time, the same problems as the microetching method and the like are inherent.

In addition, when conducting an experiment for grasping the reaction and interaction with a living body as a microreactor, the influence of the lead used in the glass is greatly enlarged because the influence of the interface is enlarged. Therefore, a proposal using a glass composition that does not contain lead or has a low lead content is desired.
In addition, in the case of a microreactor using ceramics or resin, there is a problem that an optical reaction, in particular, light in the ultraviolet region is not transmitted, and thus a reaction that handles this cannot be performed.

  An object of the present invention is to provide a microchannel having sufficient strength and not dissolving or eluting with an organic solvent or the like, and a method of manufacturing a microchannel that can easily manufacture the microchannel It is another object of the present invention to provide a microreactor that does not adversely affect the reaction using the microchannel.

The present invention is as follows.
(1) A first base, a second base opposite to the first base, and a glass composition that is fired. The height is 10 μm to 1 mm, and the first base is spaced apart from 100 μm to 1 mm. A microchannel provided with a rib provided between the second substrate.
(2) The method for producing a microchannel according to (1), wherein the rib is formed by applying the paste on the first substrate by printing using a paste containing a glass composition. And a drying step of drying the ribs formed on the first substrate, and a baking step of baking the dried ribs.
(3) A microreactor comprising the microchannel according to (1).

According to the microchannel of the present invention, the first substrate, the second substrate facing the first substrate, and the glass composition having a softening point of 300 ° C. to 600 ° C. are fired, and the height is 100 μm to Since the rib is provided between the first base and the second base at an interval of 100 μm to 1 mm at 1 mm, the first base or the second base is different from the material constituting the rib. It is possible to use materials, and the ribs are excellent in strength. Further, since the ribs are made of glass, they do not dissolve in organic solvents and are not eluted.
When the glass composition is made lead-free, when applied to a microreactor, the interface is not affected by lead when grasping the reaction and interaction with a living body, and is optimal as a microreactor.
Furthermore, by forming the first and second substrates into flat plates, there are few obstacles to the flow path such as burrs seen when cutting, and the flow path is smooth, so the production reaction can be promoted safely. Can do.
Furthermore, by setting the linear expansion coefficient of the glass composition to 75 × 10 ⁻⁷ / ° C. or more, the possibility that the ribs are cracked or the ribs are broken is reduced.
Furthermore, the first substrate and the second substrate to which the ribs are connected have an affinity for the ribs, so that the linear expansion coefficient of the glass composition constituting the ribs is equal to that of the substrate, and the rib firing step. In particular, phenomena such as peeling and fracture in the temperature lowering process are reduced.
Further, the affinity of the first substrate and the second substrate with the rib can improve the wetting characteristic by setting the contact angle with the rib to 100 ° or less.
Next, according to the method for manufacturing a microchannel according to the present invention, the application step of applying the paste onto the first substrate by printing using a paste containing a glass composition to form the ribs; Since a drying step for drying the ribs formed on one substrate and a firing step for firing the dried ribs are included, manufacture is easy, and a microchannel as designed can be easily manufactured.
In addition, the height of a rib can be easily adjusted by performing an application | coating process and a drying process several times, and the microchannel as designed can be manufactured.
Next, according to the microreactor of the present invention, since it is configured using the above-described microchannel, it does not dissolve in an organic solvent, has no eluting components, becomes a microchannel as designed, and has excellent smoothness. Also, it is advantageous for optical reaction and the like.

  Hereinafter, the present invention will be described in detail.

  The microchannel according to the present invention is formed by firing a first substrate and a glass composition having a softening point of 300 ° C. to 1400 ° C., and has a height of 10 μm to 1 mm and an interval of 100 μm to 1 mm. A rib provided on the substrate and a second substrate provided so as to close the upper surface between the ribs are provided.

FIG. 1 is an external perspective view showing an example of a microchannel according to the present invention, and FIG. 2 is an exploded perspective view of the microchannel shown in FIG.
In FIG. 1 or FIG. 2, reference numeral 1 denotes a microchannel, and a first base 2 having a softening point of 1400 ° C. or higher, and a softening point provided on the first base 2 is 300 ° C. to 1400 ° C., preferably Ribs 3A and 3B obtained by firing a glass composition of 300 ° C to 600 ° C at a firing temperature of 300 ° C to 1400 ° C, preferably 300 ° C to 600 ° C, and a softening point disposed on the upper surface of the ribs 3A and 3B is 1400 ° C. The second base 4 is configured as described above. Here, the shape of the micro flow path 1 is, for example, a space having a width (interval between the ribs 3A and 3B) of 100 μm to 1 mm and a height (height of the ribs 3A and 3B) of about 10 μm to 1 mm. It is.
The width of the ribs 3A and 3B is 1 mm.

The material constituting the first substrate used at the bottom of the microchannel of the present invention and the second substrate used at the top (hereinafter also referred to as planar material) is a glass composition having a low melting point constituting ribs (ribs). ) A material with affinity.
The affinity is grasped by a contact angle with a glass composition having a low melting point (hereinafter referred to as a glass composition), but a contact angle between a molten glass composition and a planar material is 100 ° or less, preferably 0 °. Good affinity is shown at ˜45 °.

Examples of such materials include glass, quartz, silica, Si / SiO ₂ , magnesia, zirconia, alumina, apatite, silicon nitride, and oxides, carbides, and nitrides of metals such as titanium, aluminum, yttrium, and tungsten. And ceramics such as borides and silicides. In addition, metals, plastics, and the like can be used as long as the above requirements (affinity) are satisfied. As the shapes of the first base and the second base, plate-like bodies are common, but arc-shaped bodies, spheres, granules, and the like may be used.

Next, the properties necessary for the glass composition used for the ribs on the first substrate include that the finely divided material has a lower softening point than the first substrate and the second substrate, as well as the linear thermal expansion coefficient. Is 75 × 10 ^{−7 to} 60 × 10 ⁻⁶ , preferably 75 × 10 ^{−7 to} 20 × 10 ⁻⁶ , excellent in water resistance and alkali resistance, and not containing lead as a glass component. preferable.
Here, JIS-R3104 was adopted as a method for measuring the softening point.

The components of the glass composition that satisfy the above-mentioned characteristics include (1) ZnO—SiO ₂ —B ₂ O ₃ system, (2) Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ system, and (3) Bi ₂ O. ₃ -SiO ₂ -B ₂ O ₃ -ZnO system, it may be mentioned _{(4) BaO-SiO 2 -B} 2 O 3 system, a _{(5) V 2 O 5 -SiO} 2 -B 2 O 3 system.
And it illustrates below about the preferable composition range of the component system of (1)-(5).
(1) In the ZnO—SiO ₂ —B ₂ O ₃ system, ZnO: 15 wt% to 60 wt%, SiO ₂ : 5 wt% to 55 wt%, B ₂ O ₃ : 5 wt% to 35 wt% are essential. Contains as an ingredient.
(2) In the Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ system, Bi ₂ O ₃ : 55 wt% to 75 wt%, SiO ₂ : 10 wt% to 25 wt%, B ₂ O ₃ : 5 wt% Contains -20% by weight as an essential component.
(3) In the Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ —ZnO system, Bi ₂ O ₃ : 55 wt% to 80 wt%, SiO ₂ : 2 wt% to 25 wt%, B ₂ O ₃ : 5 Weight% to 20% by weight, ZnO-based: 5% to 20% by weight as an essential component.
(4) In the BaO—SiO ₂ —B ₂ O ₃ system, BaO: 10 wt% to 30 wt%, SiO ₂ : 15 wt% to 40 wt%, B ₂ O ₃ : 15 wt% to 30 wt% are essential. Contains as an ingredient.
(5) In the V ₂ O ₅ —SiO ₂ —B ₂ O ₃ system, V ₂ O ₅ : 1 wt% to 20 wt%, SiO ₂ : 30 wt% to 55 wt%, B ₂ O ₃ : 15 wt% Contains -25% by weight as an essential component.

When lead is included, the composition of the glass having a softening point of 600 ° C. or lower is typified by PbO—SiO ₂ —B ₂ O ₃ , PbO—SiO ₂ —SnF _2, etc. is not.
In these compositions, ZnO, Bi ₂ O ₃ , BaO, and V ₂ O ₅ components form the core of lead-free (lead-free) glass that can replace conventional lead-containing glass. If these components are too small, the resulting glass composition has a drawback that the softening point becomes too high and the withstand voltage is lowered. Moreover, when too large, chemical resistance will fall.

The B ₂ O ₃ component serves to moderately lower the softening point and dielectric constant of the glass. If this component is too small, the softening point will be too high. Moreover, when too large, there exists a disadvantage that chemical resistance falls.
The SiO ₂ component is a component that becomes a skeleton of the glass. If this component is too small, vitrification becomes difficult, or the glass obtained even if vitrified is poor in chemical resistance, withstand voltage, and transparency. It will be a thing. On the other hand, if the amount is too large, it is difficult to obtain a glass composition having a softening point of 600 ° C. or lower.

In addition, the glass composition used for this invention can also contain another glass component as needed other than the predetermined amount of each said glass component. The glass component that can be added and blended as necessary and the blending amount thereof can be appropriately selected from those that do not adversely affect the properties of the glass obtained and the range. Specific examples of the glass component include SnO, SnO ₂ , WO ₃ , MoO ₃ , Al ₂ O ₃ , Tl ₂ O ₃ , La ₂ O ₃ , ZrO _{2 and the} like. These can be used singly or in combination of two or more, and it is desirable that the amount added is within 3% by weight. These formulations may be useful for fine adjustment of adhesive strength, fusing temperature, and chemical resistance.

Next, the manufacturing method of the microchannel of this invention is demonstrated.
In the method for producing a microchannel according to the present invention, a rib made of a specific glass composition is printed on a first substrate and fired to be solidified.
First, in forming the rib, the glass composition is pulverized. This pulverization can be performed according to a conventional method.
For example, the glass powder is mixed with each raw material compound so as to have the above-described component composition, the resulting mixed batch is melted at about 1150 ° C. to 1250 ° C., and the molten glass is sandwiched between water-cooled rolls and cooled to form flakes. Glass. The glass flakes are prepared by wet or dry pulverization using an appropriate pulverizer such as a ball mill. When wet pulverization is performed in water, it is particularly desirable to vacuum dry the cake-like material obtained by filtering off moisture.
The powder of the glass composition thus obtained is not particularly limited, but it is usually desirable that the powder has a particle size in the range of about 0.1 μm to 30 μm. Such a particle size can be easily adjusted according to a known and commonly used method. The powder particles obtained according to the above method can be further classified as necessary to adjust the particle size to an appropriate particle size within the above range, more preferably within the range of about 0.5 μm to 10 μm.

The glass composition for forming the rib is usually used by mixing the glass powder described above with an organic vehicle to prepare a suitable paste form. Here, the organic vehicle to be used may be any of those generally used for this kind of glass paste, and these are usually made of a solvent solution of a resin.
The organic vehicle component is preferably thermally decomposed at a temperature not higher than the firing temperature of the rib, usually not higher than 600 ° C. As applicable resin, a cellulose resin and an acrylic resin can be illustrated as a preferable thing. Examples of the cellulose resin include ethyl cellulose, hydroxyethyl cellulose, and nitrocellulose, and examples of the acrylic resin include polybutyl acrylate and polyisobutyl methacrylate. The above resin is generally blended in a glass paste composition to be adjusted in a range of about 0.5 wt% to 20 wt% in a single amount alone or in combination of two or more. Good. Further, the glass paste is appropriately mixed with known additives, for example, an anti-precipitation agent, a dispersing agent, an adhesion improver with a planar material (first base and second base), etc., if necessary. be able to.

  The solvent that constitutes the solvent solution of the resin may be any of various commonly known solvents and is not particularly limited. Usually, the resin is excellent in solubility and can form a viscous oil. This includes medium and high boiling ester solvents, ether solvents, petroleum solvents and the like. Specifically, for example, ester solvents such as butyl cellosolve acetate and butyl carbitol acetate, ether solvents such as butyl carbitol, petroleum solvents such as naphtha and mineral terpenes, and the like can be exemplified. These may be used alone or in combination of two or more.

  The preparation of the glass paste and the method of forming the ribs of the glass using the glass paste will be described in detail. First, a predetermined amount of the glass composition is placed in three rolls in oil obtained by dissolving the resin in a solvent having a relatively high boiling point. The slurry is dispersed by a dispersing machine such as a ball mill or a sand mill to prepare a slurry or paste (referred to as glass paste), and this glass paste is then subjected to stencil printing, for example, doctor blade method, roll coating method, screen printing. According to various methods such as a method, a table coater, a reverse coater, and a spray method, printing and coating are performed on the first substrate.

A coating method that is cost effective with accuracy at present, and details about the method using screen printing, which is stencil printing, will be described in detail. The squeegee is moved on the plate on which the first substrate and the screen are fixed, and extruded from the screen. The glass paste thus prepared is applied and printed on the first substrate. In this case, there is no problem with the printing method in which the squeegee is moved manually or automatically. In addition, there is no problem even if the screen used for continuous production rotates and the paste is printed and applied to the first substrate.
The screen can be exemplified by metal, plastic, cloth, etc., and the production method is one in which fibers and fine lines are knitted, or one in which a flat plate is processed by a method such as machining or laser irradiation, chemical etching, etc. If the glass paste does not dissolve, there is no particular concern. The paste-transmitting holes formed on the screen may be square, circular, hexagonal, etc., and the hole size may be 60 / inch mesh to 600 / inch mesh. It is further desirable to have a physical / chemical surface treatment to improve the wettability of the glass paste.

When creating a pattern to be printed on the screen, a method of creating a mesh by machining, laser irradiation, chemical etching, etc. on a flat plate, or when creating a pattern by making a screen in advance, a photomask or Although there is a method of performing photoetching, any method may be used.
An appropriate amount of glass paste is pressed onto the screen with a squeegee, and the paste is printed and applied onto the first substrate by extruding the glass paste from the holes of the screen.

The amount of application by printing on the first substrate controls the thickness of the rib.
Therefore, since the volume changes after drying or firing, the height of the rib is the sum of the distance between the screen and the first substrate, called the gap length, which is the coating amount, and the thickness of the screen. It is grasped as a numerical value multiplied by a coefficient.
The distance between the screen and the first substrate is generally in the range of 0 mm to 10 mm, preferably 0 mm to 5 mm. If it exceeds 10 mm, in the case of such a glass paste composition, the shape tends to collapse during drying due to the relationship between the surface tension and viscosity of the paste, and it becomes difficult to make vertical ribs.
In such a case, the height of the rib can be increased by alternately repeating printing and drying. That is, the height of the rib can also be adjusted.

Further, when the distance between the screen and the first substrate is 0 (zero), and the screen is brought into contact with the first substrate, the amount of the glass paste extruded onto the first substrate is minimized. At this time, the amount of the glass paste is only present in the screen, and the height of the ribs depends entirely on the thickness of the screen.
For the purpose of controlling the height of the rib, alternately repeating printing and drying is not limited to the first substrate. It is also possible to perform printing and drying on the upper surface of the first substrate and the lower surface of the second substrate, and melt the glass component in the firing step described later to bond the ribs together.

In the case where a resin solvent is contained in the glass paste, drying is carried out when it is necessary to disperse the resin solvent after printing. If the temperature is too high, the solvent diffusing speed is high, and there is a possibility that the growth of bubbles in the ribs and the smoothness of the surface may be lost. Since there is a decrease in accuracy, the temperature range is from room temperature to a temperature that is 10 ° C. lower than the boiling point of the solvent, preferably 25 ° C. lower than the boiling point.
There is no problem in the dry atmosphere in a normal air state, but it is more preferable to carry out deoxygenation and water vapor removal from the viewpoint of coloring and prevention of side reactions. Also, from the standpoint of industrial safety, it is desirable to actively exchange the atmosphere in order to avoid explosion limits and protect workers, and drying efficiency is also improved.

Firing is performed in a general furnace, but a heat source having a large heat capacity is desirable from the viewpoint of maintaining uniformity, regardless of electricity, gas, or the like. Further, it is more desirable that the firing atmosphere can be selected from the same viewpoint as the drying step, and the atmosphere can be positively exchanged.
The temperature at the time of baking raises temperature to the softening temperature (300 degreeC-1400 degreeC) of a glass paste, a glass component is fuse | melted, and it adheres with a 1st upper body and a 2nd base body as a rib. The temperature rise pattern at that time may reach the softening temperature at a constant rate of temperature rise, but more preferably, when an organic vehicle is mixed for the purpose of adjusting to an appropriate paste-like form, This is a method in which glass components are melted after being decomposed by holding at a temperature about 25 ° C. higher than the thermal decomposition end temperature for a certain period of time.
Since the vehicle is gasified and diffused into the atmosphere with thermal decomposition, if the glass starts to melt during the decomposition and gasification of the vehicle, the gas diffusion route of the gasified vehicle component disappears. Cause turbidity and cracks in the ribs. The decomposition temperature of the vehicle component is in the range of 150 ° C. to 200 ° C. in the case of the cellulose resin, and in the range of 120 ° C. to 220 ° C. in the case of the acrylic resin.
The holding time is in the range of 15 minutes to 120 minutes, preferably in the range of 30 minutes to 90 minutes. Even after 120 minutes, there is no further improvement in the effect.
In addition, since the glass component is an oxide, it actively induces an oxidation reaction, which is a main factor for the decomposition of the vehicle component, and when a certain amount of oxide is mixed in the glass paste at the decomposition temperature, the strength and adhesive strength of the rib itself are further increased. Favorable results are obtained with regard to transparency. The mixing ratio is in the range of 1 wt% to 10 wt%, more preferably in the range of 3 wt% to 10 wt%, but if it exceeds 10 wt%, industrial safety problems and corrosion due to equipment oxidation Such problems become prominent.

  There are various measuring methods for measuring the melting temperature of glass paste and the decomposition behavior of vehicle components, but it is simple and the method of differential thermal thermogravimetry of the thermal analysis method is a method that can simultaneously measure the melting temperature of glass and the decomposition behavior of vehicle components. The simultaneous measurement method (TG / DTA) is desirable. Although there is a differential scanning calorimetry (DSC) as long as the decomposition behavior, there are problems such as rupture of a closed cell and contamination of the measurement system due to gas release. Thermomechanical analysis (TMA) is suitable for tracking the behavior of mechanical properties associated with melting, but it cannot measure the decomposition behavior at all, and is usually compatible with powder samples such as glass paste to measure solid samples. Can not. Also, once calcined and solidified, the sample can be measured by thermomechanical analysis (TMA), but there is a possibility that the phase has changed, and there remains a problem as to whether the behavior before firing can be completely grasped. .

The upper second substrate may be installed and heated before firing, but the gas release accompanying the decomposition of the vehicle component is mostly performed on the upper surface due to the ratio of the surface area. It is more desirable to install the second substrate with respect to the strength, adhesion strength and transparency of the ribs alone.
Firing is performed at a softening temperature in the range of 60 minutes to 360 minutes, preferably 90 minutes to 180 minutes. There is no further improvement in the effect even after 360 minutes.
Cooling to room temperature after the completion of firing is preferably allowed to cool for about 4 hours. Furthermore, since glass paste is a mixture of a plurality of components, there is a temperature difference in the temperature at which each solidifies. In order to grow the crystal largely by precipitation of the crystal accompanying solidification of the steel, it is desirable from the viewpoint of the strength of the rib body and the adhesive strength to lower the temperature step by step by creating a plurality of temperature maintaining states.
In addition, when immersed in a coolant such as water or oil and rapidly cooled, there is a high possibility that the ribs are cracked or the ribs are cracked. In particular, when the linear expansion coefficients of the first substrate and the second substrate represented by metal or the like and the glass composition to be a rib are greatly different, the possibility is further increased.

The determination of the constant holding temperature when the temperature is lowered stepwise is preferably a temperature drop measurement by differential scanning calorimetry (DSC) of the glass paste sample. Once the glass once fired is pulverized and atomized, the temperature is raised to 600 ° C. or higher in the apparatus, and then the solidification temperature is determined from the endothermic endothermic behavior accompanying the temperature drop. A temperature lower by 20 ° C. to 0 ° C. than this solidification temperature, preferably a temperature lower by 10 ° C. to 5 ° C. is preferable. When the temperature is 20 ° C. or higher, almost no improvement is observed in the effect such as improvement in strength. The holding time is about 30 minutes to 120 minutes, preferably about 45 minutes to 90 minutes, and no further improvement in the effect is observed even when performed for 120 minutes or longer.
In this way, microchannels having glass ribs are created by printing and baking glass paste.

  Next, a microreactor that is an example of a use of a microchannel having ribs will be described in detail.

3 is an external perspective view showing an example of the microreactor of the present invention, FIG. 4 is an exploded perspective view of the microreactor shown in FIG. 3, and FIG. 5 is an external perspective view showing another example of the microreactor of the present invention. 6 is an exploded perspective view of the microreactor shown in FIG. 5, and the same or corresponding parts as those in FIGS. 1 and 2 are denoted by the same reference numerals.
In these drawings, reference numeral 5 denotes a microreactor, which includes a first substrate 2, ribs 3A, 3B, 3C, 3X, 3Y, 3Z provided on the first substrate 2, and ribs 3A, 3B, 3C, A second base 4 disposed on the upper surface of 3X, 3Y, 3Z, and attached to the second base 4, a reaction solution, a solvent, or the like is introduced into the microchannel 1, or a mixture or the like is taken out from the microchannel 1. Assembly 6A, 6B, 6C. The rib 3X connects the ends of the ribs 3A and 3B constituting the minute flow path 1 in an arc shape, and the rib 3Y connects the ends of the ribs 3B and 3C constituting the minute flow path 1 in an arc shape, The rib 3Z connects the ends of the ribs 3C and 3A constituting the minute flow path 1 in an arc shape.

Microreactors reduce the overall volume in unit operations such as liquid-liquid, gas-liquid reactions, mixing, extraction, and phase separation that occur at the interface, thereby increasing the proportion of the interface and increasing the efficiency of reactions and unit operations. There are no particular restrictions on the type of reaction substrate or product.
In addition, the extremely large surface area in the volume tends to make the temperature distribution extremely uniform, greatly contributing to the prevention of local heating associated with mixing and reaction.

  For example, as described above, when a rib made of glass paste is formed in a Y shape on the surface of a glass plate as a first substrate to form a microreactor having a microchannel, different types of substances or solutions from two directions are used. Reaction and mixing are performed in the micro space by flowing and joining. The reaction form at that time is, for example, oxidation reaction represented by oxidation of alcohol to aldehyde or ketone, epoxidation of olefin, reduction reaction represented by reduction of aldehyde or ketone to alcohol, or C-alkylation. For example, bond formation typified by formylation, cleavage of epoxide, deformylation, bond cleavage reaction typified by carboxyl, epimerization, sigmatropy transfer, functional group conversion reaction typified by conversion of hydroxyl group to halogen group, etc. However, the reaction form is not limited as long as no solid precipitates or the viscosity increases as the reaction proceeds.

  Moreover, as shown in FIG.3 and FIG.4, by making the exit side of a microchannel into a Y shape, the unpurified solution which is the mixture after completion | finish of reaction is poured from one direction of an inlet side, and another direction By allowing the extraction solvent to flow from, extraction can occur at the interface after merging, thereby enabling purification. The reaction mixture to be flowed is preferably a combination of solutions that are not mixed with each other, such as water-benzene, toluene, xylene, water-dichloromethane, carbon tetrachloride, water-ethyl acetate, methyl acetate, water-hexane, and heptane. preferable. The substance extracted using either of these as a reaction liquid is preferably a reaction liquid containing a component soluble in the other.

For example, hydrochloric acid gas produced as a by-product of esterification with alcohol using acid chloride or acid bromide in benzene or hydrochloride fixed with amine as a dehydrochlorinating agent is soluble in water. preferable.
By flowing this from one side of the inlet and flowing water from the other side, extraction occurs at the interface and is taken into the water.
Conversely, by combining an aqueous solution containing an organic component and the above organic extract, the organic component of the aqueous solution can be taken into the organic layer.
After the unit operation is completed, the water and the organic solvent are separated at the opposite Y-shaped portion.
Also, if one flow path is provided in the middle of the Y-shaped part and the three-way separation is performed, the mixing part at the interface flows in the middle, and at this time, the central flow path has a cross-sectional area 1 / compared to the other flow paths. It is preferable to make it 3 or less, and more preferably the cross-sectional area is 1/6 to 1/4. If it becomes larger than this, water or an organic solvent portion other than the mixing portion of the flow path will also flow in.

Thus, the Y-shaped microreactor can be manufactured by a manufacturing method similar to the above-described manufacturing method of the microchannel.
The substrate used in the reaction is not particularly limited as long as it has a composition that attacks glass typified by hydrogen fluoride and strong alkali. As for the movement of the fluid, there are a method in which the inlet side is pressurized or the outlet side is depressurized, and a piezoelectric element is embedded in the flow path to vibrate.
Also, when firing the rib during rib production, the method of inserting the electrode into the rib or the rib is produced in two steps, and after the initial rib production, the electrode is placed on the upper surface of the rib, and then the rib is printed and fired again It is also possible to embed an electrode in the rib by this method to generate an electroosmotic flow. It is also possible to use an electrophoretic flow as a drive source using this electrode.

By combining a plurality of these structures, it is possible to continuously perform multi-stage reactions and unit operations. It is also possible to perform an efficient reaction by creating a flow path for collecting a part of the reaction solution and returning it to the inlet again.
In addition to glass and transparent plastic as the first substrate and the second substrate, a wide range of physical properties can be measured by making the first substrate quartz. By using a material having excellent optical characteristics as a planar material, various physical properties can be measured by transmitting light.
The wavelength band used for the measurement depends on the optical characteristics of the planar material, and ultraviolet rays, infrared rays, laser beams, etc. are used. In addition, the rib side produced by printing and baking can be used in the same manner, and the above-described light can also be used at that time.

It is also possible to embed an optical fiber in the rib in the same manner as the electrode is embedded in the rib in order to use the electroosmotic flow or electrophoretic flow described above, and this should be used as a light introduction system to the light source and detector. Thus, analysis is possible even if the light source or detector is separated from the flow path.
The shape, dimensions, and cross-sectional structure of the optical fiber to be used are not particularly limited as long as the thickness thereof has a melting point equal to or less than the height and width of the rib and the firing temperature.
Note that the microreactor of the present invention shown in FIG. 5 and FIG. 6 is an example in which the contact time is lengthened by lengthening the microchannel compared to the Y-shape of FIG. And the method of lengthening a microchannel is not limited to this example. This microreactor can also be manufactured by a method similar to the method of manufacturing the microchannel described above.

[Manufacture of microchannels]
Example 1
Using the glass composition shown in Table 1, it was pulverized to about 5 μm according to a conventional method.
Next, the glass composition was mixed with the organic vehicle component at a weight ratio of 1: 1, and deaerated while being stirred for 10 minutes with a rotation / revolution mixer, and mixed uniformly. The organic vehicle used at this time was obtained by dispersing ethyl cellulose powder in butyl carbitol acetate at a weight ratio of 8: 2.
The glass paste after mixing described above was uniformly cloudy, and its viscosity was about 800 poise as measured with a B-type rotational viscometer.
The linear expansion coefficient of the glass composition described in Table 1 was obtained by the ASTM D696 measurement method, and the softening point was obtained by the JIS-R3104 measurement method.

Subsequently, the above-mentioned glass paste was printed and apply | coated using the screen printing method on the soda glass plate used for normal microscopes.
At that time, the screen used was a polyester 200 mesh parallel stretch pattern held in a 50 cm × 30 cm hollow aluminum screen frame and having a thickness of 50 μm and stretched at a baking angle of 45 degrees. Then, the target pattern was drawn on the screen with a diazo photosensitizer, and was produced with a film thickness of 10 μm.
The printing and coating conditions were vertical (90 °) to the soda glass plate surface, the squeegee angle was 70 °, the squeegee speed was 150 mm / sec, the printing pressure was 1.5 kg / cm, and the screen spacing was The condition was 2 mm. The squeegee used has a hardness (rubber hardness) of 70 Shore and a 9 mm thick polyurethane rubber fixed to a frame made of aluminum exclusively for screen printing.

After the printing was completed, drying was performed in a high-temperature bath (high-temperature bath NHK-170, manufactured by Nippon Ceramic Science Co., Ltd.) at 120 ° C for 30 minutes. Then, overprinting was performed several times in the same pattern according to the target rib height. In the present glass paste composition, the height of the ribs was reduced by 50% after printing and after firing, and the height of the ribs measured with a micro gauge having a resolution of 1 μm after one printing was about 20 μm.
Therefore, in order to obtain the target rib, the rib was also printed on the upper second substrate in the same manner and dried. Thereafter, printing was repeated again on the ribs of the lower first base, and then bonded to the second base and fired.

The firing conditions are as follows.
First, drying was performed in a high-temperature bath at 120 ° C. for 30 minutes, and then the temperature was raised to 400 ° C. at a rate of 1 ° C. for 1 minute, followed by firing at 400 ° C. for 40 minutes. Next, the temperature was similarly raised to 500 ° C. at a rate of 1 ° C. for 1 minute, and baked at 500 ° C. for 20 minutes. Next, the temperature was similarly raised to 560 ° C. at a rate of 1 ° C. for 1 minute and baked at 560 ° C. for 10 minutes. Then, it cooled at 130 degreeC / hour descending speed and returned to normal temperature.
The obtained microchannel is a microchannel as shown in FIG. 1 having a width of 3 mm and a rib height of 100 μm.

(Example 2) to (Example 5)
Using the glass compositions of Examples 2 to 5 shown in Table 1 as ribs, respective microchannels were produced according to Example 1.

[Microreactor using microchannel]
(Example 6)
0.91 g (0.10 mol) of acrylic acid chloride was added to methylene chloride from one side of a microreactor having a Y-shaped microchannel having a width of 3 mm, a height of 100 μm, and a reaction part length of 75 mm manufactured in the same manner as in Example 1. Dilute the whole solution to 200 ml, and dilute 0.54 g (0.95 mol) allyl alcohol and 11.2 g (0.11 mol) triethylamine in methylene chloride from the other side to make the whole solution 200 ml. Pumped into the microreactor at speed.
The liquid feeding speed into the microreactor was 4 ml / min, and the liquid feeding was completed in 50 minutes. The reaction liquid discharged from the opposite side was collected in a beaker. The microreactor was placed at room temperature (20 ° C.), and treatment such as heat removal was unnecessary.
As a result of comparing the solution after the reaction with a colorimetric liquid defined in the appearance of the liquid sample described in Section 5.1 (2) of JIS K8001, the coloration was equivalent to No. 10 (colorless).

(Comparative Example 1)
A 500 ml three-necked flask is equipped with a thermometer, a stirrer (with a stirring seal), and an isobaric dropping funnel. In the three-necked flask, 0.91 g (0.10 mol) of acrylic acid chloride is diluted with methylene chloride. A 200 ml solution was charged in advance, and an equal pressure dropping funnel was charged with a solution in which 0.54 g (0.95 mol) of allyl alcohol and 11.2 g (0.11 mol) of triethylamine were diluted in methylene chloride to make a total of 200 ml. .
The methylene chloride solution of allyl alcohol and triethylamine was added dropwise so as to be completed in 50 minutes as in Example 6.
When the three-necked flask was kept at room temperature, the temperature rose due to the reaction and heat of dilution, and boiling of the solvent (about 40 ° C.) was confirmed. In order to keep the reaction solution at 20 ° C., cooling with an ice bath was necessary.
Even when the bath was ice bathed, the solution after the reaction in Comparative Example 1 was compared with the colorimetric liquid defined in the appearance of the liquid sample described in Section 5.1 (2) of JIS K8001, and as a result, the coloring was No. 500. (Reddish yellow).

  As described above, by using a microreactor (Example 6) using a micro flow channel, heat removal is performed more efficiently than in a batch type reaction system (Comparative Example 1), and thus a reaction with less by-products. Confirmed that it was possible. This shows that it is extremely advantageous for optical materials such as lens materials and organic optical fiber materials, which are feared to have a slight influence on the transparency of the products of side reactions even if they are very small.

(Example 7)
From one side of a Y-shaped microreactor having a width of 3 mm, a height of 100 μm and a reaction part length of 75 mm manufactured in the same manner as in Example 1,

4-methoxy-2-quinolone represented by the formula: 0.306 g (0.00175 mol) diluted in methanol to give a total volume of 150 ml, 3.01 g (0.035 mol) of methyl acrylate was added from the other side. Diluted in methanol to a total volume of 150 ml was pumped into the microreactor at the same rate. The liquid feeding speed into the microreactor was 5 ml / min each, and the reaction liquid that was discharged from the opposite side in 30 minutes was collected in a beaker. The microreactor was placed in room temperature (20 ° C.) and treatment such as heat removal was unnecessary.
By irradiating the reaction part with light with a high pressure mercury lamp (output 400 W), the disappearance of the peak of the compound of [Chemical Formula 1] in the reaction solution discharged from the microreactor was confirmed by HPLC.
The solvent was evaporated and concentrated, and the residue was recrystallized from methanol to obtain 304 mg of the exo adduct of the following [Chemical Formula 2].

The mother liquor was purified by silica gel preparative thin layer chromatography using a developing solution of dichloromethane: methanol (10: 1) to obtain 92 mg of a mixture of equal amounts of exo and endo adducts.
The exo adduct is m. p. At 227-229 ° C. (DTA 10 ° C./min N ₂ flow), proton NMR spectrum assignments are δ 1.99 (1H, dt, J = 11.0 Hz, 8.0 Hz), 2.28 (1 H, dt, J = 11.0 Hz, 3.5 Hz), 3.38 (1 H, dd, J = 8.0 Hz, 3.5 Hz), 3.61 (1 H, dt, J = 11.0 Hz, 8.0 Hz), 2.95 (3H, s), 3.81 (3H, s).

(Comparative Example 2)
At room temperature, a 300 ml three-necked flask was equipped with a gas introduction part, a discharge part with a radiator, and the same high-pressure mercury lamp as in Example 7, and 0.306 g of 4-methoxy-2-quinolone represented by [Chemical Formula 1] (0 .00175 mol) and 3.01 g (0.035 mol) of methyl acrylate were diluted in methanol to prepare a total amount of 300 ml.
Under nitrogen introduction, a high-pressure mercury lamp was irradiated from the inside while stirring with a magnetic stirrer, and the disappearance of the peak of [Chemical Formula 1] was confirmed by HPLC after 1 hour.
The solvent was distilled off and concentrated, and the residue was recrystallized from methanol to obtain 272 mg of an exo adduct of [Chemical Formula 2]. The mother liquor was purified by silica gel preparative thin layer chromatography using a developing solution dichloromethane: methanol (10: 1) to obtain 86 mg of a mixture of equal amounts of exo and endo adducts.

  As described above, a microreactor (Example 7) using a microchannel made of a specific glass composition is used for a photoreaction, so that light can be efficiently emitted compared to a batch-type reaction system (Comparative Example 2). Since energy is irradiated to the reaction substrate, an efficient reaction is possible. It is also clear that the yield itself is improved because the homopolymer of methyl acrylate is not a by-product because of complete mixing. This is extremely advantageous when a highly reactive vinyl monomer or the like is used for an addition reaction without polymerization.

(Example 8)
From one side of a Y-shaped microreactor having a width of 3 mm, a height of 100 μm and a reaction part length of 75 mm manufactured in the same manner as in Example 1,

A solution obtained by diluting 0.256 g (0.002 mol) of 2,2-dimethyl-4H-1,3dioxin-4-one represented by hexene to make 10 ml as a whole was obtained from 1.36 g of cyclopentene from the other side. (0.020 mol) was diluted with hexene to make a total of 10 ml, and the solution was pumped into the microreactor at the same rate. The liquid feeding speed into the microreactor was 0.1 ml / min, and the reaction liquid discharged from the opposite side in 100 minutes was collected in a beaker. The microreactor was placed in room temperature (20 ° C.) and treatment such as heat removal was unnecessary.
The reaction part is irradiated with 300 nm light from the outside with Rayonet Photochemical Reactor, RPR3000A to form an alkene and a light [2 + 2] adduct, which immediately opens the ring,

The de Mayo reaction giving the δ-type diketone represented by
The resulting reaction solution was distilled off, concentrated and distilled to obtain 281 mg (yield 63%) of the compound. The resulting compound has a bp 110 ° C. (0.3 mmHg) proton NMR spectral assignment of δ1.13 (Me), 1.14 (Me), 3.72 (dd, J = 6.0 Hz, 2.0 Hz). there were.

(Comparative Example 3)
A 50 ml three-necked flask was equipped with a gas introduction part, a discharge part with a radiator and an ultraviolet irradiation device Rayonet Photochemical Reactor, RPR3000A, and 2,2-dimethyl-4H-1,3dioxin-4- represented by [Chemical Formula 3] A solution was prepared by diluting 0.256 g (0.002 mol) of ON and 1.36 g (0.020 mol) of cyclopentene in hexene to make a total of 20 ml.
While stirring with a magnetic stirrer under a nitrogen stream, light of 300 nm was irradiated. When traced by TLC, the spot of 2,2-dimethyl-4H-1,3dioxin-4-one disappeared after 12 hours, and the resulting reaction solution was concentrated by distillation and distilled to give 211 mg (yield 54%) To give a compound. The characteristics of the obtained compound were the same as in Example 8.

  As described above, when a microreactor (Example 8) using a microchannel made of a specific glass composition is used for a reaction by ultraviolet light, a material made of borosilicate glass having a wavelength of 300 nm and a transmittance of 30%. It can be seen that the efficiency is higher than that of the batch type even when using. Furthermore, since the air interface is extremely small as compared with the batch type reactor (Comparative Example 3), it can be seen that nitrogen introduced into the reaction system for the purpose of preventing coloring is unnecessary.

It is an external appearance perspective view which shows an example of the micro channel of this invention. It is a disassembled perspective view of the microchannel shown in FIG. It is an external appearance perspective view which shows an example of the microreactor of this invention. FIG. 4 is an exploded perspective view of the microreactor shown in FIG. 3. It is an external appearance perspective view which shows the other example of the microreactor of this invention. FIG. 6 is an exploded perspective view of the microreactor shown in FIG. 5.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Microchannel 2 1st base | substrate 3A rib 3B rib 3C rib 3X rib 3Y rib 3Z rib 4 2nd base | substrate 5 Microreactor 6A assembly 6B assembly 6C assembly

Claims (3)

A first substrate;
A second substrate facing the first substrate;
A rib formed by firing a glass composition, having a height of 10 μm to 1 mm and an interval of 100 μm to 1 mm between the first base and the second base;
A microchannel comprising: It is a manufacturing method of the micro channel according to claim 1,
An application step of applying the paste on the first substrate by printing using a paste containing a glass composition to form the rib;
A drying step of drying the rib formed on the first substrate;
A firing step of firing the dried ribs,
A method of manufacturing a microchannel characterized by the above. It was configured using the microchannel according to claim 1.
A microreactor characterized by that.

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