JP2000262871A - Microporous membrane separation device and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a micro-chemical device having, incorporated therein, an extremely microporous membrane usable as a filter device, a light-liquid separation device, a diaphragm gas dissolving device, a diaphragm degassing device or a gas vent, having a simple shape, and being easy to produce. SOLUTION: A micro-filter device has a partition wall 18 comprising an open-porous member deviding a recessed part 12' formed in the surface of a base material 11 into a plurality of parts within the plane parallel to the surface of the base material 11 or the partition wall 18 comprising the open-porous member dividing the gap parts with specific thickness in the base material into a plurality of parts in a width direction. This device is produced by a method wherein the recessed parts formed on the surface of the base material 11 or the gap parts in the base material are filled with a comps. for forming the open-porous member by the irradiation with active rays and the partition wall part thereof is irradiated with active rays to form the partition wall of the open-porous member and the uncured compsn. is removed or the recessed parts of the surface of the base material or the gap parts in the base material are filled with the active ray curable compsn. and the partition wall part thereof is irradiated with active rays excepting the parts becoming the pores of the partition wall to form the partition wall having slit-like or capillary tube-like pores and the uncured compsn. is removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to synthesis, analysis, and the like in the fields of chemistry, biochemistry, medicine, food, pharmaceuticals, and the environment.
More specifically, the present invention relates to a micro-membrane separation device used for purification, recovery, concentration, etc. and a method for producing the same. Liquid-liquid separation, liquid degassing (including devolatilization),
The present invention relates to a minute device having a membrane separation mechanism and a vent mechanism that can be used for applications such as gas dissolution in a liquid, dissolution of a liquid in a liquid, dispersion of a liquid in a liquid, and membrane distillation, and a method of manufacturing the same.

[0002]

2. Description of the Related Art As a microdialysis device incorporating a dialysis membrane, "Analytical Chemistry", Vol. 70, p. 3553 (1998) discloses two planar substrates each having a groove. A microdialysis device in which a dialysis membrane is interposed between the devices has been reported.

However, there is no known example in which a filtration membrane is incorporated in a microchemical device, and a microchemical device provided with a micro-liquid-liquid separation mechanism, a micro-diaphragm gas dissolving mechanism, a micro-diaphragm deaeration mechanism, and a micro-gas vent mechanism. No chemical device is known.

[0004]

By replacing the dialysis membrane of the above-mentioned prior art with a porous membrane, a membrane separation mechanism such as a filtration mechanism, a liquid-liquid separation mechanism, a membrane gas dissolution mechanism, a membrane deaeration mechanism, and a gas vent mechanism. Although it is possible to construct a device having a membrane separation device, it is necessary to hold the membrane in a wide range between the substrates even when a very small membrane separation device is required, and when the membrane is a porous membrane, Unlike dialysis membranes, liquid spreads through the membrane and infiltrates the entire membrane, making it difficult to filter a small amount of liquid.It is quite difficult to adhere a micromembrane to a predetermined position. It is difficult to configure a device integrated with the analysis device. There was a problem.

The problem to be solved by the present invention is to provide a filtration device, a liquid-liquid separation device, a diaphragm gas dissolving device,
It is an object of the present invention to provide a microchemical device incorporating a microporous membrane which can be used as a diaphragm degassing device, a gas vent, and the like, has a simple shape, is easy to manufacture, and a manufacturing method thereof. An object of the present invention is to provide a micromembrane separation device in which a membrane separation mechanism is formed on a substrate, and a method for manufacturing the same.

[0006]

Means for Solving the Problems The present inventors have intensively studied a fine filtration mechanism and a method for forming the same on a single substrate without laminating a porous membrane and a member, and as a result, have found that an energy ray The present inventors have found that the above problem can be solved by using a method of forming a porous body using a cured resin, and have completed the present invention.

That is, according to the present invention, in order to solve the above-mentioned problems, (I) a concave portion is formed on a surface of a substrate, and the concave portion is formed on a plurality of portions in a plane parallel to the surface of the substrate by partition walls. Provided is a micro-membrane separation device (hereinafter, referred to as a first micro-membrane separation device of the present invention) that is divided and the partition walls are formed of a communicating porous body.

In order to solve the above problems, the present invention provides (II) a recess having a depth of 0.01 to 3 mm,
A micromembrane separation device according to the above (I), wherein the width of the partition wall is in the range of 0.01 to 3 mm.

According to another aspect of the present invention, there is provided: (III) a recess having an inflow port on one side of a partition;
A micromembrane separation device according to the above (I) or (II), which has an outlet on the other side of the partition.

In order to solve the above-mentioned problems, the present invention provides (IV) the above-mentioned (I), (II) or (II) wherein the recess has an inlet and an outlet on one side of the partition wall. (I
(II) A micromembrane separation device according to (1).

Further, in order to solve the above-mentioned problems, the present invention provides (V) the communicating porous body constituting the partition wall, wherein the communication porous body is an aggregate of a plurality of groove-like pores penetrating the partition wall. (I
A micromembrane separation device according to (I), (III) or (IV) is provided.

Further, according to the present invention, in order to solve the above-mentioned problems, (VI) the base material is a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, a polyester polymer. And a polymer selected from the group consisting of vinyl chloride-based polymers and the micromembrane separation device according to any one of the above (I) to (V).

In order to solve the above-mentioned problems, the present invention provides: (VII) a cross-linked polymer selected from the group consisting of a (meth) acrylic cross-linked polymer and a maleimide cross-linked polymer. The present invention provides the micromembrane separation device according to any one of the above (I) to (VI), which is a formed porous body.

According to the present invention, in order to solve the above-mentioned problems, (VIII) a gap having an inlet and an outlet is formed inside the substrate, and the gap separates the inlet and the outlet. Partitioned by a partition wall having a height of 0.01 to 3 mm and a thickness of 0.01 to 3 mm, the partition wall is a micromembrane separation device made of a communicating porous material (hereinafter referred to as a second micromembrane separation device of the present invention). .)I will provide a.

In order to solve the above-mentioned problems, the present invention provides (IX) the above-mentioned (VII), wherein the void portion further has a primary-side outlet on the inlet side divided by the partition.
A micromembrane separation device according to I) is provided.

Further, in order to solve the above-mentioned problems, the present invention provides (X) a structure in which the communicating porous body constituting the partition is an aggregate of a plurality of capillary tubes and / or slit-like pores penetrating the partition. A micromembrane separation device according to (VIII) or (IX) is provided.

In order to solve the above-mentioned problems, the present invention provides (XI) a base material having a void having an inlet and an outlet, wherein a solid substance is provided between the member (A) and the member (B). The solid material has a depth of 0% as viewed from a direction perpendicular to the contact surface between the member (A) and the member (B) as a defective portion of the solid substance.
A substrate in which a void portion in the range of 01 to 3 mm is formed,
Alternatively, a member (A) having a concave portion on its surface and a member (A)
When the member (B) is brought into close contact with the concave portion forming surface, a gap portion having a depth in the range of 0.01 to 3 mm as viewed from a direction perpendicular to the contact surface between the member (A) and the member (B) is formed. A micromembrane separation device according to the above (VIII), (IX) or (X), which is a substrate that has been prepared.

In order to solve the above-mentioned problems, the present invention provides: (XII) a member (A) and a member (B) each comprising a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer and a polysulfone; The micromembrane separation device according to the above (XI), which is a substrate formed of a polymer selected from the group consisting of a system polymer, a polyester polymer, and a vinyl chloride polymer.

In order to solve the above-mentioned problems, the present invention provides (XIII) a crosslinked polymer selected from the group consisting of a (meth) acrylic crosslinked polymer and a maleimide crosslinked polymer. The micromembrane separation device according to any one of the above (VIII) to (XII), which is a formed porous body.

Further, the present invention provides: (XIV) (1) an energy-ray-curable compound (a) and an energy-ray-curable compound (a) in a concave portion provided on the surface of a substrate. a first step of filling an energy ray-curable composition (C) containing a phase separator (b) which is compatible with a) but does not dissolve or swell the cured product of the energy ray-curable compound (a) And (2) irradiating a part to be a partition which divides the concave portion into a plurality of parts with an energy ray to cure the energy ray-curable compound (a), thereby forming a partition made of a communicating porous body. A step of removing the uncured energy-ray-curable composition (C), and (3) a step of removing the uncured energy-ray-curable composition (C). A partition that divides the concave portion into a plurality of portions, wherein the partition has a communicating pore; Method for manufacturing micromembrane separation device made of porous body (hereinafter referred to as i-th manufacturing method of the present invention)
I will provide a.

In order to solve the above-mentioned problems, the present invention provides an energy ray-curable compound containing an energy ray-curable compound (a ') in a concave portion provided on the surface of (XV) (1') substrate. A first 'step of filling the composition (D), (2')
In the concave portion filled with the energy ray-curable composition (D), a thickness of 0.01 to 3 dividing the concave portion into a plurality of portions.
A part to be a partition wall of mm is irradiated with an energy beam except for a part to be a plurality of capillaries and / or slits penetrating the partition wall, and the energy ray-curable composition (D) is cured to form a plurality of grooves. A 2 ′ step of forming a partition wall composed of a communicating porous body composed of a plurality of pores, and (3 ′) a 3 ′ step of removing an uncured energy ray-curable composition (D). A concave portion is provided on the surface of the substrate, and the concave portion has a partition that divides the concave portion into a plurality of portions in a plane parallel to the surface of the substrate, and the partition has a plurality of groove-like shapes penetrating the partition. Provided is a method for producing a micromembrane separation device comprising a communicating porous body composed of fine pores (hereinafter, referred to as a second production method of the present invention).

In order to solve the above-mentioned problems, the present invention provides (XVI) an energy ray-curable compound (a ′),
A method for producing a micromembrane separation device according to the above (XV), which is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group.

In order to solve the above-mentioned problems, the present invention provides (XVII) (1 ") a method of forming an energy ray-curable compound (a) in a void having an inlet and an outlet provided inside a substrate. And a phase separator (b) that is compatible with the energy ray-curable compound (a) but does not dissolve or swell the cured product of the energy ray-curable compound (a). A first "step of filling (C),
(2 ″) In the gap filled with the energy ray-curable composition (C), the energy ray-curable compound (a) is irradiated by irradiating an energy ray to a part serving as a partition separating the inflow port and the outflow port. And an inflow port comprising a 2 "step of forming a partition formed of a communicating porous body by curing the composition and (3") a 3 "step of removing an uncured energy ray-curable composition (C). A method of manufacturing a micromembrane separation device comprising a porous body and having a partition wall between an inlet and an outlet in a void portion of a substrate having an outlet port (hereinafter referred to as a third manufacturing method of the present invention) Is provided.)

According to another aspect of the present invention, there is provided (XVIII) a base material having a void having an inlet and an outlet, wherein a solid substance is provided between the member (A) and the member (B). A base material which is filled and has a void portion as a deficient portion of the solid substance, or a member (A) having a concave portion on its surface and a member (B) adhered to the concave portion forming surface of the member (A) ) The method for producing a micromembrane separation device according to the above (XVII), which is a substrate comprising:

In order to solve the above problems, the present invention provides (XIX) wherein the energy ray-curable compound (a) is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group. A method for manufacturing the micromembrane separation device described above is provided.

In order to solve the above-mentioned problems, the present invention provides an energy ray-curable compound (XX) in a space having an inflow port and an outflow port provided inside a (XX) (1 ″ ′) substrate. a ′), a first step of filling the energy ray-curable composition (D) containing (a ′), (2 ″ ′) an inflow port in the gap filled with the energy ray-curable composition (D) In the part which becomes the partition of thickness 0.01-3 mm separating the outlet,
Except for a portion that becomes a plurality of capillaries and / or slits penetrating the partition wall, the energy ray is irradiated to cure the energy ray-curable composition (D), and a plurality of capillaries and / or
Alternatively, a second “″” step of forming a partition made of a communicating porous body composed of slits, and a (3 ″ ”) third step of removing the uncured energy ray-curable composition (D). Consisting of the steps, formed in the inside of the base material, in the void portion having an inflow port and an outflow port, having a partition separating the inflow port and the outflow port,
The present invention provides a method for producing a micromembrane separation device (hereinafter referred to as an iv production method of the present invention) comprising a communicating porous body in which the partition walls are constituted by a plurality of capillaries and / or slits penetrating the partition wall.

In order to solve the above-mentioned problems, the present invention provides: (XXI) an energy ray-curable compound (a ′)
A method for producing a micromembrane separation device according to the above (XX), which is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group.

According to another aspect of the present invention, there is provided (XXII) a base material having a void having an inlet and an outlet, wherein a solid substance is provided between the member (A) and the member (B). A base material which is filled and has a void portion as a deficient portion of the solid substance, or a member (A) having a concave portion on its surface and a member (B) adhered to the concave portion forming surface of the member (A) The present invention provides a method for producing a micromembrane separation device according to the above (XXI), which is a substrate comprising:

In order to solve the above problems, the present invention provides: (XXIII) an energy ray-curable compound (a ′)
The method for producing a micromembrane separation device according to the above (XXII), which is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group, is provided.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION A first micromembrane separation device of the present invention (hereinafter, "micromembrane separation device" is simply referred to as "device")
May be abbreviated. The shape of the substrate used for
There is no particular limitation, and it can take a shape according to the purpose of use. The shape of the substrate is, for example, a film shape (including a sheet shape, a ribbon shape, etc .; the same applies hereinafter), a plate shape, a coating film shape, a rod shape, a tubular shape,
It can be a cylindrical or other complicated shaped product,
It is preferably in the form of a film or a plate from the viewpoint of easy integration with other devices and ease of molding. Further, the base material may be in a form integrated with another support. When the substrate is in the form of a coating film, it is used in a state of being integrated with the support. The shape of the support is the same as that described for the substrate. A plurality of microchemical devices can be formed on a single base material, or they can be cut into a plurality of devices after manufacturing.

The material of the base material is arbitrary, and may be, for example, an organic high molecular polymer (hereinafter, simply referred to as “polymer”), glass, ceramic, metal, semiconductor or the like. From the viewpoint, it is preferably a polymer. The polymer used for the base material may be a thermoplastic polymer or a thermosetting polymer, and may be a thermoplastic polymer having good moldability or an energy ray-curable polymer having a high curing rate. Coalescence is preferred. The energy ray-curable polymer is preferably a crosslinked polymer. The substrate may be composed of a polymer blend or a polymer alloy, or may be a laminate.

Examples of the polymer preferably usable for the substrate include styrene polymers such as polystyrene, high-impact polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, and polystyrene / acrylonitrile copolymer; Polysulfone polymers such as porsulfone and polyethersulfone; poly (meth) acrylate polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide polymers;
Polycarbonate polymer; Cellulose polymer such as cellulose acetate and methyl cellulose; Polyurethane polymer; Chlorine-containing polymer such as vinyl chloride and vinylidene chloride; Polyamide polymer; Polyimide polymer; Polyolefin such as polyethylene and polypropylene Polymer; polyether-based or polythioether-based polymers such as polyphenylene oxide and polyphenylene sulfide; and polyester-based polymers such as polyethylene terephthalate and polyarylate.

The energy ray-curable polymer usable for the substrate is preferably a cured product of an energy ray-curable compound having a (meth) acryloyl group or a cured product of an energy ray-curable compound having a maleimide group. . Of course,
The polymer may be a homopolymer or a copolymer.
Among these, styrene-based polymers, (meth) acrylic-based polymers, polycarbonate-based polymers, and polysulfone-based polymers are inexpensive, have good moldability, and have excellent physical properties such as water resistance and dimensional stability. It is particularly suitable as a material for a substrate used in the micromembrane separation device of the present invention because of its good adhesion to the communicating porous body.

The substrate used in the first device of the present invention has a concave portion on its surface. The dimensions and shape of the recesses are arbitrary, and suitable dimensions and
Although the shape can be designed, the depth of the concave portion is preferably 0.01 to 3 mm. When the depth of the concave portion is less than 0.01 mm, the filtration rate tends to decrease. Therefore, it is not preferable. When the depth of the concave portion is more than 3 mm, it becomes difficult to form the partition walls and the effect of the present invention. Is undesirably small. The shape of the concave portion as viewed from a direction perpendicular to the surface of the base material is arbitrary, and may be a rectangle (including a rectangle with rounded corners.
The same applies hereinafter), a circle, a radial shape, a zigzag shape, a comb shape, and the like. The dimension of the concave portion as viewed from the direction perpendicular to the surface of the substrate is also arbitrary, but the area is preferably 1 × 10 ⁻¹² m ² or more, more preferably 1 × 10 ⁻⁸ m ² or more. .
Further, it is preferably 1 × 10 ^-2 m ² or less, and 1 × 1
More preferably, it is 0 ^-4 m ² or less. If the area is smaller than this, the application is extremely limited. If the area is larger than this, the device becomes large and the effect of the present invention is impaired.

The method of forming the concave portion on the surface of the base material is arbitrary. For example, injection molding, solvent casting, melt replica method, cutting, etching, photolithography (including energy ray lithography, the same applies hereinafter), etching method, A method such as a vapor deposition method, a gas phase polymerization method, and a method of bonding a sheet-like member and a plate-like member cut out from a portion to be a concave portion can be used. The substrate may be composed of a plurality of materials,
For example, the bottom and side surfaces of the recess may be formed of different materials. Further, the whole or a part of the concave portion may be surface-treated. The substrate may be provided with a structural portion other than the concave portion, for example, a structure serving as a liquid storage tank, a reaction tank, an analysis mechanism, or the like.

In the recess provided in the base material, a partition-like communicating porous body (hereinafter, referred to as a partition) which divides the recess into a plurality of recesses.
“Communication porous body” may be simply abbreviated as “porous body”. Also, the “communicating porous body part” is simply called “porous part”.
May be abbreviated. ) Is formed. That is,
Due to the partition wall composed of the porous body, the concave portion is formed between the primary side (also referred to as the undiluted solution side) and the secondary side in a plane parallel to the surface of the base material.
It is separated on the next side (also called the filtrate side), and the fluid can pass through the porous portion in a direction parallel to the surface of the substrate from the primary side to the secondary side of the recess.

The porous body is not particularly limited as long as its pores communicate from the primary side to the secondary side and can transmit a fluid. The pore shape of the porous body is arbitrary. For example, the porous body is formed in the form of a sintered body (agglomerated particles), spongy (three-dimensional network), filter paper, a nonwoven fabric, a woven fabric, a gap between bundled fibers, or in parallel. A plurality of grooves, a plurality of capillaries and slits formed in parallel. A plurality of grooves, capillaries, or slits formed in parallel (hereinafter, these "grooves, capillaries, or slits" are referred to as "capillaries, etc."
In some cases. ) May be generally parallel formed capillaries or the like, or may be capillaries crossed or connected to each other. For example, a two-dimensional lattice, a plurality of generally parallel shapes crossed in an X shape, a distorted 2 It may be a two-dimensional grid or two-dimensional mesh. When the pore size of the porous body is relatively large, the porous body is preferably a negative groove, a capillary, or a slit formed in parallel. Here, the groove having a groove shape is a structure that can be adopted when the partition wall is formed in the concave portion and the upper portion is opened. When the cover is attached to the surface of the groove-like pore, the pore becomes a capillary or a slit-like pore. Also, a slit refers to a capillary tube having a large aspect / width ratio in cross section.

The pore diameter of the pores of the porous portion and the diameter of the capillary and the like are arbitrary, and a suitable value can be selected depending on the purpose of use, but the average pore diameter is preferably 0.4 μm or more, more preferably 1 μm or more. It is preferably 100 μm or less, more preferably 20 μm or less. When the porous body is in the form of a sintered body (agglomerated particles) or spongy (three-dimensional network), the average pore size is preferably in the range of 0.4 to 5 μm, which is important for ease of production and strength. It is preferable from the viewpoint. When the porous body is an aggregate such as a capillary formed in parallel, it is preferable that the average pore diameter is in the range of 1 to 20 μm from the viewpoint of ease of production, strength and the like. When the porous body is an aggregate of slits formed in parallel, it is preferable that the slit width is in the range of 1 to 20 μm from the viewpoint of ease of production, strength, and the like.

The average diameter of the pores of the porous body and the diameter of the capillaries and the like refer to the diameters of circular tubes having the same sectional area. In the case of a slit, it refers to the diameter of a circular tube having the same cross-sectional area as the cross-sectional area of the slit. However, when the porous body has a large vertical / horizontal ratio of the cross-sectional shape of the pores like a slit, the minor axis (slit width) is preferably in these ranges. If the average pore size is too small, the production will be difficult, and the permeation rate will decrease. If the average pore size is too large, the separation function will be poor.

The thickness of the partition walls as seen from the direction perpendicular to the surface of the substrate, that is, the thickness of the porous body is arbitrary,
A range of 3 mm is preferred, and a range of 0.1 to 1 mm is particularly preferred. When the thickness of the partition wall made of a porous body is less than 0.01 mm, it tends to be difficult to form a partition wall made of a communicating porous body, and when the thickness of the partition wall is more than 3 mm, the filtration rate tends to decrease. Is not preferred. The length of the partition seen from the direction perpendicular to the surface of the substrate is arbitrary, and can be arbitrarily designed according to the required filtration area. The pattern of the partition seen from the direction perpendicular to the surface of the substrate is arbitrary, and may be, for example, linear, annular, comb-shaped, spiral, multiple spiral, meandering, and the like. The dimension of the partition wall in the depth direction of the substrate is preferably from the bottom of the concave portion to the surface of the substrate or higher than that. When a cover or another member is used in close contact with the substrate, the cover or the like is used. So that there is no gap between
It is preferable to be formed slightly higher than the substrate surface.
In addition. It is not necessary that the entire partition is a porous body. For example, a non-porous body portion such as a reinforcing portion for giving pressure resistance to the partition may be formed.

The concave portions divided by the partition walls are primary and secondary concave portions. Seen from the direction perpendicular to the surface of the substrate, the shape of these recesses is arbitrary, and may be a groove, a rectangle, a semicircle, a groove, or the like, but is preferably a groove, and the groove is
It can be straight, radial, spiral, zigzag, comb-like, and the like. In order to increase the filtration area, the groove is preferably spiral or comb-shaped.

It is also possible to provide an inlet to the recess in the recess on one side of the partition and an outlet from the recess on the other side of the partition.
The range of uses and methods of use are wide, and it is desirable. The way of providing the inflow port and the outflow port is arbitrary. For example, the flow path may be a groove-shaped flow path provided in the base material connected to the concave portion, or a hole formed in the base material. . When the cover is placed over the concave portion of the base material, the cover may be provided with an inlet and an outlet. The inflow port and the outflow port may be connected to the outside of the substrate, or other structural parts formed on the same substrate as the micromembrane separation device of the present invention or the substrate laminated on the device, for example, It may be connected to a storage tank, a reaction tank, an analysis mechanism, or the like.

When the first device of the present invention is used for filtration, the above-mentioned inlet and outlet are used as a primary (stock solution) inlet and a secondary (filtrate) outlet, respectively. can do. It is also preferable that a primary side outlet is further connected to the recess at the side of the partition wall where the inlet is formed. By providing the primary outlet, not only the total filtration method but also other membrane separation methods, for example, an ultrafiltration method (a method in which a part of the undiluted solution is filtered), a liquid-liquid separation such as oil-water separation, and a liquid It can be used for purposes such as dissolving and dispersing a liquid therein, degassing, and supplying air.

The material of the porous body may be, for example, a polymer, glass, crystal, metal, carbon, etc., but is preferably a polymer, more preferably a polymer comprising an energy ray-curable compound, It is more preferably a crosslinked polymer composed of a line-curable compound, further preferably a crosslinked polymer of a compound having a polymerizable carbon-carbon double bond, and a (meth) acrylic crosslinked polymer and / or Most preferably, it is a maleimide-based crosslinked polymer. By using these materials, a minute porous portion can be easily formed without cutting and pasting, and a micromembrane separation device can be manufactured with high productivity.

The porous body preferably has a hydrophilic surface when it is used for filtration, and has a hydrophobic surface when it is used for liquid-liquid separation, degassing, and air supply. It is preferable to have The control of the hydrophilicity and hydrophobicity of the porous surface can be carried out by selecting a porous material, performing a surface treatment, and applying a surfactant or a water repellent.

It is also preferred that the first device of the present invention be used with the cover in close contact with the surface on the concave side. In addition,
The term "close contact" as used in the present invention means that the contact is air-tight or liquid-tight, and includes non-adhesive contact, adhesion and adhesion. Needless to say, the adhesion or the adhesion may be a contact through an adhesive or an adhesive. By closely attaching the cover, a usage method involving pressure filtration and reduced pressure can be performed. The cover may have an inlet, an outlet, and other structures. First of the present invention
The device in which the cover is in close contact with the device of
Is a kind of micro-membrane separation device.

The first device of the present invention can be connected to form other functional parts, for example, a liquid holding part such as a liquid storage tank or a reaction tank. Outlet, an electrophoresis column, an electrode, a chromatographic column, and the like. These may be provided on a common substrate with the device of the present invention, or may be provided on the cover, and may be superimposed on the cover or on the opposite side of the substrate. It may be provided on one or more other substrates.

The second micromembrane filtration device of the present invention has a partition wall separating the inflow port and the outflow port in the gap portion of the base material having the gap portion having the inflow port and the outflow port. Is composed of a communicating porous body.

The shape of the substrate is the same as the shape of the substrate of the first device of the present invention except that the substrate has a cavity inside instead of having a concave portion on the surface.

The height of the gap is preferably in the range of 0.01 to 3 mm, assuming that the dimension in the direction of the height of the partition wall is the height of the gap among the vertical, horizontal, and height dimensions. If the height of the voids is lower than this, the filtration rate tends to decrease, which is not preferable.If the height of the voids is higher than this, it becomes difficult to form the partition walls, and the effect of the present invention is reduced. It is not preferable because it tends to be small. The vertical and horizontal dimensions of the void are the same as those described in the first device of the present invention regarding the dimensions of the concave portion as viewed from a direction perpendicular to the surface of the substrate.

The shape of the space is arbitrary, and
Similar to the shape of the concave portion in the device, the shape can be designed to be more suitable for the application field. In addition, the shape of each of the gaps divided by the partition is the same as the description of the shape of each of the recesses divided by the partition in the first device of the present invention.

The base material is composed of a member (A) and a member (B) which are in close contact with each other, and a gap is formed between the member (A) and the member (B).
It is preferable that it is formed between. In this case, for example, (a) the gap between the member (A) and the member (B)
The solid material may be filled in portions other than the voids. For example, another member (B) may be formed on the surface of the member (A) having the concave portion on the surface (B). It may be formed in close contact. The space in (a) above is composed of the member (A) on the bottom surface when the member (B) is up, a solid substance filled on the side surface, and the member (B) on the top surface. The gap in () has a bottom surface and side surfaces formed of the member (A), and a top surface formed of the member (B) or an adhesive applied to the member (B).

In the case where the gap is formed between the member (A) and the member (B) which are in close contact with each other, the height direction of the gap is defined by the members (A) and (B). It is preferable that the direction is perpendicular to the close contact surface because the production is easy. In this case, the size and shape of the first device of the present invention as viewed from the direction perpendicular to the contact surface between the member (A) and the member (B) are the same as those of the concave portion as viewed from the direction perpendicular to the substrate surface.・ Same as shape.

In the case where the gap is formed by filling a portion other than the gap between the member (A) and the member (B) with the solid substance, the thickness of the solid substance is not necessarily uniform. Although it is not, it is preferable that it is uniform. The gap is
When the member (A) having the concave portion on the surface is formed by adhering another member (B) to the surface having the concave portion, the concave portion may be formed as a so-called concave portion lower than its peripheral portion. , May be formed as a space surrounded by a wall standing on the surface of the member (A). The depth of the recess need not be constant.

Among the close contacts, the non-adhesive contacts may be in a state of being fixed by, for example, a clamp, a screw, a rivet, or the like. Adhesion is performed by using a solvent type adhesive, using a solventless type adhesive, using a melting type adhesive, bonding by applying a solvent to the surface of the member (A) and / or the member (B), and melting by heat or ultrasonic waves. Wearing or the like may be used. Among these, it is preferable to use a solventless adhesive. As a solventless adhesive, a method of using an energy ray-curable resin, curing by energy beam irradiation and bonding, is a method of precisely bonding a minute device. This is preferable because of high productivity and high productivity. Further, it is also possible to adopt a method in which the protection material is adhered in a state in which the recess is filled with the protection material, and then the protection material is removed. The member (B) may be a cured product of the adhesive itself.

The shape of the member (A) does not need to be particularly limited, and may take a shape according to the purpose of use. This is the same as for the substrate of the first device of the present invention. When the member (A) has a concave portion on the surface, it is preferable that the surface on which the concave portion is formed has a planar shape.

When the member (A) is a member having a concave portion on the surface, the method of providing the concave portion on the surface of the member (A) is arbitrary, and the concave portion is formed on the surface of the base material in the first device of the present invention. This is the same as the description on the method of providing.

The member (B) is filled with a solid substance except for a portion that becomes a gap between the member (A) and the member (B), so that the member (A) and the member (B) are solid-state. A substance capable of forming a capillary void portion with a substance, or a member having a concave portion on its surface (A) is brought into close contact with the concave surface of the member (A) to form a concave portion of the member (A) with the member (B). The shape, structure, surface condition, and the like are arbitrary as long as the gap can be formed. These are the same as in the case of the member (A). The member (B) need not have a concave portion formed on the surface, but may have a structure other than the concave portion and the concave portion. For example, member (B)
May be a mirror image of the member (A) having a concave portion formed on the surface. When the member (B) is brought into close contact with the member (A) having the concave portion using the energy ray-curable compound as an adhesive, and the energy ray used by the member (A) is not transmitted. The member (B) needs to transmit the energy beam to be used.

The method of forming the structure in which the void portion is formed as a defective portion of the solid substance filled between the member (A) and the member (B) is described in, for example, the member (A) and the member (B). After irradiating the energy ray-curable composition between the members and exposing the energy ray from the outside of the member (A) and / or the member (B) except for a portion to be a void, the uncured energy ray-curable A method of removing the composition, a method of sandwiching a sheet-like member obtained by cutting out a portion to be a gap between the member (A) and the member (B) and bringing the sheet-like member into close contact with each other, Place a rod made of ethylene tetrafluoride,
After filling and solidifying with an adhesive or a molten resin, a method of removing a protective substance can be adopted. Although this method has a small number of steps, it is difficult to remove the uncured energy-ray-curable composition and the protective substance when the void diameter is small, and thus it is suitable as a method for forming a void having a relatively large dimension. .

The way of providing the inflow port and the outflow port is optional. For example, when the base material is composed of the member (A) and the member (B), the inlet and the outlet formed between the member (A) and the member (B) in the same manner as the gap portion. It is also possible to provide an inlet or an outlet by making a hole in the member (A) and / or the member (B). The inflow port and the outflow port may be connected to the outside of the device, or other structural parts formed on the same substrate or a laminated substrate as the present micromembrane separation device, for example, a liquid storage tank, a reaction tank , May be contacted to an analysis mechanism or the like.

In the space provided in the base material, a partition-like communicating porous body which divides the space into an inlet and an outlet is formed. Dimensions and shapes of the partition walls, and other matters relating to the partition walls, and the material, shape, and pore size of the porous body,
The description regarding the other porous body is the same as the description regarding the first device of the present invention. However, the groove-like pores in the first device of the present invention are capillary and / or slit-like pores.

When the second device of the present invention is used for filtration, the above-mentioned inlet and outlet are respectively the primary side (also referred to as undiluted solution side) and the secondary side (also referred to as filtrate side).
Can be used as outlet. In the void,
It is also preferable that a primary outlet is further connected to the side where the inlet is formed. By providing the primary outlet, not only the total filtration method but also other membrane separation methods, for example, an ultrafiltration method (a method in which a part of the undiluted solution is filtered), a liquid-liquid separation such as oil-water separation, and a liquid (Including devolatilization and defoaming), dissolving a gas in a liquid, dissolving a liquid in a liquid, and dispersing a liquid in a liquid.

The i-th manufacturing method of the present invention relates to the first manufacturing method of the present invention.
(1) An energy ray-curable compound (a) is provided in a concave portion provided on the surface of a substrate.
And is compatible with the energy ray-curable compound (a),
A first step of filling an energy beam-curable composition (C) containing a phase separator (b) that does not dissolve or swell the cured product of the energy beam-curable compound (a); A second step of irradiating an energy ray to a portion serving as a partition to be divided into portions, and curing the energy ray-curable compound (a) to form a partition made of a communicating porous body; and (3) uncured A third step of removing the energy ray-curable composition (C).

The energy ray-curable compound (a), whether organic or inorganic, may be any as long as it can be polymerized by irradiation with energy rays to become a polymer.
Compounds having a carbon double bond are more preferable, and compounds having a (meth) acryloyl group having a high curing rate and compounds having a maleimide group which does not require a photopolymerization initiator are particularly preferable. These compounds can be used alone or as a mixture of two or more.

Examples of the (meth) acrylic monomer that can be used as the energy ray-curable compound (a) include, for example, ethyl (meth) acrylate and n-butyl (meth)
Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth)
Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 3-methacryloxypropyl tris (trimethylsiloxy) silane,
Trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, methyl-2-chloroacrylate,
Monofunctional monomers such as 3-chloro-2-hydroxypropyl (meth) acrylate; diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,2 Bifunctional monomers such as' -bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) acrylate Trifunctional monomers such as trimethylolethanetri (meth) acrylate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; and hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. It is. These compounds can be used alone or as a mixture of two or more.

As the energy ray-curable compound (a), a polymerizable oligomer (also referred to as a prepolymer) having a weight average molecular weight of 500 to 50,000, preferably a (meth) acrylic oligomer can be used. Examples of the (meth) acrylic oligomer that can be used as the energy ray-curable compound (a) include, for example, a (meth) acrylate of an epoxy resin, a (meth) acrylate of a polyether resin, and a (meth) acryl of a polybutadiene resin. Acid ester, (meth) at molecular end
And polyurethane resins having an acryloyl group. These oligomers can be used alone, can be used by mixing two or more kinds, or can be used by mixing with a monomer.

Examples of the maleimide-based monomer that can be used as the energy ray-curable compound (a) include maleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-ethylmaleimide, N-methylmaleimide, and N-benzylmaleimide. Monofunctional maleimides such as: 4,4'-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1,6-bismaleimidehexane, 1,2- And bifunctional maleimides such as bismaleimidoethane. These maleimide monomers can be used alone or as a mixture of two or more. Further, these maleimide-based monomers can be used as a mixture with other polymerizable compounds such as vinyl ethers and acrylic monomers and / or oligomers.

In order to sufficiently increase the strength and hardness of the formed substrate, it is necessary that the cured product of the energy ray-curable compound (a), that is, the polymer to be a porous body is a crosslinked polymer. Preferably, therefore, the energy ray-curable compound (a) is, for example, a single or mixture of 2 to 6 functional polyfunctional monomers and / or oligomers.

In the case where the porous portion is preferably hydrophilic, energy ray curing containing a hydrophilic group or a hydrophilic portion such as a hydroxyl group, a carboxyl group, a sulfone group, an amino group, an ammonium salt, an amide bond, an ether bond, or the like. Sex compounds can be used alone or in combination. Further, for the purpose of improving the adhesion to the substrate, it is preferable to use these energy ray-curable compounds having a hydrophilic group alone or as a mixture.

The phase-separating agent (b) is compatible with the energy ray-curable compound (a) and dissolves or polymerizes the polymer formed when the energy ray-curable compound (a) is irradiated with energy rays. Any material may be used as long as it does not swell and is inert to energy rays. In addition, "swelling" in the present invention is a concept relating to a crosslinked polymer corresponding to dissolution of a linear polymer, and means that the crosslinked polymer becomes a gel. The term "inert with respect to energy rays" means that its properties do not change to a nonnegligible degree due to polymerization, decomposition, reaction with the energy ray-curable compound (a), and the like. It is permissible that partial cross-linking, decomposition, reaction, etc. occur.

In the i-th production method of the present invention, the phase separation agent (b) and the energy ray-curable compound (a) need to be substantially compatible at the time of irradiation with energy rays. Irradiation with energy rays in a phase-separated state does not form a communicating porous body. However, they need not be completely compatible, and may have some insoluble parts.

The compatibility between the phase separator (b) and the energy ray-curable compound (a) varies depending on various conditions, especially the temperature of the energy ray-curable composition (C) containing these.
Further, it may vary depending on the type of the energy ray-curable compound (a). For example, when a polyurethane having a (meth) acryloyl group at a molecular terminal, which is a polymerizable oligomer, is used as the energy ray-curable compound (a), methyl caprate, ethyl caprate, Methyl laurate, methyl caprylate,
Alkyl esters such as ethyl caprylate and diisobutyl adipate, dialkyl ketones such as diisobutyl ketone, alcohols, and liquid polyethylene glycol
Monoesters, polyethylene glycol sorbitan esters, polyethylene glycol monoethers, mono-, di-, and triesters of glycerin, alkyl esters having a hydroxyl group, alkyl amines, polyethylene glycol amine, and other interfaces Activators, furthermore, mixtures of one or more of these with water and the like can be suitably used, and among them, liquid polyethylene glycol, polyethylene glycol monoester, polyethylene glycol sorbitan esters, polyethylene glycol monoether, glycerin Mono-, di- and triesters, alkyl esters having a hydroxyl group,
The use of an alkylamine, polyethylene glycolamine, or the like is particularly preferable because the polymer precipitated by irradiation with energy rays tends to form a network and the strength of the porous portion is increased.

The phase-separating agent (b) is dissolved in the liquid energy-ray-curable compound (a), and if it is inert to energy-ray irradiation, it may be a solid such as a polymer. Is also good. As such a phase separating agent (b),
For example, cellulose acetate, ethyl cellulose, nitrocellulose, chitosan, paraffin, polystyrene, polyvinyl chloride, polycarbonate, polysulfone, polyethersulfone, polyurethane, polyacrylonitrile, poly (meth) acrylate, poly (meth) acryl Acids, polymethyl methacrylate, polyacrylamide, polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, and the like, and derivatives and copolymers thereof, among which polyethylene glycol and polyvinyl pyrrolidone are preferable. The polymer used as the phase separator (b) may be a plurality of polymers. Further, the phase separation agent (b) may be a polymer solution.

It is generally preferred that the phase-separating agent (b) be water-soluble irrespective of liquid or solid, from the viewpoint of improving productivity. It is particularly preferable to form a hydrophilic porous portion by using it, because the hydrophilicity of the porous portion can be enhanced.

Further, the phase separating agent (b) may be a single composition or a mixture. In the case of a mixture, the mixture is compatible with the energy ray-curable compound (a) used in the present invention, and a polymer formed by irradiation of the energy ray-curable compound (a) with energy rays May be any as long as it does not dissolve and is inert to energy rays, and the properties of its constituent components alone are not particularly limited. Therefore, the individual components in the mixture may be incompatible with the energy ray-curable compound (a) or may dissolve or swell the polymer generated from the energy ray-curable compound (a). It may be. For example, mixing a good solvent that dissolves the energy ray-curable compound (a) and a polymer that also dissolves a polymer generated from the energy ray-curable compound (a) with water that does not dissolve both of them. Also preferred is a liquid.

The proportion of the phase separator (b) is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, per 1 part by weight of the energy ray-curable compound (a). Is more preferred. If it is lower than this range, the porosity of the porous portion becomes too low, and if it is higher than this range, the porosity tends to be too high and the strength tends to be insufficient.

According to the i-th manufacturing method of the present invention, a device in which the porous body has a three-dimensional network or aggregated particle structure can be manufactured. If the ratio of the phase separation agent (b) to the energy ray-curable compound (a) is small, it tends to be a three-dimensional network, and if it is large, it tends to have an aggregated particle structure.

The pore size of the pores of the porous portion depends on the mixing ratio of the energy ray-curable compound (a) and the phase-separating agent (b) as well as the energy ray-curable compound (a) and the phase-separating agent (b). Depends on the combination of Generally speaking, when the mixing ratio of the phase separation agent (b) is high, when the compatibility between the energy ray-curable compound (a) and the phase separation agent (b) is poor, the energy ray curability When the viscosity of the composition is low, the pore size tends to increase.

Whether the compatibility between the energy ray-curable compound (a) and the phase separation agent (b) is good or not can be determined by gradually lowering the temperature of the liquid mixture and causing the phase separation. The lower the phase separation temperature, the better the compatibility. According to the first production method of the present invention, by selecting appropriate conditions, pores having a pore diameter in the range of 0.01 to 5 μm can be easily formed.

The energy ray-curable composition (C) is a solution which is cured by irradiation with energy rays to form a porous body, and comprises an energy ray-curable compound (a) and a phase separator (b) as essential components. However, it is also possible to add other components to the composition. Examples of the other components include an ultraviolet polymerization initiator, a polymerization inhibitor and a polymerization retarder, a dye and a pigment, a hydrophilizing agent, an enzyme and a catalyst. In order to increase the resolution and form minute partition walls, it is preferable to add a small amount of a polymerization inhibitor and / or a polymerization retarder. When ultraviolet rays are used as energy rays, it is preferable to add an ultraviolet ray polymerization initiator to the energy ray-curable composition for the purpose of increasing the polymerization rate.

The photopolymerization initiator, which can be added to the energy ray-curable composition (C) as required, is active with respect to the energy ray used in the present invention, and is used as the energy ray-curable compound (a). ) Is not particularly limited as long as it can be polymerized, and may be, for example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator. Examples of the photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2'-diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, Ketones such as 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether;
Benzoin ethers such as benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone;

The photopolymerization initiator can be used in the state of being dissolved or dispersed in the energy ray-curable composition (C), but is preferably one that dissolves in the energy ray-curable composition (C). When the photopolymerization initiator is used, the concentration of the photopolymerization initiator in the energy ray-curable composition (C) is preferably in the range of 0.01 to 20% by weight, and more preferably 0.5 to 20% by weight.
A range of 10% by weight is particularly preferred.

Examples of the polymerization inhibitor which can be added to the energy ray-curable composition (C) as needed include, for example, hindant phenols such as pt-butylphenol, quinones and amines. No. Examples of the polymerization retarder that can be added as needed include, for example, styrene, α-methylstyrene, α-phenylstyrene, p-octylstyrene, 2-vinylnaphthalene, p- (4-pentylcyclohexyl) styrene , P-phenylstyrene, p- (p-ethoxyphenyl) phenylstyrene, 4,4'-divinylbiphenyl, and the like.

The suitable addition amount of the polymerization inhibitor and the polymerization retarder depends on the type of the polymerization inhibitor and the polymerization retarder, the type of the energy ray-curable compound (a), and the type and the addition amount of the photopolymerization initiator. Dependent. If the addition amount is too small, the effect of the addition is not recognized, and if the addition amount is excessive, the curing is incomplete. The optimum value of the addition amount can be determined by a simple experiment in the used system.

Dyes and pigments that can be added as necessary to the energy ray-curable composition (C) include:
For example, dyes and pigments as colorants, fluorescent dyes and fluorescent pigments such as anthracene, 2-benzotriazoyl-4-
An ultraviolet absorber such as methoxyphenol may be used.

Examples of the hydrophilic agent that can be added to the energy ray-curable composition (C) as needed include, for example, hydrophilic polymers such as polymethylpyrrolidone and polyethylene glycol, and hydrophilic inorganic materials such as silica gel. And the like.

In the first step of the i-th production method of the present invention, there is no particular limitation on the method of filling the energy beam curable composition (C) into the concave portions of the substrate.
For example, a method such as application by a coater or dipping; injection by a nozzle or an applicator may be used. The filling amount of the energy ray-curable composition (C) into the concave portions of the substrate is such that the liquid level of the filled curable composition (C) is higher than the surface of the substrate in consideration of shrinkage due to curing. The amount is preferred. The energy ray-curable composition (C) may enter a structure other than the concave portion, for example, a flow path connected to the concave portion, but may be filled only in a necessary portion by masking if necessary. Can also. Conversely, the energy ray-curable composition (C) does not need to be filled in the entire concave portion, but only needs to be filled in the portion where the porous body is formed.

The energy ray-curable composition (C) is cured by performing a second step of irradiating a part to be a porous body with an energy ray.

The energy ray is not particularly limited as long as it can cure the energy ray-curable composition (C). Examples of the energy ray include ultraviolet rays, visible rays, infrared rays, X-rays, and the like.
Electromagnetic waves such as gamma rays and emitted light; and particle beams such as electron beams, beta rays, and heavy particle beams, etc., from the viewpoint of handleability and curing speed, ultraviolet rays, visible lights, and electron beams are preferred, and ultraviolet rays are particularly preferred. The ultraviolet light is preferably a laser beam.

In order to accelerate the curing speed and complete the curing, it is preferable to perform the irradiation with the energy beam in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

The method of irradiating a portion to be a porous body with an energy beam is arbitrary. For example, a photolithography method such as a method of irradiating an unnecessary portion by photomasking or a method of scanning an energy beam. Is available. It is preferable that the energy ray is irradiated from a direction perpendicular to the surface of the substrate, but it is not necessary that the energy beam be exactly perpendicular. Irradiation can also be performed through the substrate from the substrate side.

When the energy-ray-curable composition (C) is irradiated with energy-rays, the energy-ray-curable compound (a), which is a constituent component thereof, is polymerized, and phase-separates with the phase-separating agent (b). By curing into a porous state,
A porous body having pores filled with the phase separation agent (b) is formed.

Uncured energy ray-curable composition (C)
The phase separation agent (b) in the pores is removed in the third step. The removal can be performed by any method such as washing, drying, suction, absorption, replacement, and blowing, but washing is preferable.
If a cover is attached to the device, in a third step it can be removed through the inlet and / or outlet by pressure or suction. In order to completely cure the boundary of the porous portion or to further increase the hardness of the porous portion, the energy beam-curable composition (C) is removed, and then the energy beam is irradiated again. You can also.

Before the third step, other processing such as close contact of the cover and integration with another structure can be performed. Further, after the micromembrane separation device is manufactured by the first manufacturing method of the present invention, it can be laminated or bonded to a cover or another member.

The second manufacturing method of the present invention is a method of manufacturing the first device of the present invention in which the porous body constituting the partition has a plurality of groove-like pores penetrating the partition. (1 ′) In a concave portion provided on the surface of the member (A),
A 1 'step of filling the energy ray-curable composition (D) containing the energy ray-curable compound (a'), (2 '
A) a thickness of 0.01 for dividing the recess into a plurality of portions in the recess filled with the energy ray-curable composition (D);
Irradiation is performed on a part to be a partition having a thickness of about 3 mm except for a part that becomes a groove-shaped pore penetrating the partition, thereby curing the energy ray-curable composition (D). A 2 ′ step of forming a partition wall made of a porous body composed of fine pores and a (3 ′) third step of removing the uncured energy ray-curable composition (D).

The energy ray-curable composition (D) is not particularly limited as long as it is a composition which can be cured by irradiation with energy rays to form a dense solid. It is a composition with. The energy ray-curable compound (a ') is the same as the energy ray-curable compound (a) in the first production method of the present invention, and a compound usable as the energy ray-curable compound (a) can be used. .

The energy ray-curable composition (D) preferably has a low viscosity in order to facilitate removal of the uncured energy ray-curable composition (D) in the third step.

The energy ray-curable composition (D) is cured by irradiation with an energy ray to form a dense partition, and the unirradiated portion becomes a plurality of groove-like pores as defective portions of the partition. Therefore, when making the porous body hydrophilic or hydrophobic, the energy ray-curable compound (a '), the additive to the energy ray-curable composition (D) and the like can be selected. It can be carried out by making the cured product of the hydrophilic composition (D) hydrophilic or hydrophobic. Regarding the selection of the energy ray-curable compound (a ') and the selection of the additive to the energy ray-curable composition (D), the porous material is made hydrophilic or hydrophobic in the first production method of the present invention. This is the same as the selection of the energy ray-curable compound (a) and the selection of the additive to the energy ray-curable composition (C).

The energy ray-curable composition (D) may further contain, for example, an ultraviolet polymerization initiator, a dye or pigment, a hydrophilic agent, a water repellent, a reinforcing material, and the like. In order to increase the resolution and form minute partition walls or minute groove-like pores, it is preferable to add a small amount of a polymerization inhibitor and / or a polymerization retarder. When ultraviolet rays are used as energy rays, it is preferable to add an ultraviolet ray polymerization initiator to the energy ray-curable composition for the purpose of increasing the polymerization rate.

The ultraviolet ray polymerization initiator, polymerization inhibitor, polymerization retarder, dye or pigment, and hydrophilic agent which can be added to the energy ray-curable composition (D) as required are the i-th compounds of the present invention. In the production method described above, the compounds exemplified as those that can be added as necessary to the energy ray-curable composition (C) can be used. Examples of the water repellent that can be added to the energy ray-curable composition (D) as needed include, for example, silicone oil, fluorine-substituted hydrocarbons, and the like.

The shape and dimensions of the groove-like pores are the same as those described in the second device of the present invention.

The other parts, for example, a method of filling the concave portion of the substrate with the energy ray-curable composition (D), the type of the energy ray, the method of irradiating the energy ray, the uncured energy ray-curable composition The method for removing (D) and the like are the same as those in the i-th production method of the present invention except that the energy ray-curable composition (D) is used instead of the energy ray-curable composition (C). The same is true.

The shape of the groove-shaped pores may be the shape described in the second device of the present invention. According to the second manufacturing method of the present invention, groove-shaped pores having a width of 1 μm or more can be easily formed.

The third manufacturing method according to the present invention is a method for manufacturing the second device according to the present invention, wherein (1 ″) a space having an inflow port and an outflow port provided inside a substrate, An energy ray-curable compound (a) and a phase separating agent (b) which is compatible with the energy ray-curable compound (a) but does not dissolve or swell the cured product of the energy ray-curable compound (a) 1st step of filling the energy ray-curable composition (C) to be contained, (2 ") in the gap filled with the energy ray-curable composition (C), becomes a partition separating the inflow port and the outflow port. A second "step of irradiating the shape portion with an energy ray to cure the energy ray-curable compound (a) to form a partition formed of a communicating porous body, and (3") uncured energy ray curing From the third "step of removing the conductive composition (C). .

The shape of the substrate used in the third manufacturing method is as follows:
It is optional as long as it has a cavity inside the base material, has an inflow port and an outflow port connected to the cavity, and can irradiate a part forming a partition wall with energy rays. What can be used as a substrate of the device can be used. The substrate is
It is composed of a member (A) and a member (B) which are preferably used as a substrate of the second device of the present invention and are in close contact with each other, and a gap is formed between the member (A) and the member (B). Preferably, it is

The depth of the void from the surface of the base material is preferably 1 cm or less from the viewpoint of easy irradiation of energy rays. As the material of the substrate, any material that can be used as the substrate of the second device of the present invention can be used, but it is necessary that the material transmit the energy rays used. The dimensions and shape of the gap are the same as those described for the gap of the second device of the present invention.

The filling of the energy ray-curable composition (C) in the first step can be carried out by injection from an inlet or an outlet. Alternatively, an additional inlet is provided.
Finally, it is possible to close the inlet.

Other than the above, for example, the energy ray-curable compound (a), the phase separator (b), the energy ray-curable composition (C) and the like are the same as those in the case of the i-th production method of the present invention. It is.

The irradiation of the energy rays in the second "step is the same as in the case of the i-th production method of the present invention except that the irradiation is performed through the base material.

The removal of the uncured energy ray-curable composition (C) and the separated phase separation agent (b) in the third "step is performed by applying pressure through an inlet, an outlet, a separately provided inlet, or the like. , Suction, washing and the like.

The rest is the same as the i-th manufacturing method of the present invention.

[0112] The iv manufacturing method of the present invention is the method according to the second aspect of the present invention, wherein the porous body constituting the partition is a communicating porous body composed of a plurality of capillaries and / or slits penetrating the partition.
A method for manufacturing a device according to (1), wherein the energy ray-curable compound (a ') is contained in a void portion having an inflow port and an outflow port provided inside the base material (1 "'). First step of filling the conductive composition (D), (2 ′ ″)
In the gap filled with the energy ray-curable composition (D), a plurality of capillaries and / or slits penetrating the partition are provided in a portion serving as a partition having a thickness of 0.01 to 3 mm separating the inflow port and the outflow port. Irradiation of energy rays except for the parts to be cured to cure the energy ray-curable composition (D),
A second step of forming a partition made of a communicating porous body composed of a plurality of capillaries and / or slits, and a third step of removing (3 ′ ″) the uncured energy ray-curable composition (D) Consists of

The base material used in the iv production method is as follows:
This is the same as the case of the manufacturing method iii of the present invention.

The filling of the energy ray-curable composition (D) in the first ″ ′ step can be carried out by injection from an inlet or an outlet. Alternatively, it is also possible to provide a separate inlet and finally close the inlet.

Other than the above, for example, the energy ray-curable compound (a ′), the energy ray-curable composition (D) and the like are the same as in the case of the second production method of the present invention.

The irradiation of the energy ray in the 2 ′ ″ step is the same as the 2 ′ step of the manufacturing method ii of the present invention except that the irradiation is performed through the substrate.

The removal of the uncured energy-ray-curable composition (D) in the 3 ′ ″ step is performed by removing the uncured energy-ray-curable composition (D) in the third ″ step of the production method iii of the present invention. It is the same as the removal method of C).

The other points are the same as those in the second manufacturing method of the present invention.

[0119]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the scope of these examples. In the following examples, "part"
And "%" represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

<Preparation of energy ray-curable composition (C)> [Preparation of energy ray-curable composition (C-1)] As an energy ray-curable compound (a), "Aronix M-5
50 "(ethylene oxide-modified phthalic acid monoacrylate manufactured by Toa Gosei Chemical Co., Ltd.) and 50 parts of" NK Ester A-400 "(polyethylene glycol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.), phase separator (b) Were mixed with 10 parts of ethanol and 10 parts of "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Geigy) as an ultraviolet polymerization initiator to prepare an energy ray-curable composition (C-1).

[Preparation of energy-ray-curable composition (C-2)] As an energy-ray-curable compound (a), “Unidick V-4263” (average 3 per molecule manufactured by Dainippon Ink and Chemicals, Inc.) 60 parts of an urethane acrylate oligomer having an acrylic group), 20 parts of HDDA, 8 parts of Irgacure 184 as a photopolymerization initiator, and diisobutyl ketone (manufactured by Kanto Chemical Co., Ltd.) 2 as a phase separator (b) 2
0 parts and 70 parts of methyl caprate (manufactured by Kanto Chemical Co., Ltd.) were mixed to prepare an energy ray-curable composition (C-2).

<Preparation of energy ray-curable composition (D)> [Preparation of energy ray-curable composition (D-1)] As an energy ray-curable compound (a '), "Unidic V
-4263 "and 40 parts of" M-114 "(nonylphenoxy polyethylene glycol manufactured by Toa Gosei Chemical Co., Ltd. (n =
8) Acrylate) 60 parts, 5 parts of “Irgacure 184” as an ultraviolet polymerization initiator, and polymerization retarders 2 and 4
-Diphenyl-4-methyl-1-pentene (manufactured by Kanto Kagaku Co., Ltd.) in an amount of 0.1 part was mixed to form an energy ray-curable composition (D
-1) was prepared.

[Preparation of energy ray-curable composition (D-2)] As an energy ray-curable compound (a '), 30 parts of "Unidick V-4263" and "New Frontier HDDA" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 30 parts of 1,6-hexanediol diacrylate), 40 parts of "N-177E" (nonylphenoxy polyethylene glycol (n = 17) acrylate manufactured by Daiichi Kogyo Seiyaku Chemical Co., Ltd.), and "Irgacure 184" as a photopolymerization initiator. 5 parts and 0.1 part of a polymerization retarder 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) were mixed to prepare an energy ray-curable composition (D-2).

[Preparation of energy ray-curable composition (D-3)] As an energy ray-curable compound (a '), tetramethylene glycol (number average molecular weight: 650) maleimide acetate (a synthesis example of JP-A-11-124403) 80 parts) and 20 parts of “Sartomer C2000” (a diacrylate mixture mainly composed of ω-tetradecanediol diacrylate and ω-pentadecanediol diacrylate manufactured by Somal) were mixed. , Energy ray-curable composition [D
-3].

<Example 1> In this example, an example of manufacturing a micromembrane separation device having a partition formed of a three-dimensional mesh-like porous material in a concave portion provided on the surface of a base material was described. .

[Preparation of Micromembrane Separation Device] [Preparation of Substrate] "Dick Styrene XC-520"
A plate of 5 cm × 5 cm × 3 mm was prepared by injection molding (polystyrene manufactured by Dainippon Ink and Chemicals, Inc.),
The surface was hydrophilized by immersion in concentrated sulfuric acid at 5 ° C for 5 hours. After masking the four sides of the hydrophilic substrate with a masking tape for coating, "Unidick V"
2.5 ml of a mixture consisting of 100 parts of “-4263” and 2 parts of Irgacure 184, an ultraviolet polymerization initiator, was cast. Next, a portion that becomes the concave portion (2), the inflow channel (3), the inflow port (4), the outflow port (5), the outflow channel (6), and the liquid storage tank (7) having the shape shown in FIG. Was photomasked, and 10 mW in a nitrogen atmosphere using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc.
/ Cm ² for 30 seconds, and the uncured material was washed and removed with ethanol to form a concave portion having a length of 1.5 cm, a width of 3 mm and a depth of about 0.8 mm as shown in FIG. The substrate (S-1) (1) having (2) was obtained.

[Preparation of Partition Wall] [First Step] The concave portion (2) of the base material (1), the inflow channel (3),
An energy ray-curable composition was used for a part to be an inlet (4), an outlet (5), an outflow passage (6), and a liquid storage tank (7) using a Shotmaster 2 type applicator manufactured by Musashi Engineering Co., Ltd. The product (C-1) was injected and filled to an extent slightly higher than the surface of the substrate.

[Second Step] The base material (S-1) filled with the energy ray-curable composition (C-1) obtained in the first step.
The substrate (S-1) is passed through a photomask in a nitrogen atmosphere at a portion to be the partition (8) shown in FIG.
Ultraviolet rays were irradiated for 30 seconds using the same ultraviolet irradiation apparatus as in the case of (1).

[Third Step] The uncured energy ray-curable composition (C-1) is removed from the substrate (S-1) (1) irradiated with the ultraviolet rays in the second step by washing with ethanol, and the step is repeated. By irradiating the same ultraviolet rays as in the second step for 120 seconds to completely cure the mixture, and then air-drying, a three-dimensional mesh-like porous body having an average pore diameter of about 2 μm and having a shape shown in FIG. The recess (2) has a width of 1.1 mm and a length of 1.0 mm by a partition wall (8) having a height of about 0.8 mm, a thickness of 0.8 mm, and a length of 1.5 cm.
5cm primary side recess (2 '), width 1.1mm, length 1.5cm
The micro-membrane separation device (# 1) divided into the secondary side concave portion (2 ″) was obtained.

[Water Permeability Test] A 0.1% aqueous solution of sodium alkylsulfonate as a surfactant was introduced into the storage tank (7) of the obtained device (# 1) using a micropipette. It travels along the inflow path (3) by capillary action, enters the primary recess (2 ') from the inflow port (4), passes through the partition (8) made of a porous material, and passes through the secondary recess (2 "). ) And outflow (5) through outflow (6)
Leaked to From this, it was confirmed that the porous partition wall (8) was a communicating porous body.

<Embodiment 2> In this embodiment, an example of manufacturing a micromembrane separation device in which a cover is adhered to a concave portion partitioned by a partition wall has been described.

[Production of Micromembrane Separation Device] The device (# 1) produced in Example 1 was used as a device to which a cover was attached.

[Attachment of Cover] A mixed solution composed of 30 parts of "Unidick V-4263", 70 parts of isopropanol and 2 parts of "Irgacure 184" was placed on the same polystyrene plate before surface processing as used in Example 1 for the base material. 50
After coating using a bar coater of μm, isopropanol was removed by hot air drying to obtain a cover member.

After the cover obtained above was brought into close contact with the surface of the device (# 1) with the application surface facing the device,
The same ultraviolet rays as in Example 1 were applied for 90 seconds to adhere. Further, a hole is drilled in a cover of an upper portion of the liquid storage tank (7) using a drill to form an introduction path (not shown) that connects the concave portion to the outside of the device, thereby forming a device (#).
2) got

[Filtration Test] The clay-dispersed water was discharged from a hole-like introduction passage (not shown) formed in the liquid storage tank (7) of the obtained device (# 2) using a syringe. Upon injection, the clay-dispersed water passes through the capillary inflow path (3), enters the primary-side cavity [(the covered primary-side recess (2 ')] from the inflow port (4), and removes the clay. Transparent water not containing penetrates the porous partition wall (8), enters the secondary space [[covered secondary recess (2 ″)]], and flows out from the outlet (5) to the outlet channel (6). From which,
It can be seen that the porous partition completely separates the primary side and the secondary side of the void.

<Example 3> [Production of device] In Example 1, the concave portion formed on the surface of the base material (11) was replaced with the primary concave portion (12 '), 2 Next side recess (12 ") and partition (1
8) and the partition wall (18) was irradiated with light so as to have the shape shown in FIG.
A device (# 3) was prepared in the same manner as described above, and a cover was attached in the same manner as in Example 2, and the same cover as in Example 2 was adhered except that the shapes of the concave portions and the partition walls were different. (# 3 ′) was prepared.

[Filtration test] Obtained device (# 3 ')
When the water in which the clay is dispersed is injected using a syringe through a hole-shaped introduction path (not shown) formed in the liquid storage tank (17), the clay-dispersed water is supplied to the capillary inflow path (13). Through the inflow port (14), into the primary side void [(covered primary side recess (12 ')]), and clear water containing no clay permeates through the porous partition (18). Into the secondary space [[covered secondary recess (12 ″)]
It flowed out of the outlet (15) to the outflow channel (16). From this, it was found that the primary side and the secondary side of the void were completely separated by the porous partition wall.

<Embodiment 4> In this embodiment, an example of a device having a primary-side outlet on the side (primary side) of the concave part partitioned by the partition wall on which the inlet is formed is shown.

[Production of microchemical device] Example 1
Wherein the dimensions of the polystyrene plate used as the material of the substrate (21) are 5 cm × 2.5 cm × 3 mm, and the primary side recesses (22 ′) formed by partitioning the partition walls (28, 28 ′). However, in addition to the inlet (24), the primary outlet (2
7), a partition wall (2) made of a porous body
8, 28 ') are formed on both sides of the primary recess (22'), and there are two secondary recesses (22 ", 22"') and two outlets (25, 25'). In addition, except that no liquid storage tank is provided and the inflow path (23) is directly opened to the outside of the device, the height shown in FIG. 0.8mm, thickness 0.8mm each,
A device (# 4) having two partition walls each having a length of 3 cm was prepared. Further, in the second embodiment, the device (# 4)
A device (# 4 ′) with a cover attached was prepared in the same manner as in Example 2 except for using.

[Filtration test] Obtained device (# 4 ')
When the water in which the clay was dispersed was flowed into the capillary inflow path (23) using a syringe, the clay-dispersed water flowed from the inflow port (24) to the primary-side void portion [(the covered concave portion (22) ')], And from the outlet (27) to the outlet channel (2
Spilled to 9). On the other hand, a part of the undiluted solution is a porous partition
8, 28 ') and clear water free of clay
Next side gap [(Covered recesses (22 ″, 22 ″ ′)
)], And through the outlets (25, 25 ′) to the outlet channel (2
6, 26 ').

<Example 5> [Production of microchemical device] In Example 1, instead of polystyrene as the base material,
"Delpet 670N" (acrylic resin manufactured by Asahi Kasei Kogyo), "Iupilon S-2000" (polycarbonate manufactured by Mitsubishi Engineering Plastics),
"Udel P-1700" (polysulfone manufactured by Amoco), "U-Polymer U-70" (polyarylate resin manufactured by Unitika), and transparent hard vinyl chloride resin,
Are used in the same manner as in Example 1 except that the microchemical devices [# 5-1], [# 5-2], and [#
5-3], [# 5-4] and [# 5-5], respectively.

[Liquid sending test] Microchemical device [# 5
[-1] to [# 5-5], the same test as in Example 1 was performed, and the same result as in Example 1 was obtained.

<Embodiment 6> In this embodiment, a device in which a concave portion is partitioned by a partition wall composed of a porous body having a plurality of parallel groove-like pores, and a cover is attached to the device, A production example of a device in which a void portion was partitioned by a partition wall composed of a porous body having a plurality of parallel slit-shaped pores was shown.

[Preparation of Device] [Preparation of Substrate]
"-4263" instead of 100 parts, "Unidick V-
4263 ”50 copies and“ New Frontier HDDA ”
The procedure of Example 1 was repeated, except that a mixture of 50 parts was used, and that the mixture was applied using a 50 μm bar coater instead of casting. 1.5cm long, 3mm wide, 34μm deep recess (2)
(S-6) (1) having the following formula:

[Preparation of Partition Walls] [Step 1 '] The recesses (2) of the substrate (1) were filled with the energy ray-curable composition (D-1) to an extent slightly higher than the surface of the substrate.

[2 'Step] The substrate (1) in which the energy beam curable composition (D-1) is filled in the recesses (2) obtained in the 1' step is passed through a photomask. 2
The same ultraviolet rays as in Example 1 are irradiated for 20 seconds in a nitrogen atmosphere to a portion other than the portion serving as the partition (8) and the portion serving as the groove-shaped pore (30) shown in FIG. did.

[Third Step] The uncured energy ray-curable composition (D-1) was removed from the substrate (1) irradiated with ultraviolet rays in the second step by washing with ethanol, and the second step was repeated. After completely irradiating the same ultraviolet rays as in the above process for 120 seconds to completely cure, air-dry, and having a height (h) of 34 μm, a width (w) of 17 μm and a length of the shape shown in FIGS. (D)
A device having a partition wall with a height (h) of 34 μm and a thickness (d) of 200 μm in which a number of groove-like pores (30) having a thickness of 200 μm are formed in a direction perpendicular to the surface of the partition wall with a span of 40 μm (#) 6) was obtained.

Further, in the second embodiment, the device (#
Except that 6) was used, in the same manner as in Example 2, a device (# 6 ′) provided with a cover and having slit-shaped pores of the same size as the groove-shaped pores (30) was formed. ) Was prepared.

[Filtration Test] When a 0.1% aqueous solution of sodium alkyl sulfonate was introduced from the introduction path (not shown) of the device (# 6 ') using a syringe, the aqueous solution permeated the partition wall (8). Then, it flowed out of the outlet (5) to the outflow channel (6).

<Embodiment 7> In this embodiment, a device in which a concave portion is partitioned by a partition wall composed of a porous body having a plurality of parallel groove-like pores, and a cover is attached to the device. A production example of a device in which a void portion is partitioned by a partition wall formed of a porous body having a plurality of parallel capillary pores has been described.

[Preparation of Device] [Preparation of Base Material]
"-4263" instead of 100 parts, "Unidick V-
4263 ”and“ New Frontier HDDA ”
The same shape as in Example 4 except that the depth of the concave portion was 18 μm in the same manner as in Example 4 except that a mixture of 60 parts was used and the application of the mixture was performed at a high speed. (A-7) was produced.

[Formation of Partition Walls] In Example 4, the energy ray-curable composition (D-1) was used instead of the energy ray-curable composition (C-1), and Except for irradiating the ultraviolet rays except for the part that becomes the capillary, the partition walls (28, 28 ') are formed in the same manner as in Example 4.
A plurality of parallel groove-like pores penetrating the partition (not shown).
5 except that the height (h) is 18 μm and the width (w) is 12 μm. Groove-shaped pores (30) having a rectangular cross section of height (h)
A device (# 7) having a partition wall of about 18 μm and having a thickness (d) of 100 μm and a partition wall formed in parallel with a span of 20 μm was prepared.

[Attachment of Cover] In the same manner as in Example 4, the cover obtained in the same manner as in Example 4 was irradiated with the ultraviolet ray used in Example 4 for 3 seconds to semi-harden the coating film, and the cover was replaced with a device. Capillary pores having the same dimensions as the grooved pores (30) were formed in the same manner as in Example 4 except that ultraviolet light was irradiated for a predetermined time in a state in which the pores were kept in close contact with (# 7). Then, a device (# 7 ') to which the cover was adhered was produced.

[Permeability test] Obtained device (# 7 ')
When a 0.1% aqueous solution of sodium alkylsulfonate was introduced using a syringe from the introduction path (23) of
The aqueous solution entered the primary cavity [(covered recess (22 ')] from the inflow port (24), and flowed out of the outflow port (27) to the outflow path (29). Through the partition walls (28, 28 ') having the shape of pores, into the secondary space [(covered recesses (22 ", 22'")]) and from the outlets (25, 25 '). Outflow channel (26, 2
6 ').

<Example 8> [Production of device] In Example 7, an energy ray-curable composition (D-3) was used instead of the energy ray-curable composition (D-2). A device [# 8] was produced in the same manner as in Example 7.

[Permeability Test] The same test as in Example 7 was performed on the device [# 8], and the same result as in Example 7 was obtained.

<Embodiment 9> In this embodiment, an example of manufacturing a device in which a porous partition wall is formed in a void portion in a substrate.

[Production of Device] [Production of Substrate] 3 mm × 25 mm × 5 made of “Delpet 670N” (acrylic resin manufactured by Asahi Kasei Corporation)
A 0 mm plate was prepared, and a 1 mm diameter hole was drilled through the center of a 3 mm x 50 mm surface to the opposite surface to obtain a substrate (S-9) having a hole.

[Preparation of Partition Walls] [First Step] Using a syringe, the energy ray-curable composition was introduced into one of the drilled holes (inflow port) of the base material (S-9) into the drilled hole. (C-2) was injected, and both openings were sealed with a masking tape for coating.

[Second Step] The center of the drilled hole viewed from the direction perpendicular to the 25 mm × 50 mm surface of the base material, that is, the center of the drilled hole in the longitudinal direction other than the range of 1 mm in length. After the photomasking, the same ultraviolet ray as in Example 1 was irradiated for 30 seconds from a direction perpendicular to a 25 mm × 50 mm surface of the substrate.

[Third Step] After irradiation with ultraviolet rays, the uncured energy ray-curable composition (C-2) is sucked from the inflow port.
Is removed, and ethanol is further injected from another opening (outflow port). After suction and washing is performed from the inflow port, drying is performed under reduced pressure. A device (# 9) in which a portion was formed was obtained.

[Permeability test] When a 0.1% aqueous solution of sodium alkyl sulfonate was injected under pressure into the inlet of the obtained device (# 9) using a syringe, the aqueous solution permeated through the porous portion and flowed out. did.

<Embodiment 10> In this embodiment, a device in which a porous partition wall is formed in a gap formed by bonding a member (A) having a concave portion on its surface and a member (B). An example was shown.

[Production of Device] [Production of Substrate] In Example 1, "Delpet XC-520" was used instead of "Delpet" as a material.
670N "(acrylic resin manufactured by Asahi Kasei Kogyo Co., Ltd.), and the hydrophilic treatment was not performed.
In the same manner as in Example 1, a member (A) (A-1) having the same shape as the substrate (S-1) of Example 1 and having a concave portion formed on the surface.
0) was obtained.

5 cm × 5 cm × 3 mm made of acrylic resin (“Delpet 670N” manufactured by Asahi Kasei Corporation)
(B) (B-10), 30 parts of “Unidick V-4263”, isopropanol 7
A mixed solution consisting of 0 parts and 2 parts of “Irgacure 184” was applied using a 50 μm bar coater, and isopropanol was removed by hot-air drying.
The substrate was brought into close contact with the processed surface of (A-10), and was irradiated with the same ultraviolet rays as in Example 1 for 90 seconds to adhere. Further, a hole is drilled in a part of the member (B) corresponding to the upper part of the liquid storage tank part (7) using a drill to form an introduction path (not shown) that communicates with the outside of the device, and an inflow port (not shown) is formed. 4) and a base material (S-10) having a void portion [(a concave portion (2) covered with the member (B)]) having an outlet (5) was obtained.

[Preparation of Partition] [First Step] Using a syringe, a gap [(a concave portion covered with the member (B)) was introduced from an introduction path (not shown) of the base material (S-10). 2)], the energy ray-curable composition (C-2) was injected, and the openings of the outflow path (6) and the introduction path (not shown) to the outside of the device were closed with a coating masking tape.

[Second "Step"] The same ultraviolet ray as used in Example 1 was irradiated through the photomask from the back surface of the member (A) to the portion to be the partition (8) shown in FIG. 2 for 30 seconds.

[Third “Step”] After the ultraviolet irradiation, the uncured energy ray-curable composition (C-
1) was removed by suction, and further, ethanol was suctioned from an introduction path (not shown) while being injected from an outflow path (6), and washed.

After the cleaning, the same ultraviolet light was again irradiated for 120 seconds to completely cure the film, and then dried under reduced pressure to form a member between the members (A) and (B) having the shape shown in FIG. A device (# 10) in which a partition wall (8) made of a porous material was formed in the formed void portion.

[Permeability test] Obtained device (# 10)
When a 0.1% aqueous solution of sodium alkylsulfonate was injected into the introduction path (not shown) of the sample using a syringe,
The aqueous solution permeated the porous portion (8) and flowed out of the outflow channel (6).

<Embodiment 11> In this embodiment, a solid material is filled between the member (A) and the member (B), and a porous portion is formed in a void formed as a defective portion of the solid material. An example of manufacturing a device in which barrier ribs made of a material were formed was shown.

[Production of Device] [Production of Base Material] 5 cm × 2.5 cm × made of “Delpet 670N” (acrylic resin manufactured by Asahi Kasei Kogyo Co., Ltd.)
"Unidick V-4263" 1 on a 3mm flat plate
In a state where the mixture consisting of 00 parts and 2 parts of “Irgacure 184” was cast, the uncured mixture was sandwiched with the same polystyrene plate as above, and the primary recess (22) having the shape shown in FIG. '), Secondary recesses (22 ", 22'''),
Partition walls (28, 28 '), inflow channel (23), inflow port (2
4) Photomasking the part which becomes the outlet (25), the outlet channel (26), the primary outlet (27), and the primary outlet (29), the multi light 200 manufactured by Ushio Inc. UV light of 10 mW / cm ² was irradiated for 30 seconds in a nitrogen atmosphere using a light source unit for a mold exposure apparatus. After the ultraviolet irradiation, the uncured material was washed away with ethanol to obtain a substrate (S-11) having a void having a depth of 300 μm.

[Preparation of Partition Wall] [First "Step"] In Example 10, the base material (S-11) was used.
Except for using, the energy ray-curable composition (C-2) was injected into the voids in the same manner as in Example 10.

[Second Step] In the same manner as in Example 10,
The portions serving as the partition walls (28, 28 ') were exposed to ultraviolet light.

[Third Step] In the same manner as in Example 10,
Removal of uncured energy ray-curable composition (C-2),
Washing, complete curing, and drying under reduced pressure were performed to obtain a device (# 11) having the same shape as the device (# 4 ′) manufactured in Example 4.

[Permeability test] The same test as in Example 4 was performed on the device (# 11), and the same result as in Example 4 was obtained.

<Embodiment 12> In this embodiment, a plurality of slit-shaped porous partition walls are formed in the gaps of the base material formed by bonding the members (A) and (B). An example of the formed device is shown.

[Preparation of Device] [Preparation of Substrate] A substrate having the same shape as the substrate (S-10) was prepared in the same manner as in Example 10 except that a bar coater of 127 μm was used. A material (S-12) was produced.

[Preparation of Partition Walls] [First Step] The energy ray-curable composition (D-2) was filled in the voids (2) of the base material (1 ″ ′).

[Step 2 ′ ″] With respect to the voids of the substrate (1) filled with the energy ray-curable composition (D-2),
Through a photomask, the same ultraviolet rays as in Example 1 were applied to portions other than the portions serving as the slits (30) of the portions serving as the partition walls (8) shown in FIGS.
Irradiated for seconds.

[Step 3 ″ ′] After irradiation with ultraviolet rays, the composition is sucked from the inflow port and sucked from the uncured energy ray-curable composition (D-
2) is removed and ethanol is added to the other opening (outlet)
The uncured energy ray-curable composition (D-1) is removed by washing with ethanol from the substrate (1) which has been injected from the inlet, and which has been irradiated with ultraviolet rays in the second step by suction from the inflow port, and again After irradiating the same ultraviolet rays as in the second step for 120 seconds to completely cure, and then air-dried, and formed to penetrate the partition wall in a direction perpendicular to the partition wall surface, a height of 40 μm, an average width of 17 μm,
A plurality of parallel slit-shaped pores with a span of 40 μm (3
0) having a partition wall having the shape shown in FIGS. 2 and 5 (# 12).

[Permeability test] Obtained device (# 12)
When a 0.1% aqueous solution of sodium alkylsulfonate was injected under pressure into the introduction path (not shown) of the above using a syringe, the aqueous solution passed through the porous portion (8).

<Embodiment 13> In this embodiment, a solid substance is filled between a member (A) and a member (B), and a capillary formed in a void formed as a defective part of the solid substance is provided. A production example of a device in which a porous partition having porous pores was formed was shown.

[Production of Device] [Production of Substrate] 5 cm × 2.5 cm × made of “Delpet 670N” (acrylic resin manufactured by Asahi Kasei Kogyo Co., Ltd.)
On a 1 mm flat plate, place the energy ray-curable composition (D-
Spread 2), sprinkle about 20 glass rods (homemade) with a diameter of 0.1 mm and a length of about 0.5 mm as spacers at positions where they do not cover the structural part, cover the same polystyrene plate as above, and mix the uncured mixture In the state shown in FIG. 4, the primary-side void portion [corresponding to the primary-side concave portion (22 ′)], 2
Secondary voids [corresponding to secondary concaves (22 ″, 22 ″ ′)], capillaries in partition walls (28, 28 ′) [not shown, but groove-like pores (30) in FIG. Lower the height of
Cover section], the inflow path (2
3), inlet (24), outlet (25), outlet (2
6) Primary outlet (27) and primary outlet (2
9) was photomasked, and a UV light of 10 mW / cm ² was irradiated in a nitrogen atmosphere using a light source unit for a multi-light 200 type exposure apparatus manufactured by Ushio Inc.
Irradiated for seconds. After UV irradiation, uncured material is removed by suction.
Further, after washing with ethanol, a partition having a height of 100 μm and a width of 200 μm (capillary pores having a cross section of 100 μm and a width of 43 μm) in a void having a depth of 100 μm was prepared.
8, 28 ′) and a device (# 13) having the same shape as the device (# 7).

[Permeability test] The same test as in Example 7 was performed on the device (# 13), and the same result as in Example 7 was obtained.

<Example 14> [Production of device] In Example 10, "Delpet 670N" was used as a material for the member (A) and the member (B).
Instead of (acrylic resin), “Dick Styrene XC-520” (polystyrene manufactured by Dainippon Ink and Chemicals, Inc.) and “Iupilon S-200” are used, respectively.
0 "(polycarbonate manufactured by Mitsubishi Engineering-Plastics Corporation)," Udel P-1700 "(polysulfone manufactured by Amoco)," U Polymer U-70 "
Device [# 14-1] in the same manner as in Example 10 except that a polyarylate resin (manufactured by Unitika) and a transparent hard vinyl chloride resin (manufactured by Sekisui Molding Co., Ltd.) were used.
To [# 14-5].

[Permeability test] Device [# 14-1] ~
[# 14-5] was tested in the same manner as in Example 7,
The same results as in Example 10 were obtained.

<Example 15> [Production of device] In Example 11, an energy ray-curable composition (D-3) was used instead of the energy ray-curable composition (D-2). A device [# 15] was manufactured in the same manner as in Example 11.

[Water Permeability Test] The same test as in Example 11 was performed on the device [# 15], and the same result as that in Example 12 was obtained.

[0190]

The micromembrane separation device of the present invention is a device having an extremely small membrane separation portion, and is integrated with a microreaction device or microanalysis device manufactured by forming a groove in a substrate by etching or the like. It is a simple and compact device with a simple structure. Also,
According to the production method of the present invention, there is an advantage that complicated steps such as cutting out and bonding of the porous body are not required, and the productivity is high. Further, according to the manufacturing method of the present invention, the membrane separation mechanism can be formed simultaneously with the micro reaction device and the micro analysis device.

[Brief description of the drawings]

FIG. 1 is a plan view of a substrate having a concave portion on a surface used in an example as viewed from a direction perpendicular to the surface.

[Explanation of symbols]

 DESCRIPTION OF REFERENCE NUMERALS 1 base material 2 concave portion 3 inflow path 4 inflow port 5 outflow port 6 outflow path 7 liquid storage tank

FIG. 2 is a plan view of the device manufactured in the example as viewed from a direction perpendicular to the surface.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base material 2 'concave portion (primary side) 2 "concave portion (secondary side), 3 inflow path 4 inflow port 5 outflow port 6 outflow path 7 liquid storage tank 8 partition wall (porous body)

FIG. 3 is a plan view of the device manufactured in the example as viewed from a direction perpendicular to the surface.

[Explanation of symbols]

 Reference Signs List 11 base material 12 'concave portion (primary side) 12 "concave portion (secondary side), 13 inflow path 14 inflow port 15 outflow port 16 outflow path 17 liquid storage tank 18 partition wall (porous body)

FIG. 4 is a plan view seen from a direction perpendicular to the surface of a concave portion of the device manufactured in the example.

[Description of Signs] 21 Substrate 22 'Recess (primary side) 22 "Recess (secondary side) 22"' Recess (secondary side) 23 Inflow path 24 Inlet (primary side) 25 Outlet (2 25 'Outlet (secondary side) 26 Outflow path 26' Outflow path 27 Outlet (primary side) 28 Partition wall (porous body) 28 'Partition wall (porous body) 29 Outflow path (primary side)

FIG. 5 is an enlarged bird's-eye view of a partition wall portion of a device having a partition wall made of a porous body having groove-shaped pores and manufactured in an example.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base material 2 concave portion 8 partition wall (porous body) 30 groove-shaped pores in partition wall h height of groove-shaped pores, height of partition walls w width of groove-shaped pores d of groove-shaped pores Length, partition thickness

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 35:00 F term (Reference) 4D006 GA06 GA27 GA32 MA03 MA31 MA34 MC24 MC27 MC36 MC48 MC49 MC62 MC72 NA10 NA40 NA42 4F074 AA48N AA50N AA76 AD07 AD11 CB31 CB32 CB37 DA53 DA59

Claims (23)

[Claims] 1. A concave portion is formed on a surface of a substrate, and the concave portion is divided into a plurality of portions in a plane parallel to the surface of the substrate by a partition, and the partition is formed of a communicating porous body. A micromembrane separation device characterized by the above-mentioned. 2. The micromembrane separation device according to claim 1, wherein the depth of the recess is in the range of 0.01 to 3 mm, and the width of the partition is in the range of 0.01 to 3 mm. 3. The recess has an inlet on one side of the partition and an outlet on the other side of the partition.
Or the micromembrane separation device according to 2. 4. A recess having an inflow port and one side on one side of the partition.
4. The micromembrane separation device according to claim 1, wherein the device has a secondary outlet. 5. The communication porous body constituting the partition wall is an aggregate of a plurality of groove-like pores penetrating the partition wall.
5. The micromembrane separation device according to 2, 3, or 4. 6. A polymer whose base material is selected from the group consisting of a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, a polyester polymer and a vinyl chloride polymer. The micromembrane separation device according to any one of claims 1 to 5, which is formed by: 7. The communicating porous body formed of a cross-linked polymer selected from the group consisting of a (meth) acrylic cross-linked polymer and a maleimide cross-linked polymer. The micromembrane separation device according to any one of the above items. 8. A gap having an inflow port and an outflow port is formed inside the base material, and the gap section has a height of 0.01 to 3 mm separating the inflow port and the outflow port, and a thickness of 0.01 to 0.01 mm. A micromembrane separation device, wherein the device is partitioned by a 3 mm partition, and the partition is formed of a communicating porous body. 9. The air gap according to claim 8, further comprising a primary outlet on the inlet side divided by the partition.
The micromembrane separation device according to the above. 10. The micromembrane separation device according to claim 8, wherein the communicating porous body constituting the partition is an aggregate of a plurality of capillaries and / or slit-like pores penetrating the partition. 11. A substrate having a void having an inflow port and an outflow port, wherein a solid substance is filled between the member (A) and the member (B), A base member having a void portion having a depth in the range of 0.01 to 3 mm as viewed from a direction perpendicular to the contact surface between the member (A) and the member (B), or a member (A) having a concave portion on the surface. ) And the member (A) are brought into close contact with the concave portion forming surface of the member (A), so that the depth as viewed from the direction perpendicular to the contact surface between the member (A) and the member (B) is 0.01 to 3 mm. The micromembrane separation device according to claim 8, 9 or 10, which is a substrate having a void portion formed therein. 12. The member (A) and the member (B) are made of a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, a polyester polymer, and a vinyl chloride polymer, respectively. The micromembrane separation device according to claim 11, which is a substrate formed of a polymer selected from the group consisting of: 13. The communication porous body formed of a crosslinked polymer selected from the group consisting of a (meth) acrylic crosslinked polymer and a maleimide crosslinked polymer. The micromembrane separation device according to any one of the above items. 14. (1) An energy ray-curable compound (a) is compatible with the energy ray-curable compound (a) in a concave portion provided on the surface of a base material. A first step of filling the energy ray-curable composition (C) containing the phase separation agent (b) that does not dissolve or swell the cured product of (a), (2) a partition that divides the recess into a plurality of portions Irradiate the energy beam to the
A second step of curing the energy ray-curable compound (a) to form a partition made of a communicating porous body, and (3)
A third step of removing the uncured energy ray-curable composition (C), wherein the substrate has a concave portion on the surface thereof, and the concave portion is formed in a plane parallel to the surface of the substrate. A method for manufacturing a micromembrane separation device, comprising a partition for dividing a concave portion into a plurality of portions, wherein the partition is made of a communicating porous body. 15. (1 ′) a first ′ step of filling an energy beam-curable composition (D) containing an energy beam-curable compound (a ′) into a concave portion provided on the surface of a substrate;
(2 ′) In the concave portion filled with the energy ray-curable composition (D), a thickness of dividing the concave portion into a plurality of portions is set to 0.1.
A part to be a partition wall of 0 to 1 to 3 mm is irradiated with energy rays except for a part to be a plurality of capillaries and / or slits penetrating the partition wall to cure the energy ray-curable composition (D). From the 2 ′ step of forming the partition wall made of the communicating porous body composed of the groove-shaped pores of (a) and (3 ′) the 3 ′ step of removing the uncured energy ray-curable composition (D) Characterized in that it has a concave portion on the surface of the substrate, the concave portion has a partition that divides the concave portion into a plurality of portions in a plane parallel to the surface of the substrate, and the partition has the partition. A method for producing a micromembrane separation device comprising a communicating porous body composed of a plurality of penetrating groove-like pores. 16. An energy ray-curable compound (a ′)
The method for producing a micromembrane separation device according to claim 15, wherein is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group. 17. An energy ray-curable compound (a), which is compatible with the energy ray-curable compound (a), in a void portion having an inflow port and an outflow port provided inside a base material. A first step of filling the energy ray-curable composition (C) containing a phase separator (b) that does not dissolve or swell the cured product of the energy ray-curable compound (a).
(2 ″) In the gap filled with the energy ray-curable composition (C), the energy ray-curable compound (a) is irradiated by irradiating an energy ray to a part serving as a partition separating the inflow port and the outflow port. To form a partition made of a communicating porous material, and (3 ") a third" step of removing the uncured energy ray-curable composition (C). A method for producing a micromembrane separation device, comprising: a partition wall separating an inflow port and an outflow port in a void portion of a substrate having an inflow port and an outflow port, wherein the partition wall comprises a communicating porous body. 18. A base material having a cavity having an inflow port and an outflow port, wherein a solid substance is filled between a member (A) and a member (B), and a void is formed as a defective part of the solid substance. 18. The microfilm according to claim 17, wherein the substrate is a substrate having a portion formed thereon, or a substrate comprising a member (A) having a concave portion on its surface and a member (B) closely adhered to the concave portion forming surface of the member (A). Manufacturing method of separation device. 19. An energy ray-curable compound (a) comprising:
The method for producing a micromembrane separation device according to claim 17, which is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group. 20. An energy-ray-curable composition (D) containing an energy-ray-curable compound (a ′) in a void having an inflow port and an outflow port provided in a base material (1 ′ ″). )), And (2 ''') a partition wall having a thickness of 0.01 to 3 mm separating the inflow port and the outflow port in the gap filled with the energy ray-curable composition (D). A portion to be formed is irradiated with energy rays except for a portion serving as a plurality of capillaries and / or slits penetrating the partition wall, and the energy ray-curable composition (D) is cured to form a plurality of capillaries and / or The second “″” step of forming a partition made of a communicating porous body composed of a slit, and the (3 ””) third step of removing an uncured energy ray-curable composition (D) Having an inflow port and an outflow port formed inside the substrate. A method for producing a micromembrane separation device comprising a partition in an air gap portion separating an inflow port and an outflow port, wherein the partition comprises a communicating porous body composed of a plurality of capillaries and / or slits penetrating the partition. 21. Energy ray-curable compound (a ′)
21. The method for producing a micromembrane separation device according to claim 20, wherein is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group. 22. A base material having a void having an inlet and an outlet, wherein a solid substance is filled between the member (A) and the member (B), and a void is formed as a defective part of the solid substance. 22. The microfilm according to claim 21, wherein the substrate is a substrate on which a portion is formed, or a substrate composed of a member (A) having a concave portion on its surface and a member (B) adhered to a concave portion forming surface of the member (A). Manufacturing method of separation device. 23. An energy ray-curable compound (a ′)
Is an energy ray-curable compound having a (meth) acryloyl group or a maleimide group.