JP2001137613A - Fine chemical device having extraction structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine chemical device capable of performing liquid-liquid material transfer by letting a small quantity of liquids immiscible to each other stably flow while being in contact with each other in layer and then continuously separating and recovering the liquids in contact with each other. SOLUTION: The fine chemical device has a capillary flow passage having 1×10-12 to 1×10-6 m2 cross-sectional area, the inside surface 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 and the low contact angle part and the high contact angle part continue respectively from the upstream end to the down stream end of the flow passage without a break.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a so-called minute liquid-liquid extraction device in which liquids that are immiscible with each other are brought into contact in a minute device to perform mass transfer between the liquid and the liquid. More specifically, the present invention relates to a microchemical device having a mechanism in which immiscible liquids flow in a capillary channel in a layered manner, and are separated into respective liquids and flow out.

[0002] The microchemical device of the present invention is a microdevice for liquid-liquid extraction in the fields of physical chemistry and chemical engineering; a microsynthetic device with liquid-liquid mass transfer in the fields of synthetic chemistry and biochemistry; It can be used as a sample preparation microdevice that can be combined with a microanalysis device such as integrated DNA analysis, microelectrophoresis, and microchromatography; and a microdevice for analysis sample preparation such as mass spectrum and liquid chromatography.

[0003]

2. Description of the Related Art As a microdialysis device, "Analytical Chemistry", Vol. 70, p. 3553 (1998).
) Reported a microdialysis device in which a dialysis membrane was sandwiched between two planar substrates each having a groove formed therein.

Also, "High-speed molecular transport in microchannels" [99-1 Separations Science &
Technology (SST) Seminar Lecture, sponsored by the Society of Polymer Science, 9 pages (1999)], a xylene / water-based liquid-liquid in a 250 μm wide, 100 μm deep microchannel dug in quartz. Extraction has been reported.

[0005]

However, the dialysis membrane swells and changes its volume when used, but it is considerably difficult to manufacture a microchemical device incorporating such a dialysis membrane. In addition, the mass exchange rate in prior art devices has been slower than in direct contact between liquids.

On the other hand, even if two liquids that do not mix with each other are caused to flow through a flow path to bring the liquids into direct contact with each other, it is difficult to stably bring the two liquids into contact with each other in a layered manner on a micro scale. Therefore, the mass exchange efficiency tends to decrease. Furthermore, it is quite difficult to separate the liquids again on a microscale after direct contact between the liquids.

[0007] The problem to be solved by the present invention is to provide a microchemical device in which liquids are brought into direct contact with each other on a micro-scale and stably flow in a state of being in a layered state, thereby improving the extraction efficiency. Another object of the present invention is to provide a microchemical device capable of separating the contacted liquid again.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for solving the above-mentioned problems, and as a result, have found that the diameter is 1 to 1.
By providing a portion having a low contact angle with water and a portion having a high contact angle with water on the inner surface of a capillary channel of about 000 μm, and providing both portions in a continuous shape from the inflow end to the outflow end of the flow channel, they are mixed with each other. That the liquid not flowing into the flow path can be stably flowed in a state of being in contact with the layer, and that the outflow paths are formed from the low and high contact angles of the inner surface of the flow path with water. Thus, the present inventors have found that liquids that are immiscible with each other at the outflow end can be separated again, 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 inner surface of the flow path has a low contact angle portion having a contact angle with water of 25 ° or less and a high contact angle portion having a contact angle with water at least 10 ° higher than that of the low contact angle portion. And the low contact angle portion and the high contact angle portion are continuous without interruption from the upstream end to the downstream end of the flow path, respectively. Are referred to simply as “devices”).

According to another aspect of the present invention, there is provided a microchemical device in which an outflow path is formed at a downstream end of a flow channel from a low contact angle portion and a high contact angle portion of the flow channel. The microchemical device according to the above (I) is provided.

In order to solve the above-mentioned problems, the present invention provides: (III) a contact angle δ _H of water on the inner surface of a connection portion of an outflow passage connected to a high contact angle portion of a flow passage; providing a micro chemical device according to high above (II) in claim 10 ° or more than the contact angle [delta] _L of water in the inner surface at the connecting portion of the outlet channel connected to the low contact angle portion.

In order to solve the above-mentioned problems, the present invention provides (IV) a contact angle δ _L with water on the inner surface of an inner surface at a connection portion of an outflow passage connected to a low contact angle portion of a flow passage; The contact angle δ _H of the inner surface with water at the outflow path connection portion connected to the high contact angle portion is (a) δ _L ≦ 25 °, and 35
° ≦ δ _H , (b) δ _L ≦ 90 °, and 90 ° <
δ _H , which satisfies at least one of the conditions (II
(I) A microchemical device according to the item (1) is provided.

In order to solve the above-mentioned problems, the present invention provides (V) an outflow passage connected to a high contact angle portion of a flow passage,
The microchemical device according to any one of the above (I) to (VI), which is a tube connected to a flow path.

According to another aspect of the present invention, there is provided a liquid crystal display comprising: (VI) a microchemical device connected to a low contact angle portion and a high contact angle portion of a flow path at an upstream end of the flow path, respectively; The microchemical device according to any one of the above (I) to (V), in which is formed.

According to the present invention, in order to solve the above-mentioned problem, (VII) the flow path is filled with a solid substance except for a portion serving as a flow path between the member (A) and the member (B). Of shape,
Alternatively, the member (A) having a groove on the surface is formed between the member (A) and the member (B) in a shape in which another member (B) is in close contact with a groove forming surface of the member (A). Each low contact portion of the inner surface is selected from the group consisting of a member (A) side bottom surface, a member (A) side bottom surface and at least one side surface, a member (B) surface, a member (B) surface and at least one side surface of the flow path. The microchemical device according to any one of the above items (I) to (VI) is provided.

In order to solve the above problems, the present invention provides (VIII) the microchemical device according to the above (VII), wherein the member (A) and the member (B) are made of an organic high molecular polymer. .

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

[0018]

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 other complicated shapes.
It is particularly preferred that it is plate-like or rod-like. 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 substrate may be, for example, a structure in which a portion other than the flow path between the member (A) and the member (B) is filled with a solid substance. The structure may be such that another member (B) is formed in close contact with the grooved surface of the member (A) having a groove.

The shape of the member (A) is the same as that of the above-mentioned substrate. The member (A) may be in a form integrated with another member, for example, a support. When the member (A) is in the form of 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, 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 be formed on the surface, but a groove or a structure other than the groove may be formed. For example, member (B)
Is 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 device of the present invention is arbitrary, and may be an organic polymer (hereinafter simply referred to as "polymer"), a crystal such as glass or quartz, or a semiconductor such as ceramic, carbon, metal or silicon. Although it may be present, it is preferably a polymer from the viewpoint 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 grooves are formed on the surface, energy beam curing is easy in forming grooves, high curing speed, and easy surface hydrophilicity. Crosslinkable 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 polymers; polysulfone polymers such as porsulfone and polyethersulfone; poly (meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide polymers; polycarbonate 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, polycarbonates, polyvinyl chloride, nylon, aromatic polyamides, polyimides, polyetherimides which are excellent in solvent resistance, have a wide range of usable solvents and are excellent in adhesiveness. , Polyethylene terephthalate and polyarylate are preferable, and among them, polycarbonate, polyvinyl chloride, nylon and polyarylate are particularly preferable from the viewpoint of moldability and price. Also, a poly (meth) acrylic cross-linked polymer,
Energy beam curable crosslinked polymers such as polymaleimide bridge crosslinked polymers are also preferred.

In the case where the device of the present invention comprises the member (A) and the member (B) as main members, those materials which can be used in the above-described chemical device of the present invention can be used. Can be used. The material of the member (B) may be the same as or different from that of the member (A).

The channel of the device of the present invention has a cross section 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. Maximum diameter of the flow path cross section /
The diameter ratio can be set arbitrarily according to the application and purpose.
Generally, 0.1 to 10 is preferable, and 0.25 to 4 is more preferable.
Preferably, 0.3 to 3 is most preferable. These shapes,
The dimensions need not be constant throughout the flow path.

When the flow path is formed between the member (A) and the member (B), the flow path may be, for example, (a) 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 path is formed between the member (A) and the member (B), the dimension in the horizontal direction / vertical direction on the contact surface between the member (A) and the member (B) in the flow path The dimensional ratio of.
3-10 are preferable, and 0.5-5 are more preferable.

When the shape of the flow path in the streamline direction, for example, the flow path is formed between the member (A) and the member (B),
The shape viewed from the direction perpendicular to the contact surface between the member (A) and the member (B) may be a straight line, a curve, a spiral, a zigzag, or any other shape depending on the purpose of use.

In the case where the flow path has a structure in which a portion other than the flow path between the member (A) and the member (B) is formed by filling the solid material, the thickness of the solid material is not necessarily uniform. Although it is not, it is preferable that it is uniform.

As a method of forming 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, for example, (1) the member (A) ) And the member (B) are sandwiched with an energy ray-curable composition, 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 the material is uncured. (2) a method of removing an energy-ray-curable composition, (2) a method of sandwiching an adhesive sheet-like member cut out from a portion to be a flow path between the member (A) and the member (B), and 3) A method in which a protective substance, for example, a rod made of ethylene tetrafluoride is placed in a portion to be a flow path, and after a polymerizable substance or a molten resin is filled and solidified, the protective substance is removed. These methods have a small number of steps, but when the flow path diameter is small, it is difficult to remove the uncured energy ray-curable composition and the protective substance, and thus it is suitable as a method for forming a flow path having relatively large dimensions. It is.

When the flow path is formed by bringing another member (B) into close contact with the grooved surface of the member (A) having a groove on the surface, the groove provided on the member (A) has a peripheral portion. Lower,
It may be formed as a so-called groove, or the member (A)
It may be formed between walls standing on the surface. 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 method, vapor deposition method, gas phase polymerization method, sheet-like members and plate-like parts with grooves to be cut out A method such as close contact with a member can be used. The member (A) may be made of a plurality of materials, and for example, may be made of a material whose bottom and side surfaces are different from each other. 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) can be adhered to each other by a method in which the groove on the surface of the member (A) is formed as a flow path. 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 a method such as fusion can be used, it is preferable to use a non-solvent type adhesive, and a method of bonding by curing with an energy ray irradiation using an energy ray curable resin as the solventless type adhesive is a very small method. It is preferable because it enables precise bonding of various devices and has high productivity. Further, 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 method between the member (A) and the member (B) may be, for example, a state in which the member (A) is fixed by a clamp, a screw, a rivet, or the like.

In the device of the present invention, the inner surface of the flow path has a low contact angle portion where the contact angle with water is 25 ° or less, preferably 15 ° or less, more preferably 10 ° or less, and most preferably 5 ° or less. And having a high contact angle portion where the contact angle with water is at least 10 ° higher than the contact angle with water of each low contact portion, and
The low contact angle portion and the high contact angle portion are characterized by being continuous without interruption from the upstream end to the downstream end of the flow path. The contact angle of each part with high contact with water is preferably 3
It is 5 ° or more, more preferably 45 ° or more, further preferably 70 ° or more, and most preferably 90 ° or more.

If the contact angle of the low contact angle portion with water is higher than this value, especially when the cross-sectional area of the flow passage is small or when the cross-section of the flow passage is divided into the low contact angle portion and the high contact angle portion, When the depth of each flow path is shallower than the width, when the flow rate of the liquid is high, when the flow rate of the hydrophilic liquid is smaller than the flow rate of the hydrophobic liquid, or when the viscosity difference of the immiscible liquids Is large, liquids that are immiscible with each other cannot flow in a layered manner, move in a lump, and the extraction efficiency is reduced, and liquid separation in the outflow channel tends to be difficult. The same applies when the contact angle of the high contact angle portion with water is lower than this value. Further, the lower the contact angle of the low contact angle portion with water, the less the above-mentioned inconvenience occurs even if the contact angle of the high contact angle portion with water is relatively low.

The term "contact angle with water" used in the present invention refers to a static angle determined by a droplet method. Prior to the measurement, the sample is 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 measurement is performed at a temperature of 24 ± 1 ° C. and a humidity of 65 ± 5%. The measurement is performed after a stabilization time of 3 minutes after the placement. If the contact angle changes depending on the sample drying conditions,
Take the lowest value.

When the volumetric flow ratio of the hydrophilic liquid flowing in contact with the low contact angle portion and the hydrophobic liquid flowing in contact with each of the high contact portions is close to 1: 1, the low contact angle portion corresponds to the cross section of the flow path. Preferably, the ratio to the perimeter is 1/5 or more,
It is more preferably 1/2 or more, and more preferably 4/5 or less. This value need not be constant throughout the flow path. The ratio of the high contact angle portion to the peripheral length of the cross section of the flow passage is preferably 1/5 or more,
It is more preferably at least / 3, more preferably at most １ ／. This value need not be constant throughout the flow path. The high contact angle portion can be formed as a portion other than the low contact angle portion, but the flow path inner surface may have a third portion other than the high contact angle portion and the low contact angle portion. The volume flow ratio of the hydrophilic liquid flowing in contact with the low contact angle portion and the hydrophobic liquid flowing in contact with each of the high contact portions is 1: 1.
In the case where the deviation is large, it is preferable to change the proportion of the low contact portions and the high contact portions in accordance with the volume flow ratio.

When the anisotropy of the cross section of the flow path is large, that is, when the ratio of the major axis to the minor axis is large, the high contact angle portion and the low contact angle portion correspond to the low contact angle portion and the high contact angle. When divided into parts, the depth / width ratio of each of the divided flow paths is in the range of 0.3 to 3, more preferably 0.5 to 3.
It is preferable to set the value in the range of 2. That is, it is preferable that the hydrophilic liquid and the hydrophobic liquid each flow in a shape that is nearly isotropic in cross section. When the ratio of the depth / width of each of the divided flow paths is small, the two liquids tend to flow as a lump instead of flowing in a layered form, or flow out of the low contact angle portion and the high contact angle portion. Tends to be. Conversely, a value larger than this value is not preferable because the material exchange efficiency tends to decrease.

When the flow path is provided between the member (A) and the member (B), one of the low contact angle portion and the high contact angle portion is provided on the surface on the member (A) side. Or member (B)
The surface on the side is preferable because the production becomes easy.
For example, when 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 low contact angle portion is formed on the surface of the member (A). , One or more selected from the group consisting of a filled solid substance surface and a member (B) surface;
And not all surfaces may be used. The filled solid material surface may be configured such that two opposing surfaces are respectively made of different fixed material. Further, for example, another member (B) may be provided on the surface of the channel (A) having the groove on the surface of the channel.
Are formed in close contact with each other, the low contact angle portion is formed on the member (A) side, which is the bottom and side surfaces, or the member (B)
Alternatively, the surface may be an adhesive applied to the member (B).

The low contact angle portion and / or the high contact angle portion on the inner surface of the flow path is formed by a material such as the member (A), the member (B), or the filled solid substance, which is suitable for a material constituting the flow path wall surface. It may be formed by using a material exhibiting a corner, or may be formed by surface treatment of the inner surface of the flow channel. After applying the surface treatment to the material forming the flow path,
The flow path may be formed, or may be formed after the flow path is formed.

The method of hydrophilizing the inner surface of the flow channel by the surface treatment is optional. For example, plasma treatment, plasma polymerization, corona discharge treatment, chemical modification of the surface, graft polymerization of a hydrophilic compound on the surface, and hydrophilic polymer Coating and the like. The plasma treatment or the plasma polymerization is preferably performed in the presence of oxygen; a compound having an oxygen atom in a molecule such as acetone, an organic acid or the like; or a compound having a nitrogen atom in a molecule such as an amine. Also, normal pressure plasma processing is possible. 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, for example, polyhydroxymethyl methacrylate,
Examples thereof include polyvinyl alcohol, sulfonated cellulose, and sulfonated polysulfone.

In the case where 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. The hydrophilic polymer coating is
This is preferable because a substance having a high degree of hydrophilicity can be obtained. 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.

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 method of hydrophobization by surface treatment is optional.
For example, fluorine treatment, plasma treatment, plasma polymerization, chemical modification of the surface, graft polymerization of a hydrophobic compound on the surface,
Coating of a hydrophobic polymer.

The plasma treatment and the plasma polymerization are, 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.

Examples of the chemical modification of the surface include 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 may be performed, for example, by subjecting a member to a surface treatment such as corona treatment, plasma treatment, or radiation treatment, and then contacting the member with a hydrophobic addition-polymerizable compound; And a surface grafting method utilizing the same.

The surface treatment for hydrophilization or hydrophobization may be performed only on the target portion, or may be performed on the whole while the target portion is protected, and then the protection may be removed. A suitable method can be adopted depending on the processing method.

In the device of the present invention, it is preferable that the inflow path is formed at the upstream end of the flow path so as to be connected to the low contact angle part and the high contact angle part of the flow path, respectively. That is,
The liquid flowing from one of the inflow paths is configured to flow in contact with the low contact angle portion of the flow path, and the liquid flowing from the other inflow path is configured to flow in contact with the high contact angle part of the flow path. Is preferred. The plurality of inflow channels formed by connecting to the low contact angle portion and the high contact angle portion, respectively, may be provided. The size, shape, and contact angle of the inner surface with water are arbitrary. For example, when the flow path is provided between the member (A) and the member (B), the inflow path is provided between the member (A) and the member (B) similarly to the flow path. It may be formed as a hole formed in the member (A) or the member (B).

In the device of the present invention, it is preferable that the outflow path is formed at the downstream end of the flow path so as to be connected to the low contact angle portion and the high contact angle portion of the flow path, respectively. That is,
It is preferable that the liquid flowing in contact with the low contact angle portion of the flow channel and the liquid flowing in contact with the high contact angle portion of the flow channel can flow out of different outflow paths. . There may be a plurality of outflow channels formed by connecting to the low contact angle portion and the high contact angle portion, respectively.

The contact angle of the inner surface of the outflow passage with water is arbitrary, but the contact angle δ _H of the inner surface of the flow passage at the connection portion of the outflow passage connected to the high contact angle portion of the flow passage is low. It is preferred that the contact angle δ _L with water on the inner surface at the connection portion of the outflow passage connected to the contact angle portion be at least 10 degrees. If the difference in the contact angle with water is less than this, it is not preferable because the separation of immiscible liquids tends to be unstable. Further, as the [delta] _L is low, [delta] _H is above disadvantages hardly occurs even relatively low, [delta] as _H is high, [delta] _L is relatively high above disadvantages even hardly occurs.

The relationship between δ _L and δ _H is as follows: (a) δ _L ≤ 25 ° and preferably 35 ° ≤ δ _H , δ _L ≤ 10 °, and 35 ° ≤
more preferably from [delta] _H, as the difference between the [delta] _L and [delta] _H greater preferred. (Ii) a [delta] _L ≦ 90 °, and preferably larger the difference of preferably from 90 ° <δ _H, δ _L and [delta] _H. (C) 25 ° <δ _L ≦ 90 ° and (δ _L +4
0 °) ≦ δ _H ≦ 90 °, and δ _L and δ
_The larger the difference in _H, the better.

Further, the above (a) and (b) are simultaneously satisfied.
That is, (d) δ_L ≦ 25 ° and 90 ° <δ_H Is
More preferably, δ _L ≦ 10 ° and 90
° <δ_H Is most preferred.

When δ _L and δ _H satisfy these relationships, it becomes easy for the hydrophilic liquid and the hydrophobic liquid in the flow path to independently enter different outflow paths. The contact angle between the inner surface of the connection part of the outflow passage connected to the high contact angle part of the flow path and the hydrophobic liquid to be used is preferably 90 ° or less.

At this time, the contact angle between the inner surface of the outflow passage and water is
The value at the connection where the liquid enters the inflow channel from the flow channel is of concern. When the outflow channel inner surface is composed of a plurality of water contact angle portions, the contact angles δ _L and δ _H of the outflow channel inner surface with water are weighted averages of the areas occupied. However,
Outlet passage inner surface is preferably [delta] _L, [delta] _H is formed only in the portion indicating the value of the range. The method of adjusting the contact angle with water of the outflow path may be the same as the method of adjusting the contact angle with water of each low contact portion and each high contact portion of the flow channel in the present invention.

Although the shape of the outflow channel is not limited, the outflow channel connected to the high contact angle portion of the flow path may be a tube connected to the flow path. Adjusting the back pressure by adjusting the pressure is preferable because it is easy to completely separate the liquid. Channel (A) and member (B)
In the case where the outlet channel is provided between the member (A) and the member (B), the outlet channel may be provided between the member (A) and the member (B) as in the case of the channel. It may be formed as a hole formed in a hole. The outflow path connected to the low contact angle portion is provided between the member (A) and the member (B), and the outflow path connected to the high contact angle portion is the member (A) or the member (B).
It is preferable that the tube is a hole inserted into the member or a tube inserted into the member (A) or the member (B). The tube, which is the outflow channel connected to the high contact angle portion, is preferably formed of a fluoropolymer.

In the microchemical device of the present invention, in addition to the flow path, the inflow path, and the outflow path, other structures such as a storage tank, a reaction tank, a membrane separation mechanism, a flow control mechanism, and a connection outside the device are provided. A mouth, another inflow path, another branched outflow path, and the like may be formed.

In using the microchemical device of the present invention, a hydrophilic liquid, usually an aqueous solution, is introduced into the inflow passage connected to the low contact angle portion, and the inflow passage connected to the high contact angle portion is introduced into the inflow passage connected to the low contact angle portion. Introduce a hydrophobic liquid that is immiscible with the hydrophilic liquid. The hydrophilic liquid travels through the low contact angle portion and the hydrophobic liquid travels through the high contact angle portion in a layered manner in the channel, during which mass transfer occurs between the liquids. The lower the flow rate, the longer the contact time and the higher the mass exchange efficiency. However, even if the contact is performed for an excessively long time, it is meaningless because the contact is saturated. The smaller the channel diameter, the faster the mass exchange rate and the shorter the time to reach saturation. The flow rate ratio is arbitrary, and it is possible to use one of the liquids after flowing into the device and then set the flow velocity of the liquid to zero, but it is preferable that the volume flow rate is close to 1: 1.

Depending on the combination of the hydrophilic liquid and the hydrophobic liquid, the flow rate ratio, and the size and shape of the flow path, the two liquids do not form a complete two-layer structure, and the two liquids move in a lump in the flow path. There are cases. Such a state is not preferable because the mass exchange rate is reduced and the liquid separation at the outlet is incomplete. Such a state can be prevented by adjusting the contact angle balance between the hydrophilic portion / hydrophobic portion on the inner surface of the flow channel and, in many cases, reducing the contact angle of the hydrophilic portion with water.

At the downstream end of the flow path, the liquid that has flowed through the flow path has the hydrophilic liquid flowing into the flow path connected to the low contact angle portion, and the hydrophobic liquid has flowed into the flow path connected to the high contact angle section. 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 greater the difference in hydrophilicity / hydrophobicity near the connection port of the outflow channel, the easier it is to completely separate the two liquids regardless of the flow rate ratio, viscosity, and the like.

Nevertheless, at the start of distribution, liquids that do not mix with each other may flow out of only one of the outflow channels or without being separated from each of the outflow channels. In such a case, if the outlet of any one of the outflow paths is temporarily squeezed to bring the liquid flow into a normal state, the state can be stably maintained thereafter.

The liquids to be introduced into the microchemical device of the present invention may be three liquids that are immiscible with each other. Also,
By providing a path showing the contact angles with three different waters in the flow path, it is possible to flow three immiscible liquids in layers in the flow path and then separate them into three liquids or one and two liquids. it can.

[0069]

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 preparation method of the energy radiation-curable composition used in the examples is shown below.

[Preparation of energy ray-curable composition [e1]] 40 parts of a urethane acrylate oligomer having an average of three acrylic groups per molecule (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.) , 60 parts of nonylphenoxy polyethylene glycol (n = 8) acrylate (“M-114” manufactured by Toa Gosei Chemical Co., Ltd.), 1-hydroxycyclohexylphenyl 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 a urethane acrylate oligomer (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.)
60 parts of dicyclopentanyl diacrylate (“R-684” manufactured by Nippon Kayaku Co., Ltd.), 5 parts of ultraviolet polymerization initiator 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) and polymerization retarder 2 ,
0.1 part of 4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Kagaku) 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]] 70 parts of urethane acrylate oligomer ("Unidick V-4263"), nonylphenoxy polyethylene glycol (n = 17) acrylate (manufactured by Daiichi Kogyo Seiyaku Chemical Co., Ltd.) 30 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 energy ray-curable composition [e3]
Was prepared. Table 1 shows the contact angle of the cured product of this composition [e3] with water.

[Preparation of energy ray-curable composition [e4]] 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 prepare an energy ray-curable composition [e4].
Table 1 shows the contact angle of the cured product of this composition [e4] with water.

[Preparation of energy ray-curable composition [e5]] 100 parts of a urethane acrylate oligomer ("Unidick V-4263") and 5 parts of an ultraviolet polymerization initiator 1-hydroxycyclohexylphenyl ketone ("Irgacure 184") 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 [e5]. Table 1 shows the contact angle of the cured product of this composition [e5] with water.
It was shown to.

[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 the range of 5 cm x 2.5 cm After applying the energy ray-curable composition [e1] to the area including 1) using a 127 μm bar coater, the upper half of the polyvinyl chloride plate (1) in the drawing of FIG. It was covered with a photomask, and irradiated with ultraviolet rays 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. After the ultraviolet irradiation, the uncured material is washed and removed with a water stream, so that the energy ray-curable composition [e1] cured product layer 1 (2) having a thickness of 102 μm is formed on the lower half in the drawing of FIG. ) Formed.

Next, the energy ray-curable composition [e2] was applied to the polyvinyl chloride plate (1) on which the cured product layer 1 (2) was formed in an upper half portion in the drawing of FIG.
Was applied using a bar coater, and the lower half of the drawing shown in FIG. 1 was 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, so that the thickness of the polyvinyl chloride plate (1) is 102 μm on the upper half in the drawing of FIG.
Ray curable composition [e2] cured product layer 1
(2 ′) was formed.

Further, the energy ray-curable composition [e1] was applied to the surface on which the cured product layer 1 was formed using a 127 μm bar coater, and the flow path (4) having the shape shown in FIG. (5) The portion to be the outflow channel (6) and the upper half in the drawing of the drawing shown in FIG. 1 were covered with a photomask, and the same ultraviolet rays as above were irradiated for 30 seconds in a nitrogen atmosphere. 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 [e2] was applied to the upper half portion of the sheet of the drawing shown in FIG. 1 of the polyvinyl chloride plate (1) using a 127 μm bar coater. The flow path (4), the inflow path (5 ′), the outflow path (6 ′), and the lower half in the drawing of FIG. 1 are covered with a photomask, and a nitrogen atmosphere is formed. Inside, the same ultraviolet rays as above were irradiated for 30 seconds. After irradiation with ultraviolet rays, the uncured material is washed and removed with a stream of water to form an energy ray-curable composition [e2] cured product layer 2 (3 ′), and an energy ray-curable composition [e1] cured product layer 2
(3) and energy beam curable composition [e2] 240 μm in width and 102 μ in depth as a defect in cured product layer 2 (3 ′)
m, 3 cm long grooves (4), inflow channels (5, 5 '), each 120 μm wide and 102 μm deep, and each 12 cm wide
Outflow channels (6, 6 ′) having a depth of 0 μm and a depth of 102 μm were formed. Then, the inflow channel (5, 5 ') and the outflow channel (6,
At the end of 6 ′), a hole having a diameter of 0.5 mm is formed to form an inflow port (7, 7 ′) from the outside of the device and an outflow port (8, 8 ′) outside the device, and the member (A) is formed. ) [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 [e1] is applied to the corona-treated surface (not shown) using a 127 μm bar coater, and then irradiated with the same ultraviolet rays as described above for 1 second in a nitrogen atmosphere. Although the coating film lost its fluidity but was in an incompletely cured state, and the coated surface was bonded to the grooved surface of the member (A) [A1], the same was applied from the polypropylene biaxially stretched film side. Ultraviolet rays are further irradiated for 60 seconds to completely cure the coating film, whereby the energy ray-curable composition [e1] has a thickness of 10 comprising the cured product (9).
At the same time as forming a 3 μm sheet-shaped member (B) [B1], it is adhered to the surface of the member (A) [A1], and a capillary channel (4) and an inflow channel (5, 5 ′) are interposed therebetween. And outflow channels (6, 6 '). Thereafter, the polypropylene biaxially stretched film was peeled off, and 5 cm × 2.5 cm shown in FIG.
Was cut out to obtain a microchemical device [D1].

[Contact Angle of Each Part with Water] The contact angles of the materials used with water are shown in Table 1. The microchemical device [D1] includes a lower half portion of the surface of the flow path (4) on the member (A) side in the drawing of FIG. 1 and the flow path (4) in FIG.
The lower side surface in the drawing of the drawing shown in FIG.
This was a low contact angle portion of 2 °. On the other hand, the upper half of the surface of the flow path (4) on the member (A) side in the drawing of FIG. 1 and the upper side surface of the flow path (4) in the drawing of FIG. The contact angle with water was a high contact angle portion of 91 °. Further, the entire surface of the member (B) of the flow path (4) was a low contact angle portion having a contact angle with water of 22 °. Furthermore, the inflow channel (5)
And a contact angle δ _L with the water on the inner surface at the connection portion of the outflow path (6) with the flow path (4) is 22 °, and the flow path (4) of the inflow path (5 ′) and the outflow path (6 ′). The contact angle between the surface on the member (A) side and the water on both side surfaces at the connection portion is 91 °, the contact angle with water on the member (B) surface is 22 °, and the weighted average contact angle δ _H is 67 °.

[Liquid-Liquid Contact Test] The microchemical device [D1] obtained in this way was placed with the member (B) facing upward, and micro-syringes were respectively placed in the inflow channels (7, 7 '). After connection, water was supplied from the inlet (7) and n-hexane was supplied from the inlet (7 ′) at a flow rate of 0.01 mm ^3.
Per second, water impinges on the low contact angle portion of channel (4),
The n-hexane flows in layers in each of the high contact angle sections, water enters the outlet channel (6) and flows out of the outlet (8), while n-hexane enters the outlet channel (6 '). It flowed out of the outlet (8 '). Further, even when the flow rate of n-hexane was kept constant and the flow rate of water was changed to 0.7 to 1.5 times, water and n-hexane were separated and flowed out.

In addition, almost the same results were obtained in tests using cyclohexane, xylene and ethyl acetate instead of n-hexane.

[Extraction Test] Microchemical device [D
1] is installed such that the member (B) is on the upper side, and micro-syringes are connected to the inflow channels (7, 7 ′), respectively.
When a 0.1N aqueous sodium hydroxide solution is injected from the inlet (7) and a xylene solution in which phenolphthalene is dissolved to saturation is injected from the inlet (7 ') at a flow rate of 0.01 mm ³ / sec, the aqueous solution flows through the flow path ( 4) The xylene solution flows in layers in the low contact angle portion and the high contact angle portion, respectively.
The aqueous solution entered the outflow channel (6) and flowed out of the outlet (8), while the xylene solution entered the outflow channel (6 ') and flowed out of the outlet (8'). At this time, the injected 0.1N
The aqueous sodium hydroxide solution, the xylene solution, and the outflowing xylene solution were both colorless and transparent, but the 0.1.
The 1N aqueous sodium hydroxide solution was pale red.
That is, phenolphthalene was extracted from the xylene phase to the aqueous phase.

Instead of a saturated xylene solution of phenolphthalene, 0.01% by weight of phenolphthalene was used.
Similar results were obtained using an ethyl acetate solution.

Comparative Example 1 In this comparative example, a microchemical device in which the contact angle with water at the low contact angle portion of the inner surface of the flow channel is 36 ° will be described.

[Preparation of Microchemical Device] Example 1
In the same manner as in Example 1 except that the energy ray-curable composition [e3] was used instead of the energy ray-curable composition [e1], the fine chemical device [C] was used.
D1].

[Contact Angle of Each Part with Water] The microchemical device [CD1] thus obtained has a contact angle with water of 36 ° in the low contact angle portion of the flow path (4); It was the same as the microchemical device [D1] except that the contact angle δ _L (weighted average) with the inner surface of water at the connection of the outflow channel (6) with the flow channel (14) was 31 °.

[Liquid-Liquid Contact Test] With respect to the microchemical device [CD1], the same test as in Example 1 was performed for the n-hexane / water system. As a result, water and n-hexane respectively aggregated to form a lump. The water flowed through the flow path, and both water and n-hexane flowed out from both the outflow channel (6) and the outflow channel (6 ′). In other words, it is understood that the two liquids that are immiscible with each other do not flow in a layered manner in the flow channel unless the contact angle of each low contact portion of the flow channel with water is sufficiently low. Also, it can be seen that the two liquids that do not flow in a layered manner in the channel flow out without being separated.

<Example 2> [Preparation of microchemical device] The procedure of Example 1 was repeated, except that the energy ray-curable composition [e4] was used instead of the energy ray-curable composition [e2]. In the same manner as in No. 1, a microchemical device [D2] was produced.

[Contact Angle of Each Part with Water] The microchemical device [D2] obtained as described above has a contact angle δ with the water on the inner surface at the connection part of the outflow path (6) with the flow path (4). _L is 22 °, and the contact angle δ _H with the water on the inner surface at the connection point of the outflow channel (6 ′) with the flow channel (4) is 36 ° as a weighted average.
It was the same as the microchemical device [D1] except that

[Liquid-Liquid Contact Test] The same test as in Example 1 was conducted on the microchemical device [D2]. When the volume flow ratio between water and n-hexane was 1, the example 1 was used.
In the same manner as described above, water and n-hexane flow in a layered manner in the channel (4), and are separated into the outflow channel (6) and the outflow channel (6 ′).
It flowed out from the outlet (8) and the outlet (8 '), respectively.
However, when the flow rate of n-hexane was kept constant and the flow rate of water was increased 1.5 times, water flowed out of the outlet (8 ') simultaneously with n-hexane. That is, the contact angle δ _L of the outflow path (6) with water near the connection port with the flow path and the outflow path (6 ′)
10 ° difference in contact angle δ _H with water near the connection port with the flow path
With the above, water and n-hexane can be separated and flown out, but it can be seen that if the difference is small, the range of conditions that can be separated becomes narrow.

[Example 3] [Production of member (A)] Polycarbonate ("Iupilon S-200" manufactured by Mitsubishi Engineering-Plastics Corporation)
0 ") The energy-ray-curable composition [e1] was placed in a 127-μm bar in a range including a center (5 cm × 2.5 cm) range (11) of a 10 cm × 10 cm × 2 mm plate (not shown) made of [p2]. The solution was applied using a coater, and irradiated with ultraviolet 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., so that the entire surface of the polycarbonate plate (11) was 102 μm thick. The energy ray-curable composition [e1] cured product layer 1 (12) was formed. An energy ray-curable composition [e1] is applied on the cured product layer 1 (12) using a 127 μm bar coater, and a portion to be a flow path (14) having a shape shown in FIG. Was covered with a photomask and irradiated with the same ultraviolet rays in a nitrogen atmosphere. After irradiating the ultraviolet rays, the uncured material is washed and removed with a water flow to form an energy beam having a width of 210 μm and a depth of 102 μm, which is to be a flow path (14), and a thickness of 102 μm, as shown in FIG. Forming the curable composition [e1] cured product layer 2 (13), the member (A) [A
3].

[Adhesion of member (B)] The same polycarbonate [p2] plate (not shown) as that used in member (A) was added to the area including the area (17) of 5 cm × 2.5 cm at the center (17).
The energy ray-curable composition [e2] is applied using a 7 μm bar coater, and is covered with a photomask having a mirror image pattern of the member (A) [A3] used in the preparation of the member (A) [A3]. Was irradiated for 1 second to make the coating film incompletely cured, although the fluidity was lost, and the uncured material was washed away with a water stream. The incompletely cured coating film surface is bonded to the grooved surface of the member (A) [A3] so that the pattern overlaps, and the same ultraviolet light is irradiated for another 30 seconds to complete the coating film. By curing, the energy ray-curable composition [e1] cured product layer (18) having a width of 210 μm and a thickness of 98 μm, having a groove of a mirror image pattern of the member (A) [A3] and a polycarbonate plate (17) At the same time as forming the member (B) [B3] made of the material, the member (A) is adhered to the surface of the member (A3), and a capillary channel (1) having a width of 210 μm and a height of 200 μm is formed between them.
4) was formed.

Next, a drill hole having a diameter of 0.5 mm penetrating the members (A) [A3] and (B) [B3] was formed at both ends of the flow path (14). '), After forming the outflow channels (16, 16'), 5 cm shown in FIG.
An area of × 2.5 cm was cut out to produce a microchemical device [D3].

[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
3] is the surface of the flow path (14) on the member (A) side and the flow path (1).
4) Both sides of the member (A) on both sides have a contact angle with water of 1/2.
A low contact angle portion of 2 °, a high contact angle portion where the member (B) surface of the channel (14) has a contact angle of 88 ° with water, and a channel (14)
The contact angle with water on the member (B) side 両 側 on both sides is 91 °
Was a high contact angle portion. The contact angle δ _L of the inner surface of the outflow passage (16) with the flow path (14) is 22 °, and the inner surface of the outflow passage (16 ′) in the connection portion with the flow path (14) has a contact angle δ _L of 22 °. The contact angle δ _H with water was 88 °.

[Liquid-liquid contact test] The microchemical device [D3] was connected to the inflow path (15, 15 ') and the outflow path (16, 15').
16 ′) is installed so as to face the side of the device, micro-syringes are respectively connected to the inflow channels (15, 15 ′), and water is supplied from the inflow channel (15) and n− is supplied from the inflow channel (15 ′).
When hexane is injected at a flow rate of 0.02 mm ³ / sec, water flows in layers at a low contact angle portion of the flow channel (14) and n-hexane flows in layers at a high contact portion, and water flows out of the outflow channel (16). N-Hexane flowed out from the outflow channel (16 '). Further, the flow rate of n-hexane was constant, and the flow rate of water was 0.7
Water and n-hexane were separated and flowed out even when changed to 1.5 times.

[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 mm made of polycarbonate (“Iupilon S-2000” manufactured by Mitsubishi Engineering-Plastics) [p2]
5 cm x 2.5 cm area (1
In the range including 1), the energy ray-curable composition [e1]
Was applied using a 127 μm bar coater, and then irradiated with 50 mW / cm ² ultraviolet light for 3 seconds in a nitrogen atmosphere using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc. to completely cure the product. No semi-cured coating film was obtained. Next, the coating film is put into a hydrophilic layer-forming material, and irradiated with the same ultraviolet rays as above for 40 seconds to completely cure the coating film and, at the same time, impart hydrophilicity to the surface to a substantially negligible thickness. An energy ray-curable composition [e1] cured product layer 1 (12) having a thickness of 102 μm, on which the compound was graft-polymerized, was formed. The contact angle of the coating film thus obtained with water is 5 °.
Met.

Next, the energy ray-curable composition [e1] was applied thereon using a 127 μm bar coater, and then covered with a partial photomask having the shape shown in FIG. UV light in nitrogen atmosphere
Irradiated for 2 seconds to obtain a coating film in a semi-cured state. After the uncured material is washed and removed from the semi-cured coating film with a stream of water, the coating film is poured into a hydrophilic layer forming material, and the same ultraviolet light as above is applied to the material.
By irradiating for 2 seconds to completely cure the coating film, an energy-ray-curable composition [e1] cured product layer 2 having a shape shown in FIG. (13) was formed to obtain the member (A) [A1].
Although the water contact angle of the groove serving as the flow path (14) of the cured product layer 2 (13) could not be measured due to equipment reasons, the cured product layer 2 (13) could not be measured.
The contact angle with water on the surface other than the groove of (13) was 5 °. It is also considered that the contact angle of the side surface of the groove to be the flow path (14) is the same as the contact angle of water on the surface of the cured product layer 2 (13).

[Adhesion of member (B)] The member (B) was prepared in the same manner as in Example 3 except that the energy ray-curable composition [e5] was used instead of the energy ray-curable composition [e2]. 2) and simultaneously adhered to the member (A),
Example 3 was cut out from the area of 5 cm × 2.5 cm shown in FIG.
A microchemical device [D4] having the same shape as that described above was produced.

[Contact Angle of Each Part with Water] The microchemical device [D4] has a surface on the member (A) side of the channel (14) and a member (A) side on both sides of the channel (14). / 2 is a low contact angle portion where the contact angle with water is 5 °, the member (B) of the channel (14) is a high contact angle portion where the contact angle with water is 88 °, and the channel (14) is The 側 side of the member (B) on both sides was a high contact angle portion having a contact angle with water of 68 °. The contact angle δ _L with the water on the inner surface at the connection portion of the outflow channel (16) with the flow channel (14) is 5 °, and the flow channel (14) of the outflow channel (16 ′) is used.
And the contact angle δ _H with the water on the inner surface at the connection with the was 88 °.

[Liquid-Liquid Contact Test] The microchemical device [D4] was connected to the inflow path (15, 15 ') and the outflow path (16, 15').
16 ′) is installed in a direction to be the side of the device, micro-syringes are respectively connected to the inflow paths (15, 15 ′), and water is supplied from the inflow path (15) and n− is supplied from the inflow path (15 ′).
When hexane is injected at a flow rate of 0.02 mm ³ / sec, water flows in layers at a low contact angle portion of the flow channel (14) and n-hexane flows in layers at a high contact portion, and water flows out of the outflow channel (16). N-Hexane flowed out from the outflow channel (16 '). Further, the flow rate of n-hexane was kept constant, and the flow rate of water was 0.5
Water and n-hexane were separated and flowed out even when changed by up to 2-fold.

[Example 5] In Example 3, the energy ray-curable composition [e2] of the member (A) was used.
(12) The energy ray-curable composition [e2] was applied on top of 300 μm instead of a 127 μm bar coater.
The energy beam-curable composition [e2] cured product layer 1 (13) having a thickness of 220 μm was formed by using the bar coater described above, and the energy beam-curable composition [e2] cured product layer 1 of the member (B) was used. (18) The energy ray-curable composition [e2] having a thickness of 220 μm is applied by using a 300 μm bar coater instead of the 127 μm bar coater for application of the energy ray-curable composition [e2].
The cured product layer 2 (18) was formed, and the flow path dimension was width 3
00 μm, height 440 μm, outflow channel (1
6 '), drill a drill hole with a diameter of 1.6 mm and an outer diameter of 1.6
A tube made of polytetrafluoroethylene having a diameter of 0.5 mm and an inner diameter of 0.5 mm was inserted and fixed to the position of the flow path (14), and a 0.5 mm diameter drill hole was formed as a flow path (1) as an outflow path (16).
4) drilling up to the position, and 1 /
The area up to the depth of 2 is a drill hole with a diameter of 1.6 mm, and a tube made of polytetrafluoroethylene with an outer diameter of 1.6 mm and an inner diameter of 0.5 mm is reduced to half the depth up to the position of the flow path (14). A microchemical device [D5] was produced in the same manner as in Example 3 except that the device was inserted and fixed.

[Contact Angle of Each Part with Water] The microchemical device [D5] has a contact angle δ _L with water on the inner surface of the outflow path (16) at the connection portion with the flow path (14) of 22 °, It was the same as the microchemical device [D3], except that the contact angle δ _H with the water on the inner surface including the connection with the channel (14) of the channel (16 ′) was 110 °. .

[Liquid-Liquid Contact Test] The microchemical device [D5] was connected to the inflow channel (15, 15 ') and the outflow channel (16, 15').
16 ′) is installed so as to face the side of the device, micro-syringes are respectively connected to the inflow channels (15, 15 ′), and water is supplied from the inflow channel (15) and n− is supplied from the inflow channel (15 ′).
When hexane is injected at a flow rate of 0.07 mm ³ / sec, water flows in a low contact angle portion of the flow channel (14) and n-hexane flows in a layered manner through the high contact portions, and is connected to the outflow channel (16). Water flowed out of the tube and n-hexane flowed out of the tube connected to the outflow channel (16 '). Further, even when the flow rate of n-hexane was kept constant and the flow rate of water was changed to 0.7 to 1.5 times, water and n-hexane were separated and flowed out.

<Example 6> [Production of microchemical device]
Instead of inserting and fixing a tube made of polytetrafluoroethylene as the outflow channel (16) to a half depth to the position of the flow channel (14), an outer diameter of 1.6 mm made of rigid polyvinyl chloride [p1] is used. , A 0.5 mm inner diameter tube (self-made)
4) Inserted and fixed to the position, and the outflow channel (1
6 '), instead of inserting and fixing a tube made of polytetrafluoroethylene to the position of the flow path (14),
Outer diameter of methylpentene (Mitsui Chemicals) [p5] 1.6
A microchemical device [D6] was produced in the same manner as in Example 5, except that a tube (home-made) having a diameter of 0.5 mm and an inner diameter of 0.5 mm was inserted and fixed to the position of the flow path (14).

[Contact Angle of Each Part with Water] That is, the microchemical device [D6] is connected to the flow path (14) of the outflow path (16).
Contact angle [delta] _H is 104 ° with water of the inner surface including the connection portion of the contact angle [delta] _L is 87 ° to water of the inner surface, the flow path of the outflow passage (16 ') and (14) including a connecting portion between the Except for the above, it was the same as the microchemical device [D5].

[Liquid-Liquid Contact Test] The same test as in Example 5 was performed on the microchemical device [D6], and the same result as in Example 5 was obtained.

That is, the contact angle δ _L with water near the connection port with the flow path of the outflow path (16) and the contact angle δ _H with water near the connection port with the flow path of the outflow path (16 ′). When the difference is 10 ° or more, water and n-hexane can be separated and flown out, but when the difference is small, the condition range where separation can be performed is narrowed.

<Example 7> [Preparation of microchemical device]
Instead of inserting and fixing a tube made of polytetrafluoroethylene as the outflow channel (16) to a depth of 流 路 to the position of the flow channel (14), an outer diameter of transparent rigid polyvinyl chloride [p1] of 1. A 6 mm, 0.5 mm inner diameter tube (made by hand) was inserted and fixed to the position of the flow path (14), and instead of using a polytetrafluoroethylene tube as the outflow path (16 '), a transparent hard tube was used. A microchemical device [D7] was produced in the same manner as in Example 5, except that a tube (self-made) made of polyvinyl chloride [p1] having an outer diameter of 1.6 mm and an inner diameter of 0.5 mm was used.

[Contact Angle of Each Part with Water] That is, the microchemical device [D7] has the outflow path (16) and the outflow path (1).
6 ') was the same as the microchemical device [D5] except that the contact angle with the water on the inner surface at the connection with the flow path (14) was 87 °.

[Liquid-Liquid Contact Test] The same test as in Example 5 was performed on the microchemical device [D7]. As a result, the two liquids flowed out from the outflow passage (16 ′) in a lump,
It did not flow out of the outflow channel (16). However, when the test is started with the outflow channel (16) filled with water,
In a very narrow range in which the flow rate of water is slightly smaller than the flow rate of n-hexane, water flows out of the outflow path (16), and n- flows
Hexane eluted.

That is, the contact angle δ between the outflow passage (16) connected to the low contact angle portion of the flow path (14) and the outflow passage (16 ') connected to the high contact angle portion is in contact with water. _L ,
Even when δ _H is more than 25 ° and not more than 90 ° and there is no difference, it is possible to separate water and n-hexane, but the conditions are limited.

<Example 8> [Preparation of microchemical device] In Example 5, a tube made of polytetrafluoroethylene was inserted as the outflow channel (16) to a depth of 1/2 of the position of the flow channel (14). A microchemical device [D8] was produced in the same manner as in Example 5 except that the device was inserted and fixed to the position of the flow path (14) instead of fixing.

[Contact Angle of Each Part with Water] That is, the microchemical device [D8] has the outflow path (16) and the outflow path (1).
6 ′) Both were the same as the microchemical device [D5] except that the contact angle with the water on the inner surface at the connection with the flow path (14) was 110 °.

[Liquid-Liquid Contact Test] When a test similar to that of Example 5 was performed on the microchemical device [D8], the flow rate of water from the outflow passage (16) was extremely narrow in a slightly narrower range than the flow rate of n-hexane. Water, n from outflow channel (16 ')
-Hexane eluted.

That is, the contact angle δ between the outflow passage (16) connected to the low contact angle portion of the flow path (14) and the outflow passage (16 ') connected to the high contact angle portion is in contact with water. _L ,
Even when δ _H exceeds 90 ° and there is no difference between them, it was found that water and n-hexane could be separated, but the conditions were limited.

<Example 9> [Preparation of microchemical device] In Example 1, instead of polycarbonate [p2], transparent rigid polyvinyl chloride [p] was used as a material for members (A) and (B).
1], nylon 6 (“A4 manufactured by BASF Japan Ltd.”
H ") [p3] and a microchemical device [D9-1-3] in the same manner as in Example 3 except that a polyarylate resin (" U polymer U-70 "manufactured by Unitika Ltd.) [p4] was used, respectively. ] Was produced.

[Liquid-Liquid Contact Test] The same test as in Example 3 was performed on the microchemical device [D9-1-3], and the same result as in Example 1 was obtained.

[0121]

[Table 1]

[0122]

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 diagram showing a member of a microchemical device manufactured in an 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 [e1] Cured material layer 1 2 'Energy ray curable composition [e2] Cured material layer 13 3 Energy ray curable composition [e1] Cured material layer 2 3' Energy ray-curable composition [e2] Cured product layer 2 4 Flow path 5 Inflow path 5 'Inflow path 6 Outflow path 6' Outflow path 7 Inlet 7 'Inflow 8 Outflow 8' Outflow 9 Energy ray curable composition Object [e1] cured product

FIGS. 2A and 2B are a plan view (a) of the microchemical device manufactured in the example viewed from a direction perpendicular to the surface of a member (B) and a front view (b) corresponding to the plan view.

[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 14 Flow path 15 Inflow path 15 'Inflow path 16 Outflow path 16' Outflow path 17 Polycarbonate Plate 18 Energy ray-curable composition [e2] Cured material layer 1

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) G01N 1/10 G01N 1/10 NF term (reference) 4D056 AB15 AC02 AC03 AC09 AC22 BA01 BA20 CA02 CA08 CA39 CA40 DA10 4G075 AA70 BB03 BD15 BD22 EE12 FC02 4H006 AA04 AD16

Claims (9)

[Claims] 1. A sectional area of 1 × 10 ⁻¹² m ² to 1 × 10 ⁻⁶ m ^2.
Wherein the inner surface of the flow channel has a low contact angle portion having a contact angle with water of 25 ° or less, and a low contact angle portion having a contact angle with water. Having a high contact angle portion that is at least 10 ° higher than that of the flow path, and wherein the low contact angle portion and the high contact angle portion are respectively continuous from the upstream end to the downstream end of the flow path without interruption. Micro chemical device. 2. The microchemical device according to claim 1, wherein the outflow path is formed at a downstream end of the flow channel from a low contact angle portion and a high contact angle portion of the flow channel. 3. The contact angle δ _H with water on the inner surface of the connection portion of the outflow passage connected to the high contact angle portion of the flow passage is set at the connection portion of the outflow passage connected to the low contact angle portion of the flow passage. The microchemical device according to claim 2, wherein the contact angle between the inner surface and water is greater than or equal to 10 _L. 4. A contact angle δ _L of the inner surface with water at a connection portion of the outflow channel connected to the low contact angle portion of the flow channel, and an inner surface of the outflow channel connection portion connected to the high contact angle portion of the flow channel. The contact angle δ _H with water is (a) δ _L ≦ 25 ° and 3
5 ° ≦ δ _H , (b) δ _L ≦ 90 °, and 90 ° <δ
_H, micro chemical device according to claim 3, wherein satisfies at least one of these conditions. 5. The microchemical device according to claim 1, wherein the outflow path connected to the high contact angle portion of the flow path is a tube connected to the flow path. 6. The microchemical device according to claim 1, wherein an inflow channel is formed at an upstream end of the flow channel by connecting to the low contact angle portion and the high contact angle portion of the flow channel. Item 3. The microchemical device according to Item 1. 7. The member (A) having a channel filled with a solid substance except for a portion serving as a channel between the member (A) and the member (B) or having a groove on a surface thereof. It is formed between the member (A) and the member (B) in a shape in which another member (B) is in close contact with the groove forming surface. The member (A) side bottom surface, the member (A) side bottom surface and at least one side surface, the member (B) surface, the member (B) surface and at least one side surface are any one selected from the group consisting of: The microchemical device according to any one of the above items. 8. The microchemical device according to claim 7, wherein the member (A) and the member (B) are made of an organic polymer. 9. The member (A) and the member (B) are each
8. 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. Micro chemical device.