JP2001137693A - Fine chemical device having liquid separating structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine chemical device capable of continuously performing extraction or oil-water separation by bringing a fine quantity of mutually immiscible liquids into contact with each other and separating. SOLUTION: A capillary flow passage is formed in the fine chemical device, the inside surface in the down stream end of the flow passage has a low contact angle part having <=25 deg. contact angle with water and a high contact angle part having >=10 deg. higher contact angle with water than that of the low contact angle part, a liquid separating chamber having a cross-sectional area 2-1,000 times of that of the capillary flow passage is formed and respective discharge passages from the low contact angle part and the high contact angel part are formed in the liquid separating chamber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microchemical device having a mechanism in which immiscible liquids flow in a capillary channel while contacting each other, and then are separated into respective liquids and flow out. Oil-water separation devices and liquid-liquid extraction microdevices in the fields of physical chemistry and chemical engineering; oil-water separation devices in the fields of synthetic chemistry and biochemistry, and synthesis microdevices involving liquid-liquid mass transfer; integrated type The present invention relates to a microdevice for preparing a sample that can be combined with a microanalytical device such as DNA analysis, microelectrophoresis, and microchromatography; and a microchemical device applicable to a microdevice for preparing an analytical sample such as mass spectrum and liquid chromatography.

[0002]

2. Description of the Related Art "High-speed molecular transport in microchannels" 99-1 Separations Science & Technology (SST) Seminar, sponsored by the Society of Polymer Science, 9 pages (1999) 250μm
Liquid-liquid extraction in a xylene / water system in a 100 μm deep microchannel.

[0003]

However, when the liquids are brought into direct contact with each other as described in the above-mentioned literature, it is considerably difficult to separate them again on a micro scale.

[0004] The problem to be solved by the present invention is to provide a microchemical device capable of directly contacting a very small amount of liquid that is immiscible with each other and then separating it again. An object of the present invention is to provide a microchemical device that can be used as an extraction device that increases the extraction speed by directly contacting with a scale and separates the contacted liquid again.

[0005]

Means for Solving the Problems As a result of intensive studies on a method for solving the above-mentioned problems, the present inventors have found that a room having a low contact angle and a high contact angle with water is provided at the downstream end of a narrow channel. By providing the outflow passages from the low and high contact angle portions, it is possible to separate the immiscible liquids flowing in the flow path in the form of a layer, a block, or a dispersion at the outflow end. The inventors have found that this is possible, and have completed the present invention.

That is, in order to solve the above problems, the present invention provides (I) a microchemical having a capillary channel having a cross-sectional area in the range of 1 × 10 ⁻¹² m ² to 1 × 10 ⁻⁶ m ^2. The device, wherein the cross-sectional area of the flow path is 2 to 10 at the downstream end of the flow path.
A separation chamber having a cross-sectional area of 00 times is provided,
The liquid separation chamber has a low contact angle portion having a relatively low contact angle with water on its inner surface, and a contact angle with water that is 10 times smaller than the low contact angle portion.
A micro-chemical device having a liquid separation mechanism, characterized by having a high contact angle portion higher than or equal to degrees and an outflow path provided from each of the low contact angle portion and the high contact angle portion of the liquid separation chamber. (Hereinafter, a “microchemical device having a liquid separation mechanism” is simply referred to as a “device.”).

In order to solve the above problems, the present invention provides (II) a contact angle α with water at a low contact angle portion of a liquid separation chamber and a contact angle β with water at a high contact angle portion of (a). ) Α ≦ 25 °, 35 ° ≦ β, (b) 25 ° <α ≦ 90 °, (α + 40 °) ≦ β ≦ 90 °, (c) α ≦ 9
A microchemical device according to the above (II), which satisfies at least one condition of 0 ° and 90 ° <β.

In order to solve the above-mentioned problems, the present invention is characterized in that (III) a flow path and a liquid separating chamber are formed between a member (A) and a member (B) which are in close contact with each other. A microchemical device according to the above (I) or (II) is provided.

In order to solve the above-mentioned problems, the present invention provides (IV) a microchemical device according to the above (III), wherein the member (A) and the member (B) are made of an organic polymer. .

Further, in order to solve the above-mentioned problems, according to the present invention, (V) the member (A) and the member (B) are each made of a polycarbonate polymer, a vinyl chloride polymer, a polyamide polymer, and a polyester polymer. The microchemical device according to the above (III), comprising a polymer selected from the group consisting of a coalesced polymer, a (meth) acrylic crosslinked polymer, and a maleimide crosslinked polymer.

Furthermore, in order to solve the above-mentioned problems, the present invention provides (VI) any one of the above items (I) to (V), wherein a plurality of inflow channels are formed connected to the upstream end of the flow channel. And a microchemical device according to (1).

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The shape of the substrate of the device of the present invention does not need to be particularly limited, and can take a shape according to the purpose of use. For example, it may be in the form of a sheet (including a film, a ribbon, and the like; the same applies hereinafter), a plate, a coating, a rod, a tube, and a molded article having a complicated shape. Is particularly preferred. A capillary channel (hereinafter, the “capillary channel” is simply referred to as a “channel”) is formed inside the substrate.

The base material is a member (A) and a member (B)
It is preferable that a flow path is formed between the member (A) and the member (B) which are in close contact with each other. The close contact referred to in the present invention refers to air-tight or liquid-tight contact, and includes non-adhesive contact, adhesion, and adhesion. Needless to say, the adhesion or the adhesion may be a contact through an adhesive or a pressure-sensitive adhesive. The structure of the base material may be, for example, a structure in which a portion between the member (A) and the member (B) other than the flow path is filled with a solid substance, or, for example, a groove may be formed on the surface. A structure may be used in which another member (B) is formed in close contact with the grooved surface of the member (A).

The shape of the member (A) is the same as that of the above-mentioned base material. The member (A) may be in a form integrated with another member, for example, a support. Member (A)
When is a coating film, it is used in a state of being integrated with the support. The material and shape of the support are also arbitrary, and for example, the material and shape shown in the case of the member (A) may be used. It is possible to form a plurality of microchemical devices on one member (A), or it is also possible to cut them after manufacturing to form a plurality of microchemical devices.

The shape of the member (B) is arbitrary, as long as it can be brought into close contact with the member (A) directly or via an adhesive or a pressure-sensitive adhesive. The shape and preferable shape of the member (B) are the same as those of the member (A). The member (B)
It is not necessary that a groove is formed on the surface, but a groove or a structure other than the groove may be formed. For example, the member (B)
It is also preferably a mirror image of the member (A) having a groove formed on the surface. When the member (B) is bonded on the member (A) having the groove formed thereon using the energy ray-curable compound as an adhesive, and the energy beam used by the member (A) is not transmitted. The member (B) needs to transmit the energy beam to be used.

The material of the chemical device of the present invention is arbitrary, and includes a polymer such as an organic polymer (hereinafter, simply referred to as a “polymer”), a crystal such as glass or quartz, a semiconductor such as ceramic, carbon, metal or silicon; And the like, but it is preferably a polymer in terms of ease of molding.

The polymer used as the material of the chemical device of the present invention, for example, the material of the member (A) or the member (B) may be a thermoplastic polymer or a thermosetting polymer. However, a thermoplastic polymer is preferable in terms of good moldability, and when forming grooves on the surface, it is easy to form grooves, the curing speed is high, and the surface is easily made hydrophilic. Crosslinked polymers are preferred. The material of the chemical device of the present invention may be composed of a polymer blend or a polymer alloy, or may be a composite or a laminate.

Examples of the polymer which can be preferably used as a material of the chemical device of the present invention include polystyrene, high impact polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, and polystyrene / acrylonitrile copolymer. Styrene-based polymers; polysulfone-based polymers such as porsulfone and polyethersulfone; poly (meth) acryl-based polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide-based polymers; polycarbonate-based polymers; Cellulose polymers such as polyurethane polymers; Chlorine polymers such as polyvinyl chloride and polyvinylidene chloride; Polyamide polymers such as nylon and aromatic polyamide; Aromatic polyimides and aromatic polyethers Polyimide polymers such as polyethylene and polypropylene; Polyether polymers and polythioether polymers such as polyphenylene oxide and polyphenylene sulfide; Polyester polymers such as polyethylene terephthalate and polyarylate; And fluorine-based polymers such as perfluoroalkoxyperfluoroethylene-tetrafluoroethylene copolymer (PFA). Further, as the energy ray-curable crosslinked polymer, 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 is preferable. Of course, the polymer may be a homopolymer or a copolymer.

Among these, polycarbonate, polyvinyl chloride, nylon, aromatic polyamide, polyimide, polyetherimide, and polyethylene terephthalate are excellent in solvent resistance, a wide range of usable solvents and excellent adhesiveness. , Polyarylate is preferable, from the viewpoint of moldability and price, polycarbonate, polyvinyl chloride,
Nylon and polyarylate are particularly preferred. Further, an energy ray-curable crosslinked polymer such as a poly (meth) acrylic crosslinked polymer and a polymaleimide bridge crosslinked polymer is also preferable.

When the chemical device of the present invention comprises the member (A) and the member (B) as the main members, these materials are shown as materials that can be used in the above-described chemical device of the present invention. Can be used. The material of the member (B) may be the same as the material of the member (A),
It may be different.

The channel of the device of the present invention has a cross-sectional area of 1 ×.
10^-12m^Two Or more, preferably 1 × 10^-Tenm^Two that's all
And 1 × 10^-6m^TwoOr less, preferably 1 ×
10 ^-7m^TwoThe following is a capillary channel. This channel
By flowing a plurality of liquids that are immiscible with each other,
For example, material exchange between liquids during distribution is possible.
Wear. If the flow path is smaller than this size, manufacturing and use are difficult.
If the flow path is larger than this size, the effect of the present invention
This is not preferable because the fruit tends to be small. Disconnection of flow path
The surface shape is arbitrary, for example, a rectangle (rectangular with rounded corners)
Including shape. The same applies below), trapezoid, circle, ellipse, slit
Which can be. The maximum diameter of the flow path cross section and the direction perpendicular to it
The ratio with the diameter can be set arbitrarily according to the application and purpose.
Generally, 1 to 10 is preferable, and 1 to 5 is more preferable.
No. These shapes and dimensions are constant over the entire flow path.
Need not be.

When the flow path is formed between the member (A) and the member (B), the flow path may be, for example, (a) a part other than the flow path between the member (A) and the member (B). The portion may be formed by filling a solid substance, or for example, (b)
Another member (B) may be formed in close contact with the grooved surface of the member (A) having the groove on the surface. The flow path in (a) is composed of the member (A) on the bottom surface when the member (B) is turned up, a solid substance filled on the side surface, and the member (B) on the top surface. The channel 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 or a pressure-sensitive adhesive applied to the member (B).

When the flow passage is formed between the member (A) and the member (B), the members (A) and (B) of the flow passage are formed.
The ratio of the dimension in the horizontal direction to the dimension in the vertical direction to the contact surface of
0.3-10 are preferable, and 0.5-5 are more preferable.

In the case where the flow path is formed between the member (A) and the member (B), for example, when the flow path is formed between the member (A) and the member (B), the member (A) and the member (B) are in close contact with each other. Shapes viewed from the direction perpendicular to the surface are straight, curved, spiral,
It may be zigzag or any other shape.

In the case of a structure in which the flow path is formed by filling a portion other than the flow path between the member (A) and the member (B) with a solid substance, the thickness of the solid substance is always uniform. It is not necessary, but preferably uniform.

A method for forming a structure in which a flow path is formed by filling a portion other than the flow path between the member (A) and the member (B) with a solid substance is described in, for example, the member (A) and the member (B). An energy-ray-curable composition is sandwiched between B), and energy rays are irradiated from the outside of the member (A) and / or the member (B) except for a portion serving as a flow path, and uncured energy-ray curing is performed. Method for removing the conductive composition, a method in which an adhesive sheet-like member cut out from a part to be a flow path is sandwiched between a member (A) and a member (B) to make close contact with each other, and protection to a part to be a flow path Put a substance, for example, a rod made of tetrafluoroethylene,
After filling and solidifying the polymerizable substance or the molten resin, a method of removing the protective substance can be employed. Although the number of steps in this method is small, it becomes difficult to remove the uncured energy ray-curable composition and the protective substance when the channel diameter is small,
This is suitable as a method for forming a channel having a relatively large size.

When the flow path is formed by adhering another member (B) to the grooved surface of the member (A) having a groove on the surface, the groove provided on the member (A) It may be formed as a so-called groove lower than the portion, or may be formed between walls standing on the surface of the member (A).
The method of providing a groove on the surface of the member (A) is arbitrary. For example, injection molding, solvent casting, melt replica method, cutting, etching, photolithography (including energy beam lithography), etching, vapor deposition, vapor deposition, A phase polymerization method, a method such as close contact between a sheet-like member and a plate-like member in which a portion to be a groove is cut out can be used. Member (A)
May be formed of a plurality of materials, and for example, may be formed of materials having different bottoms and side surfaces of the grooves. The member (A) may be provided with a structural portion other than the groove, for example, a structure serving as a liquid storage tank, a reaction tank, an analysis mechanism, or the like.

When the member (A) has a groove on the surface, the member (A) and the member (B) may be in close contact with each other by a method in which the groove on the surface of the member (A) is formed as a flow path. If
Optional, use of solvent type adhesive, use of solventless type adhesive, use of melt type adhesive, adhesion by applying solvent to the surface of member (A) and / or member (B), heat or ultrasonic Although fusion, etc. can be used, the use of a solventless adhesive is preferable, and a method of bonding by curing by energy beam irradiation using an energy ray-curable resin as the solventless adhesive is preferable. This is preferable because it enables precise bonding of the particles and has high productivity. It is also possible to adopt a method in which the groove is filled with a protective material and then bonded, and then the protective material is removed. The member (B) may be a cured product of the adhesive itself.

The non-adhesive contact between the member (A) and the member (B) may be, for example, a state in which the member (A) and the member (B) are fixed by a clamp, a screw, a rivet, or the like.

Although the contact angle of the microchemical device of the present invention with water on the inner surface of the flow path is arbitrary, the lower the lower, the more easily the two liquids that are immiscible with each other flow in a layer, and the higher the liquid-liquid contact efficiency. Therefore, it is preferable. The contact angle of the inner surface of the flow channel with water is preferably 25 ° or less, more preferably 15 ° or less, and most preferably 5 ° or less. The inner surface of the flow channel has a low contact angle portion where the contact angle with water is relatively low, and a high contact angle portion where the contact angle with water is at least 10 ° higher than the contact angle with water at the low contact angle portion of the flow channel. And that the low contact angle part of the flow path and the high contact angle part of the flow path are continuous without interruption from the upstream end to the downstream end of the flow path, respectively. It is preferable because it is stable and easy to flow. The contact angle of the high contact angle portion of the flow channel with water is preferably 35 ° or more, more preferably 45 ° or more, further preferably 70 ° or more, and most preferably 90 ° or more. However, in the device of the present invention, the two liquids that are immiscible with each other do not necessarily need to flow in a layered manner in the flow path, and can be separated in the liquid separation chamber even if they flow in a lump or in a dispersed state.

The device of the present invention has a cross-sectional area of 2 to 1000 times, preferably 3 to 100 times the cross-sectional area of the flow path at the downstream end of the flow path.
A liquid separation chamber having a cross-sectional area of 2 times, more preferably 4 to 30 times is provided. The cross-sectional area of the liquid separation chamber refers to the area of a cross section perpendicular to the liquid streamline direction. The sectional shape of the separation chamber is
The aspect ratio of the dimension is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. The upper limit of the aspect ratio does not need to be particularly set, but is preferably 100 or less, more preferably 30 or less from the viewpoint of ease of production. The length of the liquid in the liquid separating chamber in the streamline direction is arbitrary.

The liquid separating chamber has, on its inner surface, a low contact angle portion having a relatively low contact angle with water and a high contact angle portion having a contact angle with water higher than the low contact angle portion by 10 degrees or more. If the difference between the contact angles of the low contact angle portion and the high contact angle portion with water is less than this, it tends to be difficult to separate liquids that are immiscible with each other. Also, the lower the contact angle with water in the low contact angle part,
Even if the contact angle of the high contact angle portion with water is relatively low, the above-mentioned inconvenience is unlikely to occur.The higher the contact angle of the high contact angle portion with water, the higher the contact angle of the low contact angle portion with water. Even if it is high, the above-mentioned inconvenience is unlikely to occur.

When the contact angle of the low contact angle portion with water is α and the contact angle of the high contact angle portion with water is β, the following (A)
A combination that satisfies any one of conditions (a) to (c) is preferable.

(A) α ≦ 25 ° and 35 ° ≦ β
Is preferably α ≦ 10 ° and 35 °
≦ β is more preferable, and the larger the difference between α and β, the more preferable.

(B) It is preferable that 25 ° <α ≦ 90 ° and (α + 40 °) ≦ β ≦ 90 °.
It is preferable that the difference between β and β is large. Or,

(C) α ≦ 90 ° and 90 ° <β
It is preferable that the difference between α and β is large.

Further, the above (a) and (c) are simultaneously satisfied, that is, (d) α ≦ 25 ° and 90 °
<Β is more preferable, α ≦ 10 °, and most preferably 90 ° <β.

The high contact angle portion preferably has a contact angle with the hydrophobic liquid to be used of 90 ° or less.

A third portion other than the low contact angle portion and the high contact angle portion may be provided on the inner surface of the liquid separation chamber. The term “contact angle with water” as used in the present invention refers to a static angle measured by a droplet method. Prior to the measurement, the sample was allowed to stand in an atmosphere at a temperature of 24 ± 1 ° C. and a humidity of 65 ± 5% for 1 hour or more, and the temperature was kept at a temperature of 24 ± 1.
It is measured at 65 ° C and a humidity of 65 ± 5%. The measurement is performed after a stabilization time of 3 minutes after the placement. When the contact angle changes depending on the drying conditions of the sample, the lowest value is adopted.

In the cross section of the liquid separation chamber in a direction perpendicular to the liquid stream line, the number of portions occupied by the high contact angle portion and the low contact angle portion on the flow path surface may be singular or plural. Good, but preferably singular. In the cross section of the liquid separation chamber in the direction perpendicular to the streamline of the liquid, the location and ratio of the high contact angle portion and the low contact angle portion occupying the flow channel surface are arbitrary, but in the connection portion with the flow channel, When the cross section is divided into a low contact angle portion and a high contact angle portion, the depth / width ratio of each of the divided groove portions is preferably 1
It is more preferably 0.7 or less, most preferably 0.5 or less. The lower limit of the depth / width ratio is not particularly required, but is preferably 1/100 or more, more preferably 1/30 or more. By forming the liquid separation chamber in this manner, it becomes easy to separate the two liquids that have flowed into the liquid separation chamber in a lump or dispersed state.

In a section perpendicular to the flow line of the liquid in the liquid separation chamber at the connection portion with the outflow channel, the location and ratio of the high contact angle portion and the low contact angle portion occupying the flow channel surface are as follows. When the cross section is divided into a low contact angle portion and a high contact angle portion, the depth / width ratio of each of the divided groove portions is preferably 1 or more, more preferably 1.5 or more,
Most preferably, the shape is 2 or more. There is no particular need to set an upper limit for the depth / width ratio.
It is preferably at most 00, more preferably at most 30. By making the separation chamber in this way,
It is easy to make the two separated liquids flow out of the outflow channel independently.

In the cross section of the liquid separation chamber in the direction perpendicular to the liquid stream line, the location and ratio of the high contact angle portion and the low contact angle portion occupying the flow channel surface from the connection portion with the flow channel to the outflow channel. The intermediate state in the streamline direction leading to the connection portion is arbitrary, and may be shifted continuously, or may be shifted stepwise or discontinuously in one step. However, even in the case of a discontinuous transition, it is preferable that the high contact angle portion and the low contact angle portion are respectively continuous without interruption.

The length of the liquid separation chamber in the streamline direction is arbitrary,
The residence time of the liquid is preferably 1 second or more, preferably 10 seconds or more.
More preferably, the time is at least seconds.

The low contact angle portion and / or the high contact angle portion on the inner surface of the liquid separation chamber are used as materials constituting the wall surface of the liquid separation chamber, such as the member (A), the member (B), and the filled solid substance. It may be formed by using a material having an appropriate contact angle, or may be formed by surface treatment of the inner surface of the liquid separation chamber. The surface treatment may be performed on the material forming the separation chamber, and then the separation chamber may be formed, or may be performed after the formation of the separation chamber. The surface treatment for hydrophilization or hydrophobization may be performed only on the target site, or may be removed after the entire site is treated with the target site protected. A suitable method can be adopted depending on the processing method.

The method of hydrophilizing the surface of the liquid separation chamber by the surface treatment is optional. For example, plasma treatment, plasma polymerization,
Examples include corona discharge treatment, chemical modification of the surface, graft polymerization of a hydrophilic compound on the surface, and coating of a hydrophilic polymer.

As the plasma treatment or plasma polymerization, treatment in the presence of oxygen; a compound having an oxygen atom in a molecule such as acetone or an organic acid; or a compound such as an amine having a nitrogen atom in a molecule is preferable. Also, normal pressure plasma processing is possible.

As a method of chemical modification of the surface, for example,
Introduction of hydroxyl group, carboxyl group, amino group, amide group, etc. by halogenation and its substitution reaction, introduction of epoxy group and addition reaction thereto; sulfonation by contact with concentrated sulfuric acid, fuming sulfuric acid, persulfate; Nitration by contact with nitric acid or fuming nitric acid, and introduction of a hydroxyl group or amino group by substitution or reduction thereof; photochemical reaction using azide or the like.

Examples of the method of graft polymerization of a hydrophilic polymerizable compound include, for example, a method of subjecting a base material to a corona treatment, a plasma treatment, a radiation treatment, etc., and then contacting with a hydrophilic addition polymerizable compound, or a method of photopolymerization. Methods used, and the like.

Among these, the graft polymerization of a hydrophilic polymerizable compound is performed because the layer composed of the hydrophilic polymer is covalently bonded to the hydrophobic polymer constituting the base material. This is preferable because there is no danger of the hydrophilic layer peeling off or elution of the constituent components of the hydrophilic layer. Further, as the hydrophilic polymerizable compound, it is preferable to use a polymerizable compound having a carbon-carbon unsaturated double bond because the polymerization rate is increased.

The coating of a hydrophilic polymer is a method of applying a solution of a soluble polymer on a substrate in an arbitrary pattern by printing or the like. Examples of soluble polymers that can be used include polyhydroxymethyl methacrylate, polyvinyl alcohol, sulfonated cellulose, sulfonated polysulfone, and the like.

When the hydrophilic polymer is not chemically bonded to the substrate as in the coating method, the hydrophilic polymer may elute during use. It is preferable to use a crosslinked polymer. The layer made of a hydrophilic cross-linked polymer can be easily formed by a method of cross-linking after coating, or a coating of a hydrophilic cross-linkable polymerizable compound and cross-linking polymerization. Hydrophilic polymer coatings are preferred because they provide a high degree of hydrophilicity. When the coating of the hydrophilic polymer is performed by on-site polymerization of a hydrophilic polymerizable compound, the polymerization rate can be increased by using a polymerizable compound having a carbon-carbon unsaturated double bond as the hydrophilic polymerizable compound. It is preferable because it becomes higher.

The method of hydrophobization by surface treatment is optional, and examples include fluorine treatment, plasma treatment, plasma polymerization, chemical modification of the surface, graft polymerization of a hydrophobic compound on the surface, and coating of a hydrophobic polymer. Can be

The plasma treatment and the plasma polymerization are performed, for example,
By performing plasma treatment or plasma polymerization in the presence of fluorides such as carbon tetrafluoride, chlorides such as tetrachloroethane, and hydrocarbons such as methane and benzene,
Can be hydrophobized.

The chemical modification of the surface includes, for example, halogenation such as fluorination, chlorination, bromination, and the like, and alkylation by a substitution reaction thereof; photochemical reaction using an azide compound and the like.

The coating of a hydrophobic polymer is a method of applying a solution of a solvent-soluble polymer.

The graft polymerization of a hydrophobic compound onto the surface is, for example, a method in which a member is subjected to a surface treatment such as a corona treatment, a plasma treatment or a radiation treatment and then brought into contact with a hydrophobic addition-polymerizable compound; Surface grafting method, and the like.

The liquids that are immiscible with each other flow in the flow path of the device in a layered, dispersed, or bulk form, and enter the separation chamber. In the device of the present invention, even when liquids that are immiscible with each other flow in a lump in the flow path, the liquids can be separated in the liquid separation chamber and individually discharged from the respective flow paths.

The method of forming the liquid separation chamber is arbitrary.
It can be formed simultaneously with the flow channel in the same manner as the flow channel. That is, when the base material is formed between the member (A) and the member (B), the liquid separation chamber is also formed in the same plane as the flow path between the member (A) and the member (B). May be.

Outflow passages from the liquid separation chamber are provided from the low contact angle part and the high contact angle part of the liquid separation chamber. It is preferable to provide the outflow channels at positions separated from each other in the liquid separating chamber in order to complete the liquid separation. The contact angle with water on the inner surface of the outflow channel is arbitrary, but the contact angle with water of the outflow channel connected to the low contact angle portion is preferably 90 ° or less, and the outflow channel connected to the high contact angle portion is preferable. It is preferable that the contact angle of the channel with water is 90 ° or more, and the contact angle with the liquid discharged from the outflow channel is 90 ° or less. The outflow channel may be open to the outside of the device or may be connected to another structural part in the device.

The shape and structure of the outflow channel are arbitrary, and can be formed in the same manner as the flow channel or liquid separation chamber, or can be formed by a different structure or method. For example, when the base material is formed between the member (A) and the member (B), the outflow channel may also be formed between the member (A) and the member (B), or the member (A) ) And / or a hole penetrating the member (B). It is preferable to connect a tube to the outflow channel. The back pressure is adjusted by adjusting the length of the tube, so that even when the viscosities and flow rates of the immiscible liquids are different, stable liquid separation can be achieved.

When the device of the present invention is used for, for example, liquid-liquid extraction, it is connected to the upstream end of a flow path,
A plurality of inflow channels can be formed. Dimensions of the inflow channel,
The shape and the contact angle of the inner surface with water are arbitrary.

The device of the present invention has a structure other than these, such as a liquid storage tank, a reaction tank, a membrane separation mechanism, a flow control mechanism, a connection port outside the device,
Other inflow paths and other branched outflow paths may be formed.

In using the device of the present invention, for example, a hydrophilic liquid (usually an aqueous solution) and a hydrophobic liquid that is immiscible with the hydrophilic liquid can be introduced into the channel from an independent inflow channel. Alternatively, a dispersion solution can be introduced into the channel. Alternatively, a homogeneous mixed solution that undergoes phase separation due to a reaction or a change in temperature can be introduced into the channel. The hydrophilic liquid and the hydrophobic liquid that flowed in a layered, lump, or dispersed state in the flow path entered the separation chamber and were separated into two liquids, and the hydrophilic liquid was connected to the low contact angle portion of the separation chamber. After entering the outflow channel, the hydrophobic liquid enters the outflow channel connected to the high contact angle portion of the separation chamber, and the two liquids are separated and flow out. In order to completely separate the two liquids, adjust the balance of hydrophilicity / hydrophobicity near the connection port of the outflow channel, and adjust the outflow channel diameter and outflow channel length according to the flow rate ratio and viscosity. Can be reached. The plurality of liquids that are immiscible with each other may be three liquids.

[0064]

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"
Represents "parts by weight".

<Preparation of Energy Radiation-Curable Composition> The method of preparing the energy radiation-curable composition used in the examples was described.

[Preparation of energy ray-curable composition [e1]] Urethane acrylate oligomer having an average of three acrylic groups in one molecule (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.) 40 parts, nonylphenoxy polyethylene glycol (n = 8) acrylate ("M-114" manufactured by Toa Gosei Chemical Co., Ltd.) 60 parts, ultraviolet polymerization initiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Geigy) 5
Part and polymerization retarder 2,4-diphenyl-4-methyl-1
-0.1 parts of pentene (manufactured by Kanto Chemical Co., Ltd.) was mixed to prepare an energy ray-curable composition [e1]. Table 1 shows the contact angle of the cured product of this composition [e1] with water.

[Preparation of energy ray-curable composition [e2]] 40 parts of urethane acrylate oligomer (“Unidick V-4263”), dicyclopentanyl diacrylate (“R-684” manufactured by Nippon Kayaku Co., Ltd.) 60 parts, an ultraviolet polymerization initiator 1-hydroxycyclohexylphenyl ketone ("Irgacure 184") 5 parts and a polymerization retarder 2,4-diphenyl-4-methyl-1-pentene (Kanto Chemical Co., Ltd.) 0.1 part The mixture was mixed to prepare an energy ray-curable composition [e2]. Table 1 shows the contact angle of the cured product of this composition [e2] with water.

[Preparation of energy ray-curable composition [e3]] Urethane acrylate oligomer (“Unidick V-4263”) 100 parts, UV polymerization initiator 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184”) 5 parts And a polymerization retarder 2,4-diphenyl-
0.1 part of 4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) was mixed to prepare an energy ray-curable composition [e3]. Table 1 shows the contact angle of the cured product of this composition [e3] with water.
It was shown to.

[Preparation of energy ray-curable composition [e4]] 65 parts of urethane acrylate oligomer (“Unidick V-4263”), nonylphenoxy polyethylene glycol (n = 17) acrylate (manufactured by Daiichi Kogyo Seiyaku Kagaku) 35 parts of "N-177E"), 5 parts of an ultraviolet polymerization initiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184") and a polymerization retarder 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) )
0.1 part is mixed and the energy ray-curable composition [e4]
Was prepared. Table 1 shows the contact angle of the cured product of this composition [e4] with water.

[Preparation of energy ray-curable composition [e5]] Urethane acrylate oligomer (“Unidick V-4263”) 70 parts, nonylphenoxy polyethylene glycol (n = 17) acrylate (“N-177”)
E ") 30 parts, UV polymerization initiator 1-hydroxycyclohexyl phenyl ketone (" Irgacure 184 ")
5 parts and a polymerization retarder 2,4-diphenyl-4-methyl-
0.1 part of 1-pentene (manufactured by Kanto Chemical Co., Ltd.) was mixed to prepare an energy ray-curable composition [e5]. Table 1 shows the contact angle of the cured product of this composition [e5] with water.

[Preparation of energy ray-curable composition [e6]] Polytetramethylene glycol (average molecular weight 25
0) Maleimide capriate (JP-A-11-12440)
No. 3 by the method described in Synthesis Example 13. ) 7
0 parts and nonylphenoxy polyethylene glycol (n
= 17) 30 parts of acrylate (“N-177E”) were mixed to produce an energy ray-curable composition [e6]. Table 1 shows the contact angle of the cured product of this composition [e6] with water.

[Example 1] [Preparation of member (A)] The center of a 10 cm x 10 cm x 2 mm plate made of transparent rigid polyvinyl chloride (manufactured by Sekisui Molding Co., Ltd.) [p1] in an area of 5 cm x 2.5 cm ( The energy ray-curable composition [e1] is applied to the area including the area 1) by using a 127 μm bar coater, and the area not irradiated with a photomask is covered. Then, as shown in FIG. 1 of the polyvinyl chloride plate (1). Only the part to be the energy beam curable composition [e1] cured product layer 1 (2) was exposed to UV light of 50 mW / cm ² for 20 seconds in a nitrogen atmosphere using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc. Irradiated. After irradiation with ultraviolet rays, the uncured material is washed and removed with a water flow, so that an energy ray cured with a thickness of 102 μm and having the shape shown in FIG. The curable composition [e1] cured product layer 1 (2) was formed.

Next, the energy ray-curable composition [e
1] The energy ray-curable composition [e2] is applied to the unformed portion (2 ′) of the cured product layer 1 (2) using a 127 μm bar coater, and the portion (2) in FIG. 1 is covered with a photomask. After that, the same ultraviolet ray was irradiated in a nitrogen atmosphere. After irradiation with ultraviolet rays, the energy ray-curable composition [e
1) An energy-ray-curable composition having a thickness of 102 μm on the (2 ′) portion of the polyvinyl chloride plate (1) by washing and removing the uncured substance adhering to the surface of the cured substance layer 1 (2) [ e2] A cured product layer 1 (2 ′) was formed.

The energy ray-curable composition [e1] is applied onto the cured product layer 1 using a 127 μm bar coater, and the flow path (4), the inflow path (5), and the like shown in FIG.
Separation chamber low contact angle part (6), separation chamber high contact angle part (6 '),
After covering the part to be the outflow path (7) and the upper half part (3 ′) in the paper surface of FIG. 2 with a photomask, the same ultraviolet ray as above was irradiated in a nitrogen atmosphere for 30 seconds. After the ultraviolet irradiation, the uncured material was washed and removed with a stream of water to form a cured material layer 2 (3) of the energy ray-curable composition [e1].

Further, the energy ray-curable composition [e1] of the polyvinyl chloride plate (1) was formed on the portion where the cured product layer 2 (3) was not formed.
2] was applied using a 127 μm bar coater, and FIG.
The flow path (4), the inflow path (5 '), the separation chamber low contact angle section (6), the separation chamber high contact angle section (6'), and the outflow path (7 ') have the shapes shown in FIG. Part and the lower half part (3) in the drawing of FIG.
Was covered with a photomask, and then irradiated with the same ultraviolet rays for 30 seconds in a nitrogen atmosphere. After irradiating the ultraviolet rays, the energy beam-curable composition [e1] cured product layer is washed and removed by a water stream to remove the uncured material attached to the surface of the cured product layer 2 (3). 2 (3 ′) was formed.

The member having undergone the above-described steps is provided as a defective portion of the energy ray-curable composition [e1] cured product layer 2 (3) and the energy ray-curable composition [e2] cured product layer 2 (3 ′). A groove-shaped flow path (4) having a width of 240 μm, a depth of 102 μm, and a length of 3 cm, an inflow channel (5, 5 ′) having a width of 120 μm and a depth of 102 μm, and a separation chamber (6) of 3 mm × 3 mm, respectively. Outflow channel with a width of 120 μm and a depth of 102 μm (7,
7 ′) is formed. Then the inflow channel (5, 5 ')
In addition, a hole having a diameter of 0.5 mm is formed at the end of the outflow channel (7, 7 ') to form an inflow port (8, 8') from outside the device and an outflow port (9, 9 ') outside the device. And the member (A)
[A1] was obtained.

[Adhesion of member (B)] Polypropylene biaxially stretched film (“FOR” manufactured by Nimura Chemical Co., Ltd., thickness 30 μm)
m) The energy ray-curable composition [e3] is applied to the corona-treated surface (not shown) using a 127 μm bar coater, and then irradiated with the same ultraviolet ray as described above for 1 second in a nitrogen atmosphere. The coating film was in an incompletely cured state although the fluidity was lost. The coating film surface is bonded to the grooved surface of the member (A) [A1], and the same ultraviolet light is irradiated from the polypropylene biaxially stretched film side for another 60 seconds to completely cure the coating film. A sheet-shaped member (B) [B1] having a thickness of 103 μm and composed of the energy ray-curable composition [e3] cured product (10) is simultaneously formed and adhered to the surface of the member (A) [A1]. Capillary channel (4) having a height of 102 μm, a width of 240 μm, and a length of 3 cm, a capillary inflow channel (5, 5 ′) having a width of 120 μm and a depth of 102 μm, 3 mm × 3 mm × 102 μm
Separation chamber (6, 6 ′), width 120 μm, depth 102 μm
Outflow channels (7, 7 ′) were formed. afterwards,
The polypropylene biaxially stretched film was peeled off, and a 5 cm × 2.5 cm area shown in FIG. 2 was cut out to obtain a microchemical device [D1].

[Contact Angles of Each Part with Water] The contact angles of the raw materials used with water are shown in Table 1. Micro chemical device [D
The liquid separation chamber (6, 6 ′) of [1] has a low contact angle of 22 ° with water on the surface on the member (A) side near the connection port with the flow path and on the upper side surface in FIG. The remaining portion of the surface on the member (A) side and the surface on the member (B) side in the liquid separation chamber (6, 6 ′) having a contact angle with water of 68 ° are corner portions (6). The contact angle portion (6 '), the lower side surface of the liquid separation chamber in FIG.
Was a high contact angle portion. Further, the surface on the member (A) side near the connection port with the outflow channel (7 ′) of the liquid separation chamber (6) is as follows:
The contact angle with water was a high contact angle portion of 91 °. In the flow path (4), the contact angle with water on the surface on the member (A) side and one side surface was 22 °, the other side surface was 91 °, and the surface on the member (B) side was 68 °. . The outflow channel (7) has a contact angle of 22 ° with water on the surface on the member (A) side and both side surfaces, and a contact angle with water of 68 ° on the member (B) side. '), The contact angle with water on the surface on the member (A) side and on both side surfaces was 91 °, and the surface on the member (B) side was 68 °.

[Liquid-Liquid Contact Test] The microchemical device [D1] was placed so that the member (A) was on the upper side, water was injected from the inlet (7) with a microsyringe, and the outlet ( after starting the outflow from 9) at microsyringe inlet (7 ') from the injected n- hexane and the flow rate both the 0.01 mm ³ / sec, the two-liquid flow path (4)
Flows in a layer form, passes through a liquid separation chamber (6), and water flows out of an outflow path (7).
Then, n-hexane entered the outflow channel (7 ') and flowed out of the outlet (9').

When the flow rate of water was increased by 0.5 times and the flow rate of n-hexane was increased by 1.5 times, the water and n-hexane respectively aggregated and formed a lump in the flow path (4). As it flows, water adheres to the low contact angle part (6) of the separation chamber, and n-hexane adheres to the high contact angle part (6 ′) of the separation chamber and is separated. (7) and outflow from the outflow channel (7 '). Furthermore, at this time, there was no change in the state of independent outflow even if there was a sudden change in the flow rate or a change in the attitude of the device accompanying acceleration.

<Comparative Example 1> In this comparative example, the difference between the contact angle with water at the low contact angle portion and the contact angle with water at the high contact angle portion of the liquid separation chamber was less than 10 °. .

[Production of microchemical device] Example 1
In the same manner as in Example 1 except that the energy ray-curable composition [e4] was used instead of the energy ray-curable composition [e2] and the energy ray-curable composition [e3], Device [CD1] was produced.

[Contact Angle of Each Part with Water] In other words, the liquid separation chambers (6, 6 ') of the microchemical device [CD1] are located on the surface of the member (A) near the connection port with the flow path and in FIG. Is a low contact angle portion (6) having a contact angle of 22 ° with water on the upper side surface of the paper surface, the remaining portion of the surface on the member (A) side in the liquid separation chamber (6, 6 ′), and The surface on the member (B) side had a high contact angle portion (6 ′) having a contact angle with water of 68 °, and the lower side surface of the liquid separating chamber in FIG. 2 was 30 °. In addition, the surface on the member (A) side near the connection port with the outflow path (7 ′) of the liquid separation chamber (6) had a contact angle with water of 30 °. In the channel (4), the contact angle between the surface on the member (A) side and one side surface with water was 22 °, the other side surface was 30 °, and the surface on the member (B) side was 68 °. . The outflow channel (7) has a contact angle of 22 ° with water on the surface on the member (A) side and both side surfaces, and a contact angle with water of 68 ° on the member (B) side. '), The contact angle with water on the surface on the member (A) side and on both side surfaces was 30 °, and the surface on the member (B) side was 68 °.

[Liquid-Liquid Contact Test] The same test as in Example 1 was conducted on the microchemical device [CD1]. At a volume flow ratio of 1: 1, water and n-hexane flowed in layers, and fine adjustment was performed. When this was done, it was possible to make it flow out independently from the outflow channel, but it was quite difficult, and it was not separated in the separation chamber due to slight flow rate changes and changes in the device attitude.
Both water and n-hexane flowed out from both or one of the outflow channel (7) and the outflow channel (7 ′).

When the volume flow ratio is 0.5: 1.5,
The two liquids are respectively agglomerated, aggregated and flow through the flow path, and are not separated in the liquid separation chamber, and both water and n-hexane are discharged from both or one of the outflow path (7) and the outflow path (7 ′). Leaked.

That is, if the difference between the contact angle with water at the low contact angle portion and the contact angle with water at the high contact angle portion of the separation chamber is 8 °, the two immiscible liquids will not be sufficiently separated. I understand.

<Embodiment 2> In this embodiment, an example was shown in which the difference between the contact angle with water at the low contact angle portion and the contact angle with water at the high contact angle portion of the liquid separation chamber was slightly more than 10 °. .

[Production of microchemical device] Example 1
In the same manner as in Example 1 except that the energy ray-curable composition [e2] was used instead of the energy ray-curable composition [e2] and the energy ray-curable composition [e3], Device [D2] was produced.

[Contact Angle of Each Part with Water] The microchemical device [D2] is provided on the surface on the member (A) side near the connection port with the flow path (4) of the liquid separation chamber (6, 6 '). The contact angle of the side surface of the member with water is 22 °, the portion of the member (A) side near the connection port with the outflow passage (7 ′), and the member (B) side surface and the other side surface are 36 °. there were. The flow path (4) has a contact angle of 22 ° with water on the surface on the member (A) side and one side surface,
The other side surface and the surface on the member (B) side were 36 °. The outflow channel (7) has a contact angle with water on both sides of 22 °, the surface on the member (A) side and the surface on the member (B) side is 36 °, and the outflow channel (7 ′) has an entire inner surface. Was 36 °.

[Liquid-Liquid Contact Test] The same test as in Example 1 was conducted on the microchemical device [D2]. When the volume flow ratio of water to n-hexane was 1: 1, the same as in Example 1 was performed. , Water and n-hexane flow in layers in the flow path (4), are separated in the separation chambers (6, 6 '), and are separated into the outflow path (7) and the outflow path (7'). , And flowed out from the outlet (9) and the outlet (9 '), respectively. However, when the flow rate of n-hexane is constant and the flow rate of water is 1.5
As a result, water flowed out of the outlet (8 ') simultaneously with n-hexane.

When the volume flow ratio is 0.5: 1.5,
The two liquids agglomerated each other and formed a lump and flowed through the flow path.
The liquid was separated in the liquid separation chamber, and could be independently discharged from the outflow channel (7) and the outflow channel (7 ′). However, it is not separated in the liquid separation chamber due to a change in the flow rate or a change in the position of the device accompanied by an acceleration, and both water and n-hexane are discharged from both or one of the outflow channel (7) and the outflow channel (7 ′). Tend to spill.

That is, if the difference between the contact angle with water at the low contact angle portion and the contact angle with water at the high contact angle portion of the liquid separation chamber is 14 °,
It can be seen that it is possible to separate and flow out two liquids that are immiscible with each other.

[Example 3] [Production of member (A)] Polycarbonate ("Iupilon S-200" manufactured by Mitsubishi Engineering-Plastics Corporation)
0 ") The energy ray-curable composition [e1] of 127 μm in a range including a range (11) of 5 cm × 2.5 cm at the center of a 10 cm × 10 cm × 2 mm plate (not shown) made of [p2]. After application using a bar coater, through a photomask, into a 3 mm × 1.5 mm area (12) shown in FIG. 3 using a light source unit for a multilight 200 type exposure apparatus manufactured by Ushio Inc. in a nitrogen atmosphere. 50 mW / cm ² UV light 2
Irradiation was performed for 0 second to form a cured product layer 1 (12) of the energy ray-curable composition [e1] having a thickness of 102 μm in a range (12) of 3 mm × 1.5 mm shown in FIG. After the ultraviolet irradiation, the uncured portion was washed and removed with running water.

Next, 12 parts of the energy ray-curable composition [e2] was added to the remaining part of the polycarbonate plate (11).
After applying using a 7 μm bar coater, the same ultraviolet ray is irradiated for 20 seconds to the portion other than the energy ray-curable composition [e1] cured product layer 1 (12) for 20 seconds, and the energy ray-curable composition [e2] cured product Layer 1 (12 ') was formed.

Next, the energy ray-curable composition [e2] was applied on these layers using a 127 μm bar coater, and then, through a photomask, the flow path (14) and the liquid separation chamber shown in FIG. The part to be (15, 15 ') was covered with a photomask and irradiated with the same ultraviolet ray in a nitrogen atmosphere. After the ultraviolet irradiation, the uncured material is washed and removed with a water stream and acetone to form a groove having a width of 210 μm and a depth of 102 μm to be a flow path (14) and a separation chamber (15) having the shape shown in FIG. , 15 ′) having a recess having a width of 3 mm, a length of 3 mm and a depth of 102 μm, and a thickness of 102 μm.
m of the energy ray-curable composition [e1] cured product layer 2 (1
3) was formed to obtain the member (A) [A3]. At this time,
Energy ray curable composition [e1] cured product layer 1 of FIG.
(12) was formed on the bottom surface on the lower side in the drawing of FIG. 4 of the concave portion that should become the liquid separation chamber (15, 15 ′).

[Adhesion of the member (B)] The ultraviolet irradiation pattern is a mirror image in the case of the member (A), and the cured layer 3 (19 ') of the energy ray-curable composition [e2] is formed. 5 was applied to the polycarbonate plate (18) shown in FIG. 5 in the same manner as in the first half of the production of the member (A) except that the ultraviolet irradiation time was 2 seconds. Composition [e1] cured product layer 3 (19)
And the energy ray-curable composition [e2] cured product layer 3 (1
The precursor of the member (B) in which a layer of the semi-cured material having lost the fluidity to be 9 ′) was formed was obtained.

Next, the layer of the semi-cured material formed on the member (B) is bonded to the surface of the member (A) [A3] where the groove is formed so that the pattern overlaps, and then the same ultraviolet rays as above are applied. By further irradiating for 30 seconds to completely cure the coating film, the energy ray-curable composition [e1] cured product layer 3
(19) At the same time as forming the members (B) and [B3] composed of the energy ray-curable composition [e2] cured product layer 3 (19 ′) and the polycarbonate plate (18), the member (A)
Adhered to the surface of [A3], between them 210 μm wide,
A capillary channel (14) having a height of 102 μm and a length of 3 cm,
And a liquid separation chamber (1 mm wide, 3 mm long, 102 μm deep)
5, 15 ').

Next, at the end of the flow path (14), the end of the low contact angle part (15) of the separation chamber and the end of the high contact angle part (15 ') of the separation chamber, the member (A) , Member (B)
, A drill hole with a diameter of 0.5 mm is drilled into the member (A) [A3]
After forming the inflow channel (16), the outflow channel (17), and the inflow channel (16 ′) and the outflow channel (17 ′) that penetrate the member (B) [B3], 5 cm × 2.5cm
Was cut out to produce a microchemical device [D3].

[Contact Angles of Each Part with Water] The contact angles of the materials used with water are shown in Table 1. Micro chemical device [D
In [3], the inner surface of the liquid separation chamber (15, 15 ') has a low contact angle of 22 [deg.] With the lower half of the member (A) surface and the member (B) surface in FIG. Part (1
5), the upper half of the surface of the member (A) and the surface of the member (B) in FIG. 6 in FIG. 6 has a high contact angle portion (15 ′) having a contact angle with water of 91 ° and a height of 91 ° on all side surfaces It was the contact angle part. The inner surface of the channel (14) has a contact angle with water of 91%.
°, the contact angle of the inner surface of the outflow passage (16) with water at the connection portion with the low contact angle portion (15) of the separation chamber is 22 °, and the contact angle with the high contact angle portion (15 ′) at the connection portion. Outflow channel (16)
The contact angle of the inner surface with water was 91 °.

[Liquid-liquid contact test] The microchemical device [D3] was connected to the inflow path (16, 16 ') and the outflow path (17, 16).
17 ′) is installed so as to face the side of the device, micro-syringes are connected to the inflow channels (16, 16 ′), and water is supplied from the inflow channel (16) and n− is supplied from the inflow channel (16 ′).
When hexane was injected at a flow rate of 0.01 mm ³ / sec, water and n-hexane respectively flowed in a lump, but the low contact angle portion (15) of the separation chamber and the high contact angle of the separation chamber (15). N-Hexane gathered in the portion (15 '), water flowed out of the outflow channel (17), and n-hexane flowed out of the outflow channel (17'). Even when the flow rate of n-hexane was kept constant and the flow rate of water was changed 0.5 to 2 times, water and n-hexane were separated and flowed out.

Example 4 [Preparation of Material for Forming Hydrophilic Layer] 5 parts of polyethylene glycol mono-4-nonylphenyl ether (n ′ = 10) (“PMNE10” manufactured by Tokyo Chemical Industry Co., Ltd.), 2-methacryloyloxy A solution composed of 5 parts of ethyl acid phosphate (“MR200” manufactured by Daihachi Chemical Industry Co., Ltd.) and 90 parts of water was prepared as a material for forming a hydrophilic layer.

[Production of member (A)] 10 cm × 10 cm × 2 made of polycarbonate (“Iupilon S-2000” manufactured by Mitsubishi Engineering-Plastics Corporation) [p2]
5cm x 2.5cm area (1
In the range including 1), the energy ray-curable composition [e1]
Was applied using a 127 μm bar coater, and then passed through a photomask into a 3 mm × 1.5 mm area (12) shown in FIG. 3 using a light source unit for a multilight 200 type exposure apparatus manufactured by Ushio Inc. 50mW / cm in atmosphere
^By irradiating the ultraviolet ray of No. ² for 3 seconds, a semi-cured coating film which was not completely cured was obtained. After the ultraviolet irradiation, the uncured material in the non-irradiated portion was removed with a water stream. After removing the uncured material, the semi-cured coating film is put into a hydrophilic layer forming material, and the same ultraviolet light is irradiated for 40 seconds to completely cure the coating film,
A cured product layer 1 (12) having a thickness of 102 μm, in which a hydrophilic compound was bonded by graft polymerization to a substantially negligible thickness on the surface, was formed. The contact angle of this coating film with water was 5 °.

Further, 12 parts of the energy ray-curable composition [e2] was added to the remaining part of the polycarbonate plate (11).
After applying using a 7 μm bar coater, the same ultraviolet ray is irradiated for 20 seconds to the portion other than the energy ray-curable composition [e1] cured product layer 1 (12) to form the energy ray-curable composition [e2]. A cured product layer 1 (12 ′) was formed.

Next, the energy ray-curable composition [e2] was applied on these layers using a 127 μm bar coater, and then, through a photomask, the flow path (14) and the liquid separation shown in FIG. The portions to be chambers (15, 15 ') were covered with a photomask and irradiated with the same ultraviolet rays as described above in a nitrogen atmosphere. After the ultraviolet irradiation, the uncured material is washed and removed with a water stream and acetone to form a flow path (14) having the shape shown in FIG.
3mm wide to be a groove and a liquid separation chamber (15, 15 ')
Thickness 102 having a concave portion having a length of 3 mm and a depth of 102 μm
μm energy ray-curable composition [e1] cured product layer 2
(13) was formed to obtain the member (A) [A4]. At this time, the energy ray-curable composition [e1] cured product layer 1 (12) in FIG. 1 is positioned below the bottom of the concave portion that should become the low contact angle portion (15) of the liquid separation chamber, in the paper plane in FIG. It was formed in a position occupying half.

[Adhesion of Member (B)] A portion to be the mirror image body when the ultraviolet irradiation pattern is the member (A) and to become the layer 3 (19 ') of the cured product of the energy ray-curable composition [e2]. The polycarbonate plate (18) having the shape of the mirror image of FIG. 3 shown in FIG. 5 in the same manner as in the first half of the production of the member (A) [A4], except that the ultraviolet irradiation time to the member was 3 seconds.
The energy ray-curable composition [e1] cured product layer 3 (1
9) and energy ray-curable composition [e2] cured product layer 3
A member (B) precursor in which a layer of a semi-cured material having lost fluidity to be (19 ′) was formed was obtained.

Next, the layer of the semi-cured material formed on the member (B) is bonded to the groove-formed surface of the member (A) [A4] so that the pattern is overlapped, and the same ultraviolet rays as described above are further applied for 30 minutes. The cured product layer 3 of the energy ray-curable composition [e1] is obtained by completely irradiating the coating film by irradiating for 2 seconds.
(20) At the same time as forming the members (B) and [B4] composed of the cured product layer 3 (19 ′) of the energy ray-curable composition [e2] and the polycarbonate plate (18), the member (A)
Adhered to the surface of [A4] with a width of 210 μm between them,
Capillary channel (14) with a height of 102 μm and a width of 3
mm, length 3 mm, depth 102 μm
5 ′).

Next, the upstream end of the flow path (14), the low contact angle part (15) end of the liquid separation chamber, and the high contact angle part (1) of the liquid separation chamber
5 ') An inflow passage (16) and an outflow passage (17) penetrating through the member (A) [A3] and an inflow penetrating through the member (B) [B3] are drilled at the ends. Road (1
After forming 6 ′) and the outflow channel (17 ′), a range of 5 cm × 2.5 cm shown in FIG. 2 was cut out to produce a microchemical device [D3].

[Contact Angles of Each Part with Water] The contact angles of the materials used with water are shown in Table 1. Micro chemical device [D
3] is that the inner surface of the liquid separation chamber (15, 15 ′) is a member (A)
2 is a low contact angle portion where the contact angle with water is 5 °, and the lower half of the surface of the member (A) and the surface of the member (B) in FIG. The high contact angle part where the half part has a contact angle with water of 91 ° and all sides are 91 °
Of high contact angle. In addition, the flow path (1
The contact angle with water on the inner surface of 4) is 91 °, and the contact angle with water on the inner surface of the outflow passage (16) at the connection portion with the low contact angle portion (15) of the liquid separation chamber is 22 ° and high. The contact angle with the water on the inner surface of the outflow channel (16 ') at the connection with the contact angle portion (15') was 91 °.

[Liquid-Liquid Contact Test] The same test as in Example 3 was performed, and the same result as in Example 3 was obtained.

Example 5 In Example 3, the energy ray-curable composition [e2] of the member (A) was used.
Energy ray-curable composition [e2] on (12 ′)
When coating with a bar coater of 127 μm, 30
By using a bar coater of 0 μm, a thickness of 220 μm can be obtained.
μm energy ray-curable composition [e2] cured layer 2
(13) that the flow path dimension is 300 μm in width,
A height of 220 μm, a drill hole of 1.6 mm in diameter as an outflow channel (17 ′), an outer diameter of 1.6 mm and an inner diameter of 0.
Pass a 5 mm polytetrafluoroethylene tube through the channel (1
4) Inserted and fixed to the position, and the outflow channel (1
As 7), a drill hole having a diameter of 0.5 mm is drilled up to the position of the flow path (14), and a half hole up to the depth of the flow path (14) is formed as a drill hole having a diameter of 1.6 mm. Microchemical device [D5] in the same manner as in Example 3 except that a tube made of polytetrafluoroethylene having a diameter of 6 mm and an inner diameter of 0.5 mm was inserted and fixed to half the depth of the position of the flow path (14). Was prepared.

[Contact Angle of Each Part with Water] The microchemical device [D5] has a contact angle with water on the inner surface of the outflow path (17) at the connection part with the low contact angle part (15) of the separation chamber.
°, and the same as the microchemical device [D3], except that the contact angle with water on the inner surface of the connection portion of the outflow passage (17 ′) with the liquid separation chamber high contact angle portion (15 ′) was 110 °. there were.

[Liquid-Liquid Contact Test] The microchemical device [D5] was connected to the inflow path (16, 16 ') and the outflow path (17, 16).
17 ′) is installed so as to face the side of the device, micro-syringes are connected to the inflow channels (16, 16 ′), and water is injected from the inflow channel (16) at a flow rate of 0.04 mm ³ / sec. Water flowed out of the tube connected to the outflow channel (17). Then, while n-hexane was injected at a flow rate of 0.04 mm ³ / sec from the inflow path (16 ′) while water was similarly injected, the water and n-hexane respectively aggregated and flowed in a lump. In the chambers (15, 15 '), they were coagulated and separated, and water flowed out of the tube connected to the outflow channel (17), and n-hexane flowed out of the tube connected to the outflow channel (17').

Further, even if the flow rate of n-hexane is fixed and the flow rate of water is changed to 0.5 to 2 times, water and n-hexane are separated and flow out, and the volume flow ratio of water and n-hexane is changed. Was set to 1, and even if the total flow rate was tripled, water and n-hexane were separated and flowed out. Furthermore, there was no change even if there was a stepwise change in the flow rate or a change in the attitude of the device accompanying acceleration.

<Example 6> [Preparation of microchemical device] Example 1 was repeated except that the energy ray-curable composition [e6] was used in place of the energy ray-curable composition [e2]. In the same manner as in No. 1, a microchemical device [D6] was produced.

[Contact Angle of Each Part with Water] The microchemical device [D6] has a high contact angle portion where the member (B) surface and the side surface of the liquid separation chamber (6, 6 ') have a contact angle of 45 ° with water. (6 ′), the contact angle of the outflow path (7 ′) with the water on the surface of the member (B) is 45 °, and the entire inner surface of the outflow path (7) has a contact angle of 45 °. Other than the micro chemical device [D
1].

[Liquid-Liquid Contact Test] The same test as in Example 1 was performed on the microchemical device [D6]. When the volume flow ratio between water and n-hexane was 1, the same as in Example 1 was performed. Then, water and n-hexane flow in a layered manner in the flow path (4) and are separated in the separation chambers (6, 6 ′), and the water and n-hexane are separated in the outflow path (7) and the outflow path (7). '), Respectively, and flowed out from the outlet (9) and the outlet (9'). However, when the flow rate of n-hexane was kept constant and the flow rate of water was increased by a factor of 1.5, n-hexane was supplied from the outlet (8 ').
Water eluted with hexane.

When the volume flow ratio of water to n-hexane was 0.5: 1.5, the two liquids were agglomerated and formed a lump and flowed through the flow path. )
The outflow path (7) and the outflow path (7 ′) can be independently discharged. However, it is not separated in the liquid separation chamber due to a stepwise change in the flow rate or a change in the attitude of the device accompanying acceleration, and both water and n-hexane are discharged from both or one of the outflow channel (7) and the outflow channel (7 ′). Tend to spill.

That is, when the difference between the contact angle of water at the low contact angle portion and the contact angle of water at the high contact angle portion of the liquid separation chamber is 10 ° or more, two liquids that are immiscible with each other are separated and discharged. It turns out that it is possible.

<Embodiment 7> This comparative example shows an example in which the sectional area of the liquid separation chamber is 2.5 times the sectional area of the flow path.

[Preparation of Microchemical Device] Example 5
In Example 5, a microchemical device [D7] was produced in the same manner as in Example 5, except that the dimensions of the low contact angle portion and the high contact angle portion of the liquid separation chamber were 750 μm in width and 220 μm in height.

[Liquid-Liquid Contact Test] The same test as in Example 5 was performed on the microchemical device [D7]. As a result, water and n-hexane respectively aggregated and separated in the liquid separating chamber, and the outflow path (17) ) And n-hexane flowed out of the tube connected to the outlet channel (17 '). However, when the volume flow ratio of water and n-hexane was set to 1 and the total flow rate was tripled, the separation was incomplete.

<Comparative Example 2> In this comparative example, an example in which the cross-sectional area of the liquid separation chamber is the same as the cross-sectional area of the flow channel is shown.

[Production of microchemical device] Example 5
In Example 5, except that the widths of the low contact angle portion and the high contact angle portion of the liquid separation chamber section were each set to １ ／ of the flow path width, and the liquid separation chamber cross-sectional area was the same as the flow path cross-sectional area. Similarly, a microchemical device [CD2] was manufactured.

[Liquid-Liquid Contact Test] When the same test as in Example 5 was performed on the microchemical device [CD2], water and n-hexane were not separated in the liquid separating chamber, and were connected to the outflow channel (17). Both water and n-hexane flowed out of both the tube connected and the tube connected to the outflow channel (17 '). That is, when the cross-sectional area of the liquid separation chamber is the same as the cross-sectional area of the flow path, it can be seen that the two liquids that have flowed in the flow path in a lump are not separated in the liquid separation chamber.

<Example 8> [Production of microchemical device] In Example 1, instead of polycarbonate [p2], transparent rigid polyvinyl chloride [p1] was used as a material for members (A) and (B). ], Nylon 6 (“A4H” manufactured by BASF Japan) [p3], and a polyarylate resin (“U polymer U-70” manufactured by Unitika Ltd.) [p4], respectively, except that they were used. Thus, microchemical devices [D8-1 to D8-1] were produced.

[Liquid-Liquid Contact Test] The same test as in Example 3 was performed on the microchemical device [D8-1-3], and the same result as in Example 3 was obtained.

<Application Example> [Extraction Test] The microchemical device [D3] prepared in Example 3 was connected to the inflow path (16, 16 ′) and the outflow path (17, 16 ′).
17 ′) is installed so as to face the side of the device, micro-syringes are respectively connected to the inflow channels (16, 16 ′), and a 0.1N aqueous sodium hydroxide solution and an inflow channel (16 ′) are connected through the inflow channel (16). ) From which xylene solution in which phenolphthalene is dissolved until saturation is 0.01 mm ³ respectively.
The solution and the xylene solution flowed together in a lump when injected at a rate of 1 / sec.
In 5), the aqueous solution and the xylene solution collected in the high contact angle portion (15 ') of the liquid separating chamber, and the aqueous solution and the xylene solution flowed out of the outflow channel (17) and (17'). At this time, the injected 0.1N sodium hydroxide aqueous solution and xylene solution, and the outflowing xylene solution were both colorless and transparent, but the outflowing 0.1N sodium hydroxide aqueous solution was pale red. That is, phenolphthalene was extracted from the xylene phase to the aqueous phase.

[0128]

[Table 1] Contact angle with water of the material used in this example

[0129]

The microchemical device of the present invention does not require a diaphragm or a batch type liquid separation device, has a simple structure, and is an extremely small chemical device for extraction. And so on.

[Brief description of the drawings]

FIG. 1 is a crushed plan view of a member (A) in the process of manufacturing a microchemical device manufactured in an example as viewed from a direction perpendicular to the surface thereof.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyvinyl chloride board 2 Energy ray curable composition [e1] Cured material layer 1 2 'Energy ray curable composition [e2] Cured material layer 1

FIG. 2 is a diagram showing a member of the microchemical device manufactured in the example.
It is the crushing top view seen from the direction perpendicular | vertical to the surface of (B).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyvinyl chloride board 2 'Energy-ray-curable composition [e2] Cured material layer 1 3' Energy-ray-curable composition [e2] Cured material layer 2 4 Flow path 5 Inflow path 5 'Inflow path 6 Separation chamber ( 6 'Separation chamber (high contact angle section) 7 Outflow path 7' Outflow path 8 Inflow port 8 'Inflow port 9 Outflow port 9' Outflow port 10 Cured product of energy ray-curable composition [e3]

FIG. 3 is a crushed plan view of a member in the process of manufacturing the microchemical device manufactured in Example 3 as viewed from a direction perpendicular to the surface of the member (B).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Polycarbonate board 12 Energy beam curable composition [e1] Cured material layer 1 12 'Energy beam curable composition [e2] Cured material layer 1

FIG. 4 is a crushed plan view of a member in the course of manufacturing the microchemical device manufactured in Example 3 as viewed from a direction perpendicular to the surface of the member (B).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Polycarbonate board 12 Energy beam curable composition [e1] Cured material layer 1 12 'Energy beam curable composition [e2] Cured material layer 1 13 Energy beam curable composition [e1] Cured material layer 2 14 Channel 15 Separation chamber (low contact angle) 15 'Separation chamber (high contact angle)

FIG. 5 is a crushed plan view of a member in the process of manufacturing the microchemical device manufactured in Example 3, viewed from a direction perpendicular to the surface of the member (B).

[Explanation of symbols]

 Reference Signs List 18 polycarbonate plate 19 energy ray-curable composition [e1] cured layer 3 19 'energy ray-curable composition [e2] cured layer 3

FIG. 6 is a diagram showing a member of the microchemical device manufactured in the example.
It is the crushing top view seen from the direction perpendicular | vertical to the surface of (B).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Polycarbonate board 12 'Energy beam curable composition [e2] Cured material layer 1 13 Energy beam curable composition [e1] Cured material layer 2 14 Flow path 15 Separation chamber (low contact angle part) 15' Separation chamber (High contact angle part) 16 Inflow path 16 ′ Inflow path 17 Outflow path 17 ′ Outflow path 19 Energy ray curable composition [e1] Cured material layer 3

FIG. 7 shows a member of the microchemical device manufactured in the example.
It is the front view seen from the direction parallel to the surface of (B).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Polycarbonate board 12 Energy beam curable composition [e1] Cured material layer 1 13 Energy beam curable composition [e1] Cured material layer 2 16 Inflow path 16 'Inflow path 17 Outflow path 17' Outflow path 18 Polycarbonate plate 19 ' Energy ray-curable composition [e2] cured product layer 3

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // G01N 31/20 G01N 31/20

Claims (6)

[Claims] 1. A sectional area of 1 × 10 ⁻¹² m ² to 1 × 10 ⁻⁶ m ^2.
A microchemical device having a capillary flow path in the range of, wherein a liquid separation chamber having a cross-sectional area of 2 to 1000 times the cross-sectional area of the flow path is provided at the downstream end of the flow path, The liquid separation chamber has a low contact angle portion having a relatively low contact angle with water on its inner surface, and a contact angle with water that is 10 times smaller than the low contact angle portion.
A microchemical device characterized by having a high contact angle portion higher than or equal to a degree, and an outflow passage provided from each of a low contact angle portion and a high contact angle portion of a liquid separation chamber. 2. A contact angle α of water at a low contact angle portion of a liquid separation chamber.
The contact angle β between water and the water at the high contact angle is
35 ° ≦ β, (b) 25 ° <α ≦ 90 °
And (α + 40 °) ≦ β ≦ 90 °, (c) α
The microchemical device according to claim 1, wherein ≤ 90 ° and at least one condition of 90 ° <β is satisfied. 3. The microchemical device according to claim 1, wherein the flow path and the liquid separating chamber are formed between the member (A) and the member (B) which are in close contact with each other. 4. The microchemical device according to claim 3, wherein the member (A) and the member (B) are made of an organic polymer. 5. The member (A) and the member (B) are:
4. A polymer selected from the group consisting of a polycarbonate polymer, a vinyl chloride polymer, a polyamide polymer, a polyester polymer, a (meth) acrylic crosslinked polymer, and a maleimide crosslinked polymer. The microchemical device as described. 6. The microchemical device according to claim 1, wherein a plurality of inflow paths are formed by being connected to an upstream end of the flow path.