JP2004277590A - Base material for microchemical process and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base material for a microchemical process, having a fine complicated outer shape, surface ruggedness, inner passages, inner voids or the like, and providing improved functionality and treatability; and to provide a method for producing the base material. <P>SOLUTION: The base material for the microchemical process comprises a polymer gel containing a water-swellable clay mineral, includes the passages in the interior, and/or has the ruggedness on the surface. The base material is produced by pouring an aqueous solution containing a water-soluble organic monomer and the finely dispersed water-swellable clay mineral in a mold, polymerizing the water-soluble organic monomer to provide the polymer gel, and removing the polymer gel from the mold. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a substrate for a microchemical process having a complicated channel, a fine surface shape, and the like, and a method for producing the same.
[0002]
[Prior art]
A microchemical process that can react, culture, sort, purify, adsorb, analyze, etc. using a small amount of solution or sample solution, transfer fine patterns, or drive in response to microstimulation From the viewpoints of speed, accuracy, low cost, safety, environmental compatibility, and the like, attention has been paid to the development of various purposes (see, for example, Non-Patent Document 1).
In recent years, microchemical processes have come to include those called by their names, such as microreactors, microanalysis, biochips, microfiltration, micromachines, and lithography, depending on the purpose. For such a microchemical process, it has a small and complicated external shape, has a fine flow path designed to allow a small amount of liquid or gas to flow, and has a fine surface There is a need for a substrate for a microchemical process having a fine uneven pattern or the like.
As such a substrate for microchemical processing, the external shape must be processed into a shape according to the purpose, it must have a fine uneven pattern on the surface, and pressure and strain may be applied to a part of the substrate. Or, to which heating or cooling is applied, or, for example, a straight or complicated channel including a straight portion, a curved portion, a branch portion, an enlarged portion, a reduced portion, etc. Alternatively, it is necessary to have a mixer, a filter, a stop valve, a flow path changing valve, a liquid reservoir, an adsorption unit, a heating / cooling unit, and the like in the vicinity thereof as necessary.
On the other hand, a polymer gel is a three-dimensional cross-linked product of an organic polymer swollen with water or an organic solvent, and is made of a soft material (flexible material), a vibration control material, a super absorbent material, a drug release control agent, Applications such as actuators and the like have been widely studied in fields such as medical / medicine, food, civil engineering, bioengineering, and sports (for example, see Non-Patent Document 2).
However, most of the substrates for microchemical processes have so far been made of solid glass, metal, or plastic. For example, in a microreactor, fine particles of a temperature-responsive polymer gel are used as a part of the valve material. Although there was an example in which use was considered, a base material for a microchemical process using a polymer gel as a main material or one of the main materials has not been obtained. One of the reasons is that the polymer gel is a soft material, which is generally brittle and fragile. In addition, complicated flow paths including branches, curves, enlarged / reduced parts, etc. This is because it was difficult to stably form surface irregularities and external shapes. In some cases, bonding or embedding with other members cannot be performed sufficiently.
[Non-Patent Document 1] Edited by Ehrfeld, "Microreaction Technology: Industrial Products (IMRET3)", Springer, Berlin-Heidelberg (2000).
[Non-Patent Document 2] "Gel Handbook", edited by Yoshihito Nagata and Kanji Kajiwara: NTTN Corporation, 1997
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a microchemical process substrate having a fine and complicated external shape, surface irregularities, internal flow paths, internal voids and the like, and having excellent functionality and handleability, and a method for producing the same. To provide.
[0004]
[Means for Solving the Problems]
The present inventors have worked diligently to solve the above problem, and as a result, using a polymer gel obtained by polymerizing a water-soluble organic monomer in an aqueous solution in the presence of a clay mineral, a fine and complicated flow path It has been found that an excellent substrate for a microchemical process having voids, surface irregularities, external shape, and the like can be prepared, and the present invention has been completed.
That is, the present invention relates to a substrate for a microchemical process, comprising a polymer gel containing a water-swellable clay mineral, including a flow channel inside, and / or having irregularities on the surface.
The present invention also provides a method for injecting an aqueous solution containing a water-soluble organic monomer and a finely dispersed water-swellable clay mineral into one or a plurality of molds capable of molding the substrate for microchemical processing. The present invention relates to a method for producing a substrate for a microchemical process, comprising releasing a polymer gel from a template after polymerizing a reactive organic monomer to prepare a polymer gel.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The substrate for a microchemical process in the present invention is mainly composed of a polymer gel containing a water-swellable clay mineral, and is preferably one in which a water-swellable clay mineral and a polymer form a three-dimensional network. Thus, other components can also be included.
[0006]
The other components used together with the polymer gel containing the water-swellable clay mineral are not particularly limited, and one or a combination of those effective as a part of the substrate for the microchemical process is used. Specifically, for example, silica glass and quartz, silicon, copper, metals such as aluminum, metal oxides such as titania and alumina, olefin resins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, tetrafluoro Examples include fluorine resins such as ethylene, acrylic resins such as polymethyl methacrylate and polyhydroxyethyl acrylate, amide resins such as nylon 6 and nylon 66, and epoxy resins.
[0007]
The substrate for a microchemical process in the present invention preferably has a flow path including at least one portion having a shape selected from a curved shape, a branched shape, a shape having an enlarged portion and / or a reduced portion, and / or a surface. Having irregularities. Along with these shapes, those having a flow path portion having a linear shape can also be used. In particular, a substrate for a microchemical process having a portion having a shape selected from a curved shape, a branched shape, a shape having an enlarged portion and / or a reduced portion, or having a complex and fine unevenness on the outer surface is used water. Production can be made by utilizing the properties of the polymer gel containing the swellable clay mineral, that is, high toughness and strength.
[0008]
The channel formed in the substrate for microchemical process in the present invention is composed of one continuous channel, and when there is a portion having a shape having an enlarged portion and / or a reduced portion, disconnection of the enlarged portion. The ratio (a / b) of the area (a) to the cross-sectional area (b) of the minimum part is preferably 1.1 to 200, more preferably 1.5 to 150, particularly preferably 2 to 100, and most preferably 3 to 100. 50. When the ratio of (a / b) is in the above range, the effect of changing the shape of the flow channel is easily exerted, and the preparation of the substrate for a microchemical process becomes easier.
In the present invention, the size of the flow channel, the diameter of the cross section or the length of one piece from nanometer size to centimeter size, can be selected according to the purpose from a wide range, is not particularly limited, preferably, Micrometer or nanometer level of 1 mm or less.
[0009]
The substrate for a microchemical process in the present invention can be used even if its surface has irregularities. As such unevenness, the ratio of the depth / width of the concave portion or the ratio of the height / width of the convex portion is preferably 0.1 to 30, and more preferably the width of the concave portion or the convex portion is from 0.05 μm. Those having a range of 50 mm and containing one or more, preferably continuous, surface irregularities are usually used.
[0010]
The polymer gel of the present invention is a polymer gel containing a water-swellable clay mineral, and is preferably a polymer gel composed of a polymer of a water-soluble organic monomer and a water-swellable clay mineral that has been exfoliated in a layer, and Preferred is a gel formed by forming a three-dimensional network in water by interaction of both components at the molecular level. In the case of a polymer gel in which a three-dimensional network is formed using a conventional organic cross-linking agent, the polymer gel is fragile in strength, so that the polymer gel is broken or the structure of the gel surface is damaged when removing the mold or in subsequent handling. It often breaks and does not reflect the mold shape or surface irregularities. Particularly preferred is a polymer gel containing a water-swellable clay mineral prepared without using an organic crosslinking agent.
[0011]
As the water-soluble organic monomer used for the polymer gel of the present invention, those having the property of dissolving in water and having an interaction with a water-swellable clay mineral are preferable. Those having a functional group capable of forming a coordination bond, a covalent bond, or the like are preferably used. Specific examples of the water-soluble organic monomer having these functional groups include a water-soluble organic monomer having an amide group, an amino group, an ester group, a hydroxyl group, a carboxyl group, a tetramethylammonium group, a silanol group, and an epoxy group. Among them, a water-soluble organic monomer having an amide group or an ester group is preferable. In addition, the water referred to in the present invention includes not only water alone but also a mixture of an organic solvent miscible with water and water as a main component.
[0012]
Specific examples of the water-soluble organic monomer having an amide group include acrylamides such as N-alkylacrylamide, N, N-dialkylacrylamide, acrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide, and methacryl. And methacrylamides such as amides. Here, an alkyl group having 1 to 4 carbon atoms is particularly preferably selected. Specific examples of the water-soluble organic monomer having an ester group include methoxyethyl acrylate, ethoxyethyl acrylate, methoxyethyl methacrylate, and ethoxyethyl methacrylate.
[0013]
Examples of such a water-soluble organic monomer polymer include poly (N-methylacrylamide), poly (N-ethylacrylamide), poly (N-cyclopropylacrylamide), poly (N-isopropylacrylamide), and poly (acryloylmorpholine). ), Poly (methacrylamide), poly (N-methylmethacrylamide), poly (N-cyclopropylmethacrylamide), poly (N-isopropylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylaminopropylacrylamide), poly (N-methyl-N-ethylacrylamide), poly (N-methyl-N-isopropylacrylamide), poly (N-methyl-Nn-propylacrylamide), poly (N, N-diethylacrylamide), (N-acryloylpyrrolidin), poly (N-acryloylpiperidin), poly (N-acryloylmethylhomopiperadin), poly (N-acryloylmethylpiperadin), poly (acrylamide), poly (methoxyethyl acrylate) , Poly (ethoxyethyl acrylate), poly (methoxyethyl methacrylate), and poly (ethoxyethyl methacrylate).
[0014]
In addition, as the water-soluble organic monomer polymer, in addition to the polymer from the single water-soluble organic monomer as described above, a copolymer obtained by polymerizing a plurality of different water-soluble organic monomers selected from these is used. It is also effective. Further, a copolymer of the above water-soluble organic monomer and another water-soluble organic monomer or an organic solvent-soluble organic monomer may be used as long as the obtained polymer forms a complex with a water-swellable clay mineral. it can.
[0015]
The polymer of the water-soluble organic monomer in the present invention has hydrophilicity or amphipathic property having water-solubility or water-absorbing property, and among them, functions such as responding to heat, pH and light, and the like. Those having characteristics such as biocompatibility including bioabsorbability and biodegradability are more preferably used depending on applications. For example, a water-soluble organic monomer polymer having the property that the polymer physical properties (for example, hydrophilicity and hydrophobicity) in an aqueous solution are largely changed by a slight temperature change around a lower critical solution temperature (LCST). And specific examples thereof include poly (N-isopropylacrylamide) and poly (N, N-diethylacrylamide). Examples of materials having excellent biocompatibility include poly (methoxyethyl acrylate) and poly (2-hydroxyethyl methacrylate). The polymer gel of the present invention may contain a dye, a protein, a saccharide, a pharmaceutical component, an aromatic component, or the like, or may be released from the gel interface, depending on the purpose.
[0016]
The clay mineral used in the polymer gel of the present invention has water swelling properties, and preferably has the property of swelling between layers with water. More preferably, at least a part of the layered clay mineral can be exfoliated and dispersed in water, and particularly preferably, a layered clay mineral which can be exfoliated and uniformly dispersed in water in a layer having a thickness of 1 to 10 layers or less. For example, water-swellable smectite and water-swellable mica are used, and more specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, water-swellable synthetic mica, and the like. Is mentioned.
[0017]
The solvent used for the polymer gel of the present invention is water or an organic solvent, but may be a mixed solvent thereof. Further, an aqueous solution containing a salt or the like can also be used. Examples of the organic solvent include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylacetamide, dimethylformamide, dimethylsulfoxide, and a mixed solvent thereof.
[0018]
In the present invention, the polymer gel is formed by first bringing an aqueous solution containing a water-soluble organic monomer and a water-swellable clay mineral into contact with a template, and then polymerizing the water-soluble organic monomer. Next, the resulting polymer gel is released from the mold to obtain a substrate for a microchemical process in which the shape of the mold, that is, the inner flow path and the surface irregularities are formed. In addition, in order to form a polymer gel in the present invention, one or a plurality of templates are immersed in an aqueous solution containing a water-soluble organic monomer and a water-swellable viscosity mineral in an independent or connected state, and the water-soluble organic monomer is Polymer gel is prepared by polymerization. Next, by removing a part or all of the template from the generated polymer gel, a substrate for a microchemical process having a three-dimensionally complicated shape can be obtained.
[0019]
The polymerization reaction of the water-soluble organic monomer at the time of the formation of the polymer gel can be performed, for example, by radical polymerization using a conventional method such as the presence of a peroxide, heating or irradiation with ultraviolet rays. The radical polymerization initiator and the catalyst can be appropriately selected from conventional radical polymerization initiators and catalysts. Preferably, those having dispersibility in water and uniformly contained in the whole system are used. Particularly preferred is a cationic radical polymerization initiator having a strong interaction with the water-swellable clay mineral exfoliated in layers. Specifically, a water-soluble peroxide such as potassium peroxodisulfate or ammonium peroxodisulfate as a polymerization initiator, a water-soluble azo compound, for example, VA-044, V-50 manufactured by Wako Pure Chemical Industries, Ltd. V-501 and the like are preferably used. In addition, a water-soluble radical initiator having a polyethylene oxide chain is also used.
[0020]
As the catalyst, tertiary amine compounds such as N, N, N ', N'-tetramethylethylenediamine and β-dimethylaminopropionitrile are preferably used. The polymerization temperature is set in the range of 0 ° C. to 100 ° C. in accordance with the type of the water-soluble organic polymer used, the polymerization catalyst and the initiator. The polymerization time also varies depending on the polymerization conditions such as the catalyst, initiator, polymerization temperature, and amount (thickness) of the polymerization solution, and cannot be specified unconditionally.
[0021]
The ratio of the polymer of the water-soluble organic monomer and the water-swellable clay mineral constituting the polymer gel in the present invention may be such that a gel structure composed of the polymer and the clay mineral is prepared, and the water-soluble It varies depending on the type of the organic monomer and the clay mineral, and is not necessarily limited. However, since the gel synthesis is easy and the uniformity is excellent, the solid content of the polymer gel is 1 to 90 mass%. % Is preferably a water-swellable clay mineral, more preferably 3 to 70% by mass, and particularly preferably 10 to 50% by mass. When the amount is within the above range, a fine or complex shape can be easily obtained, the preparation of the polymer gel is easy, and the obtained polymer gel has excellent physical properties.
[0022]
Further, the water content of the polymer gel in the present invention can be set in a wide range, and specifically, it is preferably 30 to 99% by mass, more preferably 40 to 95% by mass, particularly preferably at the time of polymerization of the water-soluble organic monomer. 50 to 90% by mass. However, in the present invention, a polymer gel having a low water content can be obtained by drying after preparing the polymer gel. Specifically, the polymer gel has a water content of 0 to 99% by mass. Can range.
[0023]
The mold used to manufacture the substrate for microchemical processes of the present invention has various desired shapes including basic shapes such as spheres, rods, cubes, ellipses, stars and wedges. And those having surface irregularities can be selected and used. Examples of the template shape include fine particles having a size of millimeter to nanometer level, a fine wire having a spiral shape, a rod partially including different sizes, a rectangular parallelepiped having various projections, and the like. Complex shapes combined with In addition, the surface of the mold, from a smooth surface with no irregularities to fine irregularities, from a single irregularity to a pattern with irregularities in a repeated pattern, from a simple groove or depression to a complex irregularity A wide variety can be used. For example, a mold having surface irregularities in which the width of the concave portion or the convex portion is in the range of 0.05 micron to 50 mm is preferably used. For the formation of such a mold shape and surface irregularities, a mechanical cutting process, a lithography technology, a molecular self-organization technology, a morphological utilization of a natural product, and the like are selected and used. The substrate for a microchemical process obtained by contacting these molds has the characteristic that the shape and the surface irregularities almost completely reflect those of the mold and the surface irregularities.
[0024]
The template used in the present invention can be used in a state in which one or more templates are included in the aqueous solution before the reaction, in addition to bringing the entire surface or a specific surface of the template into contact with the aqueous solution before the reaction. When using multiple templates in an aqueous solution, it is possible to select the individual templates according to the purpose, or to arrange them individually. The method of connecting a plurality of molds is arbitrarily selected from known and commonly used methods such as a simple contact, a connection by screwing or pushing, a method of matching a mold, and the like. When removing these molds, they can be sequentially removed in the reverse order of assembly.
[0025]
The material of the mold used in the present invention can be selected from organic materials and inorganic materials according to the purpose, and is not particularly limited. Examples of the organic material include natural or synthetic organic polymers, crystalline or amorphous low-molecular organic compounds, organic liquids and organic gels. Examples of the inorganic material include various metals, metal oxides, carbon materials, and inorganic salts. The material of the template must be completely insoluble in water or difficult to dissolve under specific conditions.
[0026]
In the present invention, it is necessary to remove at least a part of the template after preparing the polymer gel. Methods for removing the mold from the polymer gel include removing the mold by removing it in one direction, dissolving or disassembling the mold, removing the mold, shrinking or deforming the mold before removing The method is used effectively. Here, the dissolution and decomposition of the template include immersing the polymer gel in an organic solvent miscible with water, changing the pH, heating, and irradiating light or ultrasonic waves with a specific wavelength. It is possible. In the present invention, since the polymer gel is a high-strength gel with high elasticity, for example, even in the case of a mold having deep irregularities on the surface, or in the case of a deformed rod-shaped mold having a bulging shape in the middle, It has the feature that the mold can be peeled or pulled out without breaking the gel.
[0027]
In this way, one or more molds are brought into contact with or contained in an aqueous solution, a polymer gel is synthesized, and then at least a part of those molds is removed. For microchemical processing, which has a microscopic part of the surface, and a substrate for microchemical processing, which has a flow path consisting of straight lines, curved parts, and pools (passages of voids through which liquids and gases can flow). In addition, when a plurality of molds are used in combination, it is possible to manufacture a base material for a microchemical process having a three-dimensionally complicated flow path having branches. Further, in the present invention, a polymer gel using an organic solvent as a solvent is prepared by replacing the solvent (water or a mixed solvent of water and an organic solvent) with an organic solvent after producing the polymer gel as described above. It is possible to Here, as the solvent replacement method, a method of immersing in a large amount of an organic solvent to perform solvent exchange, or a method of drying the produced polymer gel at one end and immersing it in an organic solvent is used.
[0028]
The substrate for a microchemical process in the present invention can be made to have a low solvent concentration or to be dried by drying by a conventional method and removing a part or all of the solvent. By immersing the dried product in a solvent such as water or an organic solvent, it can be regenerated into a substrate for microchemical processes having internal channels and surface irregularities. At this time, the substrate for a microchemical process containing an organic solvent can also be produced by a solvent exchange method in which a polymer gel is formed in water and then immersed in a large amount of an organic solvent.
[0029]
Thus, the microchemical process substrate has a fine and complicated external shape, surface irregularities, internal flow paths, internal voids, etc., and is excellent in functionality and handleability. It is useful for chemical processes, ie microreactors, microanalysis, biochips, microfiltration, micromachines, lithography and the like.
[0030]
【Example】
Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples described below.
[0031]
(Examples 1 and 2)
Clay minerals include [Mg_5.34Li_0.66Si₈O₂₀(OH)₄] Na_0.66 ⁺Water-swellable synthetic hectorite (trade name: Laponite XLG, manufactured by Nippon Silica Co., Ltd.) having the following composition: As a water-soluble organic monomer, N-isopropylacrylamide (NIPA: manufactured by Kojin Co., Ltd.) was recrystallized using a mixed solvent of toluene and hexane to be purified into colorless needle crystals before use.
As the polymerization initiator, potassium peroxodisulfate (KPS: manufactured by Kanto Chemical Co., Ltd.) was diluted with pure water at a ratio of KPS / water = 0.192 / 10 (g / g) and used as an aqueous solution. As the catalyst, N, N, N ', N'-tetramethylethylenediamine (TMEDA: manufactured by Kanto Chemical Co., Ltd.) was used as it was. As the water, pure water obtained by distilling ion-exchanged water was used. All water was used after removing the contained oxygen using high-purity nitrogen. 0.662 g of Laponite XLG was added to a glass container containing 18.96 g of pure water with stirring, and 2.0 g of NIPA was added thereto with stirring, and then 16 μl of TMEDA and 1.06 g of KPS aqueous solution were stirred in an ice bath. The mixture was added to obtain a colorless transparent aqueous solution. The obtained aqueous solution was glass having a line width of 120 microns and a depth of 50 microns (depth / width ratio of 0.42) in which five rows of saw-toothed patterns were formed (Example 1), a line width of 2 microns and a depth of 5 microns. Flow is performed so that the thickness becomes 1 mm on a substrate including a silicon wafer (Example 2) in which 5 rows of a rectangular parallelepiped pattern of 10 μm (depth / width ratio is 3) are formed at a line interval of 5 μm as a template. And polymerized at 20 ° C. for 15 hours. The polymer gel was peeled from the mold to obtain a polymer gel sheet having a thickness of 1 mm. The water content (mass fraction of water contained in the polymer gel) in the polymer gel was 88% by mass, and the viscosity mineral in the solid content contained in the polymer gel was 24.9% by mass. The fine shape of the obtained polymer gel in contact with the mold was examined using a scanning laser microscope (1LM15W manufactured by Lasertec Co., Ltd.). As a result, it was observed that a concavo-convex pattern corresponding to the line width and shape of the glass and silicon wafer molds was formed, and a substrate for a microchemical process using a polymer gel as a raw material was obtained. Each of the obtained substrates for microchemical processes is uniform and transparent, and is not broken by deformation even when subjected to, for example, 50% compression deformation and 100% stretching deformation, and reversibly retains its original shape. It was confirmed to return to. It was also confirmed that the surface was changed from hydrophilic to hydrophobic by contacting the surface with water at 50 ° C.
[0032]
(Example 3)
As in Example 1, except that 5.28 g of N, N-dimethylacrylamide (DMAA: Wako Pure Chemical Industries, Ltd.) was used as the water-soluble organic monomer and 0.397 g of inorganic clay was used. A colorless and transparent aqueous solution before polymerization was obtained. A 40-micron aluminum mold (height / width ratio: 16) placed on the upper surface with a gap of 400 microns in a grid pattern with a gap interval of 400 mm (a whole 15 mm square). After casting the aqueous solution to a thickness of 3 mm, polymerization was performed at 20 ° C. for 15 hours. The polymer gel was peeled from the mold to obtain a 3 mm thick sheet-like polymer gel. The water content of the polymer gel was 78% by mass, and the mass ratio of the viscous mineral in the solid content of the polymer gel was 7.0% by mass. As a result of observing the obtained polymer gel using a multiviewer system (VH5910 manufactured by KEYENCE CORPORATION), it was observed that a regular concave portion having a size of 40 μm and a depth of 640 μm was prepared. Was obtained as a substrate for microchemical processes. The obtained substrate for microchemical processing is uniform and transparent, and does not break due to deformation even when subjected to, for example, 50% compression deformation and 200% stretching deformation, and reversibly returns to its original shape. It was confirmed that. In addition, even when the surface was brought into contact with water at 50 ° C., the surface did not become hydrophobic and showed hydrophilicity.
[0033]
(Example 4)
Four differently shaped aluminum bar molds (the surface is smooth) shown in FIG. 1 (the ratio (a / b) of the cross-sectional area a of the enlarged portion to the cross-sectional area b of the minimum portion is 25) are directed vertically. An aqueous solution prepared in the same manner as in Example 1 was placed in a container having a side of 50 mm and a height of 60 mm held at regular intervals, and then kept at 20 ° C. for 15 hours to carry out polymerization. Thereafter, the polymer gel was taken out of the container, and the rod mold was slowly pulled upward. The polymer gel obtained is deformed during the removal of the rod mold, but is not destroyed, and is made of a polymer gel having voids (channels) having the same shape and surface smoothness as the rod mold after removal. The substrate for microchemical process was obtained. The obtained substrate for microchemical processing is uniform and transparent, and does not break due to deformation even when subjected to, for example, 50% compression deformation and 300% stretching deformation, and reversibly returns to its original shape. It was confirmed that. In addition, it was confirmed that by alternately flowing water at 50 ° C. and 20 ° C. through the flow channel, the inner wall surface of the flow channel alternately changed to hydrophobic and hydrophilic.
[0034]
(Example 5)
An aluminum bar mold having the same shape as that of FIG. 1 except that the diameter of the details is 0.9 mm (the surface is smooth) (ratio (b / a) of the cross-sectional area a of the minimum part to the cross-sectional area b of the enlarged part). A polymer gel was produced in the same manner as in Example 4 except that No. 123) was used, and an aqueous solution prepared in the same manner as in Example 3 was used. Thereafter, the polymer gel was taken out of the container, and the rod mold was slowly pulled upward. The polymer gel obtained is deformed during the removal of the rod mold, but is not destroyed, and is made of a polymer gel having voids (channels) having the same shape and surface smoothness as the rod mold after removal. The substrate for microchemical process was obtained. The obtained substrate for microchemical processing is uniform and transparent, and does not break due to deformation even when subjected to, for example, 50% compression deformation and 300% stretching deformation, and reversibly returns to its original shape. It was confirmed that. Further, when an aqueous solution containing methylene blue was allowed to flow through the flow channel, it was observed that methylene blue was adsorbed on the wall surface of the flow channel.
[0035]
(Example 6)
Includes a mold composed of a combination of an aluminum rod (diameter 2 mm and maximum diameter 9 mm) and a hollow Y-shape (inner diameter 1 mm: the end is covered with a connecting rod) shaped as shown in FIG. A polymer gel was produced in the same manner as in Example 4 except that a container having a side of 60 mm was used. The aqueous solution was put in a container containing a mold, kept at 20 ° C. for 15 hours, and after polymerization was carried out, a rod constituting the mold was pulled out in its length direction, and all the molds except for the Y-shaped hollow mold were removed. . For microchemical processes using polymer gel as a raw material, which has a hollow aluminum channel in the center and has a three-dimensional void channel connected to it, after the mold is deformed but not destroyed during the removal of the mold. A substrate was obtained. The obtained substrate for a microchemical process is uniform and transparent, and does not break due to deformation even when subjected to, for example, 50% compression deformation and 300% stretching deformation, and reversibly returns to its original shape. It was confirmed that. Further, by flowing different liquids (hexane and heptane) from the upper part (A, B) of the flow path, they are mixed in the flow path, and the mixed liquid is discharged to the lower part (C, D) of the flow path. Was observed.
[0036]
(Comparative Example 1)
The aqueous solution prepared in the same manner as in Example 1 was poured into a glass plate having a thickness of 5 mm and kept at 20 ° C. for 15 hours to obtain a polymer gel having a thickness of 5 mm. An attempt was made to cut the surface using a cutter knife or the like so as to have a shape similar to that of the polymer gel obtained in Example 3, but one having a shape similar to the polymer gel of Example 3 was not used. It was not obtained, and the intended substrate for microchemical processes was not obtained.
[0037]
(Comparative Example 2)
The procedure was performed in the same manner as in Example 4 except that N, N'-methylenebisacrylamide (manufactured by Kanto Chemical Co., Ltd.), which is an organic crosslinking agent, was used at 1 mol% of a water-soluble organic monomer (DMAA) without using a clay mineral. Thus, a polymer gel was produced. When the template was pulled out from the obtained polymer gel, the gel was broken, and a gel having a flow path reflecting the shape of the template was not obtained, so that the gel could not be used as a substrate for a microchemical process.
[0038]
【The invention's effect】
The substrate for a microchemical process obtained by the present invention has three-dimensional complicated fine channels, fine surface irregularities and shapes, and has handleability, mechanical deformation resistance (compressibility and stretchability) and It has features such as excellent transparency. In addition, for example, by changing the temperature of the flowing liquid, the surface property of the channel can be reversibly changed from hydrophilic to hydrophobic, or a specific (for example, cationic) contained in the flowing liquid. ) The solute can be adsorbed to the substrate from the wall surface and removed.
Further, the substrate for a microchemical process in the present invention is used in a reaction experiment system using a minute reaction solution, a chemical or biochemical analysis system, and a purification, adsorption, and separation system of a minute solution. In addition, those with fine surface irregularities and those containing precise shaped cavities and heterogeneous components inside are used as soft lithography materials suitable for micromachining and as tissue culture substrates with shape control at the micron level, In addition, it can be used as a base material for various microchemical processes, such as a micromachine member or a microvibration control member that is driven in response to a microstimulus.
[Brief description of the drawings]
FIG. 1 is a view showing an aluminum bar mold used in Example 4.
FIG. 2 is a view showing an aluminum bar mold used in Example 6.

Claims (10)

A base material for a microchemical process, comprising a polymer gel containing a water-swellable clay mineral, including a flow channel inside, and / or having irregularities on the surface. The substrate for a microchemical process according to claim 1, wherein the flow path includes at least a part of a shape selected from a curved shape, a branched shape, and a shape having an enlarged portion and / or a reduced portion. The flow path has a portion having a shape having an enlarged portion and / or a reduced portion, and a ratio (a / b) of a sectional area (a) of the enlarged portion to a sectional area (b) of the minimum portion is 1.1 to 200. The substrate for a microchemical process according to claim 2, which is: The polymer gel according to any one of claims 1 to 3, comprising a polymer gel having one or more surface irregularities having a depth / width ratio of the concave portion or a height / width ratio of the convex portion of 0.1 to 30. Substrate for micro chemical process. The substrate for a microchemical process according to any one of claims 1 to 4, wherein 1 to 90% by mass of the solid content constituting the polymer gel is a water-swellable clay mineral. The substrate for a microchemical process according to any one of claims 1 to 5, wherein the polymer of the water-soluble organic monomer constituting the polymer gel has an amide group or an ester group. An aqueous solution containing a water-soluble organic monomer and a finely dispersed water-swellable clay mineral is injected into one or more molds capable of forming the microchemical process substrate according to claim 1, A method for producing a substrate for a microchemical process, comprising: after polymerizing an organic monomer to prepare a polymer gel, releasing the polymer gel from the template. An aqueous solution containing a water-soluble organic monomer and a finely dispersed water-swellable clay mineral is poured into a mold having concaves and convexes having a surface unevenness in the range of 0.05 μm to 50 mm, and the water-soluble organic monomer is polymerized. A method for producing a substrate for a microchemical process, comprising: releasing a polymer gel from a template after preparing the polymer gel by performing the method. 9. The method for producing a substrate for a microchemical process according to claim 7, wherein 1 to 90% by mass of the solid content constituting the polymer gel is a water-swellable clay mineral. The method for producing a substrate for a microchemical process according to any one of claims 7 to 9, wherein the polymer of the water-soluble organic monomer constituting the polymer gel has an amide group or an ester group.

Images