JP2003190768A - Method for manufacturing micro-fluid device having porous part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a micro-fluid device having a porous part by accurately laminating and fixing a film-like member having a microporous part provided thereto or an extremely thin and flexible film-like member having a porous part to another member in an industrially stable manner. <P>SOLUTION: The method for manufacturing the micro-fluid device having a flow channel and the porous part connected thereto includes a process for coating a coating support with an energy beam curable composition to form a first member comprising a cured or semicured coating film having the porous part, which comprises pores reaching the upper and rear surfaces of the member, provided to at least a part thereof, a process for laminating and fixing the first member to a second member having a deficient part becoming a flow channel reaching the surface thereof so as to superpose the porous part of the first member on the deficient part of the second member and a process for removing the coating support from the first member. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a microfluidic device having a porous portion, which comprises forming a layered member having a porous portion on a coated support and transferring the layered member onto another member. The present invention relates to the manufacturing method.

The microfluidic device manufactured by the manufacturing method of the present invention has a minute fluid channel inside, and the channel is outside the microfluidic device or in the microfluidic device through the pores of the porous portion. A microfluidic device that is in communication with other channels and is used, for example, for filtration, concentration, degassing, air supply, immobilization of substances, and the like. The microfluidic device of the present invention is, for example, a microreaction device (microreactor) used in a wide field such as chemistry, biochemistry, or physical chemistry; integrated DNA analysis device, microelectrophoresis device, microchromatography device, It is used as a micro analysis device such as a micro sensor.

[0003]

2. Description of the Related Art "Analytical Chemistry (AN
ALYTICAL CHEMISTRY) ", 70th
Vol. 3553-3556 (1998), a dialysis membrane is sandwiched between two plate-shaped members having narrow grooves dug in a symmetrical shape and screwed together. By flowing the stock solution into the groove in contact with the surface (which is a capillary flow path by sandwiching the dialysis membrane) and flowing the dialysate into the groove in contact with the other surface of the dialysis membrane (same as above), Microfluidic devices that perform dialysis between channels have been described.

However, when a porous membrane having a large number of pores penetrating both sides of the membrane is used instead of the dialysis membrane which is a gel membrane, the above-mentioned structure gives the following unfavorable results. Tended to. That is, when used for filtering a fluid, the fluid not only flows in a direction penetrating the front and back of the porous membrane, but also flows in the pores communicating with each other in a direction parallel to the membrane, and flows to the outside of the device. Leaking out,
There was a defect that it caused contamination with other flow paths. This problem has been a serious problem in a microfluidic device in which the distance between the flow paths and the distance between the flow path and the outside of the device are short.

In order to eliminate such a problem, a porous film portion is formed on a part of a film-shaped member, and this is laminated and adhered to two members having a groove serving as a flow path, It is possible to adopt a method of sandwiching between the members, but when the porous portion is minute, it is considerably difficult to accurately align and sandwich the positions of the porous membrane portion and the thin groove. ,
Further, when a member having a porous portion is so thin and flexible that it cannot stand on its own, it was industrially very difficult to align and stack the member without stretching it.

[0006]

The problem to be solved by the present invention is to provide a film-like member having a minute porous portion in a part thereof, and a very thin and flexible film-like member having a porous portion. It is an object of the present invention to provide a method for manufacturing a microfluidic device having a porous portion by precisely stacking and fixing a member on another member by an industrially stable method.

[0007]

Means for Solving the Problems As a result of intensive studies on the method for solving the above-mentioned problems, the present inventors have found that a first member having a porous portion formed of pores on a coated support is provided on a surface thereof. On the second member having a defective portion which will be a flow path to reach, a part of the defective portion and the porous portion are laminated and fixed so as to overlap with each other, and the coating support is removed from the first member, thereby The inventors have found that a microfluidic device having a channel and a porous portion connected to the channel can be easily manufactured, and completed the present invention.

That is, according to the present invention, the active energy ray-curable composition (x) containing the active energy ray-polymerizable compound (a) is coated on a coated support, and at least a part of the member is coated. Step (I) of forming a first member made of a cured or semi-cured coating film having a porous portion made of pores reaching from the front surface to the back surface of the member, second having a defective portion serving as a flow path reaching the surface A step of laminating and fixing the porous portion of the first member so as to overlap with at least a part of the defective portion of the member (I
I), and a step of transferring the first member to the second member by removing the coating support from the first member (III), and having a flow path and a porous portion connected to the flow path. A method for manufacturing a microfluidic device is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION According to the manufacturing method of the present invention, the porous portion of the first member is overlapped with at least a part of the defective portion of the second member having the defective portion reaching the surface. By laminating and fixing, a microfluidic device having a channel and a porous portion connected to the channel is manufactured.

The microfluidic device manufactured by the manufacturing method of the present invention has a capillary channel inside. The cross-sectional area of the channel is preferably 1 × 10 ⁻¹² m ² to 1 × 10 ^−6.
m ² , more preferably 1 × 10 ⁻¹⁰ m ^{2 to} 2.5 ×
It is 10 ⁻⁵ m ² . The width and height of the cross section of the flow path are both preferably 1 μm to 1000 μm, and more preferably 10 μm to 500 μm. If the cross section of the flow channel is smaller than these dimensions, it becomes difficult to manufacture, and if it exceeds this range, the characteristics as a microdevice are reduced. The microfluidic device manufactured by the present invention has a flow path having a cross-sectional area in this range, so that reaction / analysis time can be shortened, synthesis / analysis can be performed with a small amount of sample, small amount of waste, and improvement of temperature control accuracy. The characteristics of the microfluidic device such as, are exhibited.

The width / height ratio of the cross section of the flow channel can be arbitrarily set according to the use and purpose, but is generally preferably 0.5 to 10 and more preferably 0.7 to 5. The cross-sectional shape of the flow path is arbitrary such as a rectangle (including a rectangle with rounded corners; the same applies hereinafter), a trapezoid, a circle, a semicircle, and a slit. The width of the channels need not be constant. The flow path may or may not be connected to the outside of the microfluidic device manufactured by the present invention, and other structures inside the device, such as a liquid storage tank, a waste liquid absorption unit, and a pressure You may contact the tank, decompression tank, etc.

The shape of the flow channel as viewed from the outside of the microfluidic device, for example, the shape as viewed from the direction perpendicular to the surface of the formed microfluidic device on the side of the first member is straight, branched or comb-shaped depending on the purpose of use. It may be curved, spiral, zigzag, or any other shape. The flow path is a capillary space in which a fluid flows, and is used as a reaction field, a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, etc., in addition to a flow channel for merely transferring a fluid. May be. A structure other than the flow path, a waste liquid absorption part, a detection part, a waste liquid absorption part, a connection port to the outside of the device, etc. may be formed by being connected to the flow path.

The coated support used in the production method of the present invention is a coating film-like first support having a porous portion, which is obtained by applying the composition (x), which is a material for forming the first member, onto the composition and solidifying the composition. One member can be formed and can be removed from the first member in some way. In the present invention, "coating" includes "casting", and "coating" includes "casting". That is, the coating support may have irregularities on the surface, and the coating film may have portions having different thicknesses.

The shape of the coated support is not particularly limited and may be any shape. For example, sheet shape (including film shape, ribbon shape, belt shape), plate shape, roll shape (coating support using a large roll as a coating support, curing, lamination,
And the steps such as peeling are performed while the roll makes one revolution), a mold in which the portion forming the porous portion is convex,
Although it may be a molded product or mold having a complicated shape, the composition (x) can be easily applied onto it, and the active surface can be easily irradiated with active energy rays. A curved shape is preferable, and a flexible sheet shape is preferable from the viewpoint of easy removal by peeling. Further, from the viewpoint of productivity, it is also preferably in a roll form.

The material of the coated support is not particularly limited as long as the above conditions are satisfied, but the required characteristics differ depending on the method of forming the porous portion in the first member in step (I). That is, in the step (I), when the coated support is in contact only with the composition (x) and its cured product, it is not substantially attacked by the composition (x) and the active energy rays used. , For example, dissolution, decomposition, polymerization, etc. do not occur, and
It is sufficient that the composition (x) is not substantially attacked.
When the film-forming solution (e), the film-forming solution (f), or the film-forming solution (g) is used in the step (I), it must be substantially unaffected by the film-forming solution used. There is.

Examples of materials that can be used as the coating support include polymers (polymers); glass; crystals such as quartz; ceramics; semiconductors such as silicon; metals and the like. Among these, polymers and metals Is particularly preferable.

The polymer used for the coating support may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. . Also,
The coated support may be composed of a polymer blend or a polymer alloy, or may be a laminate or other composite. Further, the coated support may contain additives such as a modifier, a colorant, a filler and a reinforcing material.

When the removal of the coated support is by peeling, it is difficult to dissolve in many kinds of the composition (x), and peeling from the cured product is easy.
Polyolefin-based polymers, chlorine-containing polymers, fluorine-containing polymers, polythioether-based polymers, polyetherketone-based polymers and polyester-based polymers are preferably used.

The coated support, whether a polymer or other material, may be surface-treated. The surface treatment is intended to prevent dissolution by the composition (x), to facilitate separation of the composition (x) from the cured product, and to improve wettability of the composition (x). And a composition (x) which prevents the infiltration of the composition (x).

The surface treatment method of the coated support is arbitrary,
For example, corona treatment, plasma treatment, flame treatment, acid or alkali treatment, sulfonation treatment, fluorination treatment, primer treatment with a silane coupling agent or the like, surface graft polymerization, application of a surfactant or a release agent, rubbing or the like. Physical treatments such as sandblasting are included.

When the coating thickness of the composition (x) is thin, the coating support is preferably wet with the composition (x) or has a weak repellency.
That is, the contact angle with the composition (x) used is preferably 90 degrees or less, more preferably 45 degrees or less, further preferably 25 degrees or less, and most preferably 0 degree. preferable.

A material whose coating support has a low surface energy,
For example, in the case of polyolefin, fluoropolymer, polyphenylene sulfide, polyether ether ketone, etc., the contact angle with the composition (x) to be used can be reduced by surface treatment of the adhesive surface of the coated support. preferable.

The surface treatment makes it possible to adjust the cured first member so that it will not adhere so strongly that it cannot be peeled off. As a surface treatment method for improving the wettability, for example, corona discharge treatment, plasma treatment,
Acid or alkali treatment, sulfonation treatment, primer treatment, and application of a surfactant are preferable.

On the other hand, when the coated support is formed of a material having good adhesiveness and difficult to peel off the first member, fluorine treatment, application of a fluorine-based or silicon-based release agent, surface grafting Surface treatment such as introduction of a hydrophilic group or a hydrophobic group by a method is preferable. Further, when the coated support is a porous body such as paper, non-woven fabric or knitted fabric, the surface is made non-porous by treatment with a fluorine compound or coating in order to prevent the intrusion of the composition (x). It is preferable to carry out. In addition to the surface treatment, the wettability can be controlled by selecting a modifier to be blended with the coating support.

Examples of the modifier that can be contained in the coated support include hydrophobizing agents (water repellents) such as silicone oil and fluorine-substituted hydrocarbons; water-soluble polymers, surfactants, silica gel, etc. Inorganic powders, etc., and hydrophilizing agents; dioctyl phthalate, and other plasticizers. Examples of the colorant that can be contained in the coating support include arbitrary dyes and pigments, fluorescent dyes and pigments, and ultraviolet absorbers. Examples of the reinforcing material that can be contained in the temporary support include inorganic powders such as clay, organic and inorganic fibers and woven fabrics.

The energy ray-polymerizable compound (a) contained in the composition (x) is an addition-polymerizable, ring-opening-polymerizable, radical-polymerizable, anionic compound as long as it can be polymerized and cured by active energy rays. It may be any one such as polymerizable and cationically polymerizable. The compound (a) is not limited to a compound that is polymerized in the absence of a polymerization initiator, and a compound that is polymerized by an active energy ray only in the presence of a polymerization initiator can also be used.

The compound (a) is preferably a chain-polymerizable compound because it has a high polymerization rate, and preferably has a polymerizable carbon-carbon double bond as an active energy ray-polymerizable functional group. , Highly reactive (meta)
Acrylic compounds, vinyl ethers, and maleimide compounds that cure even in the absence of a photopolymerization initiator are preferred.

Further, the compound (a) is a compound which is polymerized to form a crosslinked polymer because it is easy to form a semi-cured state in which the fluidity is lost but the polymerizable functional group remains. Preferably there is. Therefore, 2 in one molecule
A compound having one or more polymerizable carbon-carbon double bonds (hereinafter, "having two or more polymerizable carbon-carbon double bonds in one molecule" may be referred to as "multifunctional").
Is more preferable.

Examples of polyfunctional (meth) acrylic monomers that can be preferably used as the compound (a) include, for example, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth). ) Acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, neopentyl glycol hydroxydipivalate Di (meth) acrylate, dicyclopentanyl diacrylate,

Bifunctional monomers such as bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tris (acryloxyethyl) isocyanate. Examples thereof include trifunctional monomers such as nurate and caprolactone-modified tris (acryloxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; and hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate.

As the compound (a), a polymerizable oligomer (including a prepolymer; the same applies hereinafter) can be used, and examples thereof include those having a mass average molecular weight of 500 to 50,000. Examples of such a polymerizable oligomer include (meth) acrylic acid ester of epoxy resin, (meth) acrylic acid ester of polyether resin,
Examples thereof include (meth) acrylic acid ester of polybutadiene resin and polyurethane resin having a (meth) acryloyl group at the molecular end.

Examples of the maleimide compound (a) include 4,4'-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1, 2-bismaleimideethane,
1,6-Bismaleimide hexane, triethylene glycol bismaleimide, N, N'-m-phenylene dimaleimide, m-tolylene dimaleimide, N, N'-1,4
-Phenylene dimaleimide, N, N'-diphenylmethane dimaleimide, N, N'-diphenyl ether dimaleimide, N, N'-diphenylsulfone dimaleimide,

1,4-bis (maleimidoethyl) -1,
Bifunctional maleimides such as 4-diazoniabicyclo- [2,2,2] octane dichloride; maleimides having a maleimide group such as N- (9-acridinyl) maleimide and a polymerizable functional group other than the maleimide group, and the like. .
The maleimide-based monomer can also be copolymerized with a compound having a polymerizable carbon-carbon double bond such as a vinyl monomer, vinyl ethers, and an acrylic monomer.

These compounds (a) can be used alone or in combination of two or more. Further, the energy ray-polymerizable compound (a) is used for adjusting the viscosity,
A mixture of a polyfunctional monomer and a monofunctional monomer may be used for the purpose of increasing adhesiveness or tackiness in a semi-cured state.

Examples of monofunctional (meth) acrylic monomers include methyl methacrylate and alkyl (meth).
Acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate,
Alkylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, hydroxyalkyl (meth)
Acrylate, glycerol acrylate methacrylate,

Butanediol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, ethylenoxide-modified phthalic acid acrylate, w-cargoxyaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyrihexahydrohydrogenphthalate, fluorine-substituted alkyl (meth) acrylate,

Chlorine-substituted alkyl (meth) acrylate,
Sulfonic acid soda ethoxy (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, phosphoric acid ester group-containing (meth) acrylate, sulfonic acid ester group-containing (meth) acrylate, silano group-containing (meth) acrylate, (( Di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl)
Examples thereof include acrylamide, (N, N-dialkyl) acrylamide, achloroylmorpholine and the like.

Examples of monofunctional maleimide-based monomers include N-methylmaleimide, N-ethylmaleimide,
N-butylmaleimide, N-alkylmaleimide such as N-dodecylmaleimide; N-alicyclic maleimide such as N-cyclohexylmaleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-diyl Alkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide,

2,3-dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2
N-, such as -ethyl-6-methylphenyl) maleimide.
(Substituted or unsubstituted phenyl) maleimide; maleimide having halogen such as N-benzyl-2,3-dichloromaleimide, N- (4'-fluorophenyl) -2,3-dichloromaleimide; hydroxyl group such as hydroxyphenylmaleimide A maleimide having; a maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide;

Maleimides having an alkoxyl group such as N-methoxyphenylmaleimide; maleimides having an amino group such as N- [3- (diethylamino) propyl] maleimide; polycyclic aromatic maleimides such as N- (1-pyrenyl) maleimide. A maleimide having a heterocycle such as N- (dimethylamino-4-methyl-3-coumarinyl) maleimide and N- (4-anilino-1-naphthyl) maleimide.

Other components can be added to the composition (x) if necessary. Examples thereof include active energy ray polymerization initiators, polymerization retarders, polymerization inhibitors, thickeners, modifiers, colorants, and solvents.

When a mixture which is copolymerized with each other is used as the compound (a), the copolymerizable compound is a monofunctional polymerization compound, an amphipathic compound, a hydrophilic compound,
It may be a hydrophobic compound or the like. The hydrophilic compound which can be mixed and used as the compound (a) has a hydrophilic group in the molecule and gives a hydrophilic polymer.

Examples of such a hydrophilic compound include vinylpyrrolidone; N-substituted or unsubstituted "acrylamide; acrylic acid; polyethylene glycol group-containing (meth) acrylate; hydroxyl group-containing (meth) acrylate; amino group-containing (meth). Acrylate; carboxyl group-containing (meth) acrylate; phosphoric acid group-containing (meth) acrylate; sulfone group-containing (meth) acrylate and the like.

The hydrophobic polymerizable compound which can be mixed and used as the compound (a) has a hydrophobic group in the molecule and gives a hydrophobic polymer. Such compounds include:
For example, alkyl (meth) acrylate; fluorine-containing (meth) acrylate; (alkyl-substituted) siloxane group-containing (meth) acrylate and the like can be exemplified.

The copolymerizable amphipathic compound which can be mixed and used as the compound (a) is preferably a compound having at least one polymerizable carbon-carbon unsaturated bond in one molecule. The amphipathic compound does not need to be a polymer whose homopolymer becomes a crosslinked polymer, but may be a compound which becomes a crosslinked polymer.

Further, the amphipathic compound can be the composition (x) which is uniformly dissolved. In this case, "dissolve uniformly" means that macroscopic phase separation does not occur,
The state in which micelles are formed and stably dispersed is also included.

The amphipathic compound referred to in the present invention is a compound having a hydrophilic group and a hydrophobic group in the molecule and compatible with both water and a hydrophobic solvent. Even in this case, the term "compatible" means that macroscopic phase separation does not occur, and includes a state in which micelles are formed and stably dispersed. The amphipathic compound has a solubility in water at 0 ° C. of 0.5% by mass or more and 25 ° C. cyclohexane: toluene =
Solubility in 5: 1 (mass ratio) mixed solvent is 25% by mass
The above is preferable.

The solubility referred to here, for example, the solubility is 0.
5% by mass or more means that at least 0.5% by mass of the compound can be dissolved, and although 0.5% by mass of the compound is not soluble in the solvent, a very small amount of the compound is present in the compound. It does not include those in which the solvent is soluble. Solubility in water or cyclohexane: toluene =
When a compound having at least one of solubility in a 5: 1 (mass ratio) mixed solvent is lower than these values, it becomes difficult to satisfy both high surface hydrophilicity and water resistance.

When the amphipathic compound has a nonionic hydrophilic group, particularly a polyether type hydrophilic group, the hydrophilicity and hydrophobicity are balanced by the HLB (H.L.B.) value of Griffin. Those in the range of 10 to 16 are preferable, and those in the range of 11 to 15 are more preferable. Outside this range, it is difficult to obtain a molded article having high hydrophilicity and excellent water resistance, or the combination and mixing ratio of the compounds for obtaining it are extremely limited, and the performance of the molded article becomes poor. Tends to be stable.

The hydrophilic group possessed by the amphipathic compound is arbitrary, and examples thereof include cationic groups such as amino group, quaternary ammonium group and phosphonium group; anionic groups such as sulfone group, phosphoric acid group and carbonyl group; hydroxyl group, It may be a polyether group such as a polyethylene glycol group, a nonionic group such as an amide group, or a zwitterionic group such as an amino acid group.
The hydrophilic group is preferably a polyether group, particularly preferably a compound having a polyethylene glycol chain having a repeating number of 6 to 20.

As the hydrophobic group of the amphipathic compound, for example, an alkyl group, an alkylene group, an alkylphenyl group,
Examples include long-chain alkoxy groups, fluorine-substituted alkyl groups, siloxane groups, and the like. The amphipathic compound preferably contains, as a hydrophobic group, an alkyl group having 6 to 20 carbon atoms or an alkylene group. The C6-C20 alkyl group or alkylene group may be contained in the form of, for example, an alkylphenyl group, an alkylphenoxy group, an alkoxy group, a phenylalkyl group, or the like.

The amphipathic compound has a polyethylene glycol chain having a repeating number of 6 to 20 as a hydrophilic group, and
A compound having an alkyl group or an alkylene group having 6 to 20 carbon atoms as a hydrophobic group is preferable. As an amphipathic compound that can be more preferably used, a compound represented by the general formula (1)
The compound represented by

General formula (1) CH_Two= CR¹COO (R^TwoO)_n-Φ-R^Three (In the formula, R¹Is hydrogen, a halogen atom or a lower alkyl group
And R^TwoRepresents an alkylene group having 1 to 3 carbon atoms
, N is an integer of 6 to 20, φ is a phenylene group, R ^ThreeIs charcoal
Represents an alkyl group having a prime number of 6 to 20)

Here, R ³ is more specifically a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or a pentadecyl group, preferably a nonyl group or a dodecyl group. In the general formula (1), n
It is preferable that the larger the number of R ³ , the larger the number of carbon atoms of R ³ .

Among these amphipathic compounds, nonylphenoxy polyethylene glycol (n = 7 to 20)
(Meth) acrylate, nonyl polyethylene glycol (n = 7 to 20) (meth) acrylate, and nonylphenoxy polypropylene glycol (n = 7 to 20) (meth) acrylate are particularly preferable.

The active energy ray polymerization initiator that can be added to the composition (x) is active with respect to the active energy ray used in the present invention and is capable of polymerizing the compound (a). There is no particular limitation as long as it is a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator. The active energy ray polymerization initiator is particularly effective when the active energy ray used is a light ray.

As such a photopolymerization initiator, for example, p-tert-butyltrichloroacetophenone,
Acetophenones such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methyl Ketones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone;

Benzoin, benzoin methyl ether,
Examples thereof include benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; and azides such as N-azidosulfonylphenyl maleimide. Further, a polymerizable photopolymerization initiator such as a maleimide compound can be used.

The amount of the photopolymerization initiator used in the composition (x) is 0.
The range of 005 to 20 mass% is preferable, and the range of 0.1 to 5 mass% is particularly preferable. The photopolymerization initiator may be a polymerizable one, for example, a polyfunctional or monofunctional maleimide-based monomer exemplified as the energy ray-polymerizable compound (a). The amount used in this case is not limited to the above.

Examples of the polymerization retarder which can be added to the composition (x) include styrene, α-methylstyrene and α-phenylstyrene when the energy ray-polymerizable compound (a) is an acryloyl group-containing compound. , P-
Octylstyrene, p- (4-pentylcyclohexyl) styrene, p-phenylstyrene, p- (p-ethoxyphenyl) phenylstyrene, 2,4-diphenyl-4-methyl-1-pentene, 4,4'-divinylbiphenyl , 2-vinylnaphthalene, and other vinyl monomers having a lower polymerization rate than the energy ray-polymerizable compound (a) used.

Examples of the polymerization inhibitor which can be added to the composition (x) include hydroquinone and methoxyhydroquinone when the energy ray-polymerizable compound (a) is a polymerizable carbon-carbon double bond-containing compound. Derivatives such as hydroquinone; butylhydroxytoluene, te
Examples thereof include hindant phenols such as rt-butylphenol and dioctylphenol.

When light rays such as ultraviolet rays are used as the active energy rays, it is preferable to use at least one of a polymerization retarder and a polymerization inhibitor together with a photopolymerization initiator in order to improve patterning accuracy. In addition, examples of the thickener that can be added to the composition (x) include chain polymers such as polystyrene.

Examples of the modifier that can be added to the composition (x) include hydrophobic compounds such as silicone oil and fluorine-substituted hydrocarbon that function as water repellents and release agents; hydrophilizing agents and adsorption inhibitors. Water-soluble polymers such as polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol that function as agents; nonionic, anionic, cationic, and other surfactants that function as wettability improvers, release agents, and adsorption inhibitors To be Examples of the colorant that can be mixed and used in the composition (x) as needed include any dyes and pigments, fluorescent dyes, and ultraviolet absorbers.

The solvent which can be added to the composition (x) is not particularly limited, but the polymerizable compound (a) to be used and the additive added to the composition part (x), and the required viscosity. The type and addition amount of the solvent may change depending on the conditions. For example, such solvents include alcohols such as ethanol, ketones such as acetone,
Examples thereof include amide solvents such as N, N-dimethylformamide and chlorine solvents such as methylene chloride.

In the production method of the present invention, first, the composition (x) is applied to a coated support, and at least a part of the member is a porous portion having pores reaching from the front surface to the back surface of the member. And a film-shaped first member made of a cured or semi-cured product of the composition (x). [This step is referred to as "step (I)"]. As a method of applying the composition (x) to the coating support, any coating method can be used,
For example, spin coating method, roller coating method, casting method,
Dipping method, spray method, bar coater method, XY
Applicator method, screen printing method, letterpress printing method, gravure printing method, extrusion from a nozzle, casting, etc. can be mentioned. In addition, when the composition (x) has a high viscosity or when it is applied particularly thinly, a method of applying a solvent to the composition (x) and then applying the solvent may be employed. it can.

The coating film of the composition is irradiated with active energy rays to polymerize the compound (a) contained therein to cure or semi-cure the coating film of the composition (x). Active energy rays that can be used include ultraviolet rays, visible rays,
Light rays such as infrared rays, laser rays, and synchrotron radiation; ionizing radiation such as X-rays, gamma rays, and synchrotron radiation; particle rays such as electron rays, ion beams, beta rays, and heavy particle rays. Among these, ultraviolet light and visible light are preferable, and ultraviolet light is particularly preferable, from the viewpoints of handleability and curing speed. For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to perform irradiation with the active energy ray in a low oxygen concentration atmosphere.
The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, or a vacuum or reduced pressure atmosphere.

The cured or semi-cured coating film serving as the first member is subjected to patterning irradiation with an active energy ray in order to provide a defective portion to be a pore and a defective portion of the coating film for forming a porous portion. . The patterning irradiation method is arbitrary, and for example, irradiation is performed by masking unnecessary irradiation portions.
Alternatively, a photolithography technique such as scanning with a beam of active energy rays such as a laser can be used.

By setting the degree of curing of the coating film of the composition (x) to be semi-cured, it is possible to fix the coating to the second member without using an adhesive, and when an adhesive is used, Can improve the adhesive strength. When the cured state of the composition (x) is semi-cured,

It is preferable to carry out post-curing in any step before forming the final microfluidic device to completely cure it, but it is not necessary to completely cure the microfluidic device of the present invention unless the function of the microfluidic device of the present invention is hindered. No need to cure. In the case of curing with active energy rays, the post-curing may be the same as or different from the active energy rays used for semi-curing. Post-curing can also be thermal curing, in addition to curing with active energy rays.

Although the thickness of the first member is arbitrary, it is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. If it is thinner than this, manufacturing and transfer become difficult. The thickness of the first member is 10
The thickness is preferably 00 μm or less, more preferably 400 μm or less, still more preferably 200 μm or less. If it is thicker than this, the permeation resistance becomes too large when the porous part is used for filtration, and it is limited to uses other than filtration. In the step (I) of the present invention, when the porous portion is formed by the following "photolithographic method", the thickness of the first member needs to be made thinner as the pore diameter to be formed is smaller, in manufacturing. . The aspect ratio of pores, that is, the value of diameter / length (length = thickness of first member) is preferably 3 or less,
It is more preferably 1.5 or less.

The method of providing the porous portion on a part of the first member is arbitrary, and for example, the following first to fourth methods of the present invention can be preferably used. In the step (I), a preferred first method (hereinafter referred to as "photolithography method") in which a porous part is provided in a part of the cured or semi-cured coating film of the composition (x) which is the first member In the process of irradiating the composition (x) coating film with active energy rays to form a cured or semi-cured coating film, the pores are to be uncured without irradiation with active energy rays. Then, the uncured composition (x) in the non-irradiated portion is removed to form a porous portion composed of a large number of pores as defective portions of the cured or semi-cured composition (x) coating film. It is a method of forming the first member.

In this case, in order to increase the resolution, it is preferable to add a polymerization retarder, a polymerization inhibitor or an ultraviolet absorber to the composition (x). This method is preferable as a method for forming a porous part having a relatively large pore size. The pore size formed by the first method is arbitrary, but preferably 1
-30 μm, more preferably 5-10 μm.

In the step (I), a preferable second method (hereinafter referred to as "reaction-induced phase") in which a porous part is provided in a part of the cured or semi-cured coating film of the composition (x) which is the first member Separation method "
In some cases, the cured or semi-cured coating film of the composition (x) is treated as a portion forming a porous part instead of pores in the same manner as in the above-mentioned first preferred method. A defective portion of the coating film is formed, and an active energy ray-polymerizable compound (b) [hereinafter simply referred to as "compound (b)"] and a poor solvent (r) for the compound (b) are formed in the defective portion.
Active energy ray curable film forming liquid containing (e)
[Hereinafter, simply referred to as "film forming liquid (e)"] is applied (filled), and the active energy ray-curable resin film forming liquid (e) is applied.
To the active energy ray to polymerize the active energy ray-polymerizable compound (b) and to phase-separate the polymer and the poor solvent (r) to form a porous portion, thereby forming a porous portion. It is a method of forming a first member having: on a coated support.

The compound (b) used in the reaction-induced phase separation method of step (I) may be the same as the polymerizable compound (a), and is listed as the usable compound (a). It may be selected from the compound group and combined.

The poor solvent (r) is compatible with the compound (b), but the polymer formed from the compound (b) is soluble (compatible).
It does not. The degree of compatibility between the poor solvent (r) and the compound (b) may be such that a uniform film forming solution (e) can be obtained. Such poor solvent (r) may be a single solvent or a mixed solvent. In the case of a mixed solvent, a compound which is incompatible with the compound (b) by itself alone or a compound (b)
The polymer may be dissolved. Examples of the poor solvent (r) include alkyl esters of fatty acids such as methyl decanoate, methyl laurate and diisobutyl adipate; ketones such as diisobutyl ketone; alcohols such as butanol; a mixture of 2-propanol and water. And a mixture of water and an alcohol.

The content of the compound (b) in the film-forming solution (e) is preferably 15% by mass to 50% by mass, and 25% by mass to
40% by mass is more preferable. Depending on the composition ratio of the compound (b), the pore diameter and the strength of the porous part produced by this production method may change. When the content of the compound (b) is 15% by mass or less, the strength of the porous part is largely reduced, and when the content of the compound (b) is 50% by mass or more, it is difficult to adjust the pore size of the porous part. It is not preferable. When the content of the compound (b) is high, the porous shape is likely to have a three-dimensional mesh shape (sponge shape), and when the content is low, it tends to be agglomerated particle shape.
Moreover, the larger the content of the compound (b), the smaller the pore size tends to be.

The film-forming solution (e) contains, for example, other additives such as a solvent for adjusting the pore size, coating properties, smoothness, resolution, degree of hydrophilicity, and other functional properties, if necessary. For example, polymerization initiator, solvent, surfactant, hydrophobic compound, polymerization inhibitor, polymerization retarder, thickener, modifier, colorant, fluorescent dye, ultraviolet absorber, enzyme, protein, cell, catalyst, etc. It can be added. Specific examples of the additive that can be added to the film-forming solution (e) are the same as the examples of the additive that can be added to the composition (x) used in the present invention.

In this reaction-induced phase separation method,
A so-called isotropic film is formed in which the pore size is uniform in the thickness direction of the film, but a volatile solvent is added to the film-forming solution (e), and after application, before irradiation with active energy rays. By volatilizing and removing a part thereof, a so-called heterogeneous film (also referred to as an asymmetric film) having a pore size distribution in the film thickness direction can be formed. At this time, by adding a volatile good solvent, a layer with a small pore size (also referred to as a dense layer) can be formed on the contact surface with the coating support, and a volatile poor solvent or non-solvent is added. By doing so, a dense layer can be formed on the surface opposite to the coated support.

In this reaction-induced phase separation method, it is easy to form a porous body having a pore size of about a microfiltration membrane, and for example, a porous portion having a pore size of 0.05 to 1 μm can be formed. The dense layer formed by the method of adding the volatile solvent can have a pore size of 0.01 to 0.5 μm.

In the step (I), a preferred third method (hereinafter referred to as "UV wet method") in which a porous portion is provided in a part of the cured or semi-cured coating film of the composition (x) which is the first member May be referred to as “) in the cured or semi-cured coating film of the composition (x) in the same manner as in the above-mentioned first preferred method, as a portion forming a porous portion instead of pores. A defective portion of the membrane is formed, and the chain polymer (p), the active energy ray-polymerizable compound (m), the chain polymer (p) and the compound (m) are dissolved in the defective portion. , And compound (m)
The film-forming solution (f) containing a solvent (s) which does not dissolve the polymer of (1) is applied (filled) to the cured (or semi-cured) composition (x) to form a defect in the film-forming solution ( f) A coating film is formed, the coating film (f) coating film is irradiated with an active energy ray, the coating film (f) coating film is pre-cured into a gel, and the pre-cured film forming liquid ( f) by bringing the coating film into contact with a solvent (n) which is miscible with the solvent (s) but does not dissolve the chain polymer (p), and the chain polymer (p) is aggregated and deposited in a porous form, It is a method of forming a first member having a porous portion on a coated support.

Compound (m) used in this UV wet method
May be the same as the polymerizable compound (a),
A combination of compounds selected from the group of compounds listed as compounds usable as the compound (a) may be used. The chain polymer (p) used in this UV wet method is not particularly limited as long as it is a solvent (s) soluble polymer. For example, styrene-based polymers such as polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymers, polystyrene / acrylonitrile copolymers; polysulfone-based polymers such as porsulfone and polyethersulfone;

(Meth) acrylic polymer such as polymethylmethacrylate and polyacrylonitrile; polymaleimide polymer; bisphenol A polycarbonate,
Examples thereof include polycarbonate-based polymers such as bisphenol F-based polycarbonate and bisphenol Z-based polycarbonate; cellulose-based polymers such as cellulose acetate and methyl cellulose; polyurethane-based polymers; polyamide-based polymers; polyimide-based polymers. You may use these polymers in mixture of 2 or more types. By mixing and using two or more polymers that are incompatible with each other,
It is possible to obtain a porous body having a relatively large pore size.

The solvent (s) used in the UV wet method is not particularly limited as long as it can dissolve the compound (m) and the chain polymer (p) but does not dissolve the polymer of the compound (m). It is not something that will be done. Here, "does not dissolve the polymer of the compound (m)" includes the following two cases. That is, in one of them, the compound (m) is a monofunctional polymerizable compound, and the solvent (s) does not dissolve the chain polymer which is a polymer of the compound (m). The other is the case where the compound (m) is a polyfunctional polymerizable compound, and in this case, the solvent (s) swells a crosslinked polymer which is a polymer of the compound (m). Alternatively, it may not be swollen. That is, in these cases, when the film-forming liquid (f) is irradiated with an active energy ray, the film-forming liquid (f) loses fluidity and becomes in a pre-cured state.

Solvents that can be used as the solvent (s) are, for example, N, N-dimethylformamide, N, N
Examples include amide solvents such as dimethylacetamide, chlorine solvents such as dimethyl sulfoxide and methylene chloride. The solvent (s) may be a mixed solvent.

The content of the polymer (p) in the film-forming liquid (f) containing the chain polymer (p), the compound (m) and the solvent (s) is 5% by mass to 40% by mass. % Is preferable, and 10% by mass to 25% by mass is more preferable. When the content is 5% by mass or less, the strength of the porous portion is largely reduced, and the content is 40%.
If it is more than mass%, it becomes difficult to adjust the pore size of the porous part, which is not preferable.

The content of the compound (m) in the film-forming solution (f) is preferably 3% by mass to 40% by mass, and 3% by mass to
25% by mass is more preferable. The solvent (n) used in this UV wet method is miscible with the solvent (s) and does not dissolve the chain polymer (p). The solvent (n) may or may not swell the polymer of the compound (m). As the solvent (n) which can be preferably used, for example, water, alcohols such as propanol,
Examples include a mixture of water and alcohol.

The film-forming liquid (f) in a pre-cured state in which the fluidity is lost is brought into contact with the solvent (n) to cause the chain polymer (p) to aggregate and precipitate. The contact method is arbitrary, and may be immersion in a solvent (n), spraying, contact of an impregnant, contact of foam, contact of vapor, etc., but curing of the composition (x) formed on the support Alternatively, dipping is preferably performed for each semi-cured coating film.

When the chain polymer (p) is coagulated and deposited in the solvent (n), the polymer of the compound (m) entwined with the polymer (p) is also coagulated and deposited. That is, a polymer mixture in which the polymers of the polymer (p) and the compound (m) are entangled with each other is aggregated and deposited in a porous state. The porous shape may be a three-dimensional network shape (sponge shape), an agglomerated particle shape, or a complicated shape having macro voids.

As in the case of the preferred first and second methods, the additives described in the above-mentioned production method can be added to the film-forming solution (f), if necessary. This UV wet method usually forms a heterogeneous film (asymmetric film) having a dense layer on the opposite surface of the support, but does not have a dense layer.
So-called isotropic membranes can also be manufactured. In the UV wet method, it is easy to form a porous body having a pore size of about ultrafiltration membrane to microfiltration membrane, and typically, the pore size is 0.00
A 1-2 μm porous portion can be formed.

In the step (I), a preferred fourth method (hereinafter referred to as "wet method") in which a porous part is provided in a part of the cured or semi-cured coating film of the composition (x) which is the first member May be referred to as) in the cured or semi-cured coating film of the composition (x),
In the same manner as in the above-mentioned preferred first method, instead of the pores, a defective part of the coating film is formed as a part forming a porous part, and the chain polymer (p) is added to the defective part, A film-forming solution (g) containing a solvent (s) for dissolving the chain polymer (p) is applied (filled) to form a film-forming solution (g) coating film,
The film-forming solution (g) coating film is brought into contact with a solvent (n) which is miscible with the solvent (s) but does not dissolve the chain polymer (p), and the chain polymer (p) is aggregated into a porous state. By depositing, the first member having a porous portion can be formed on the coated support.

Chain polymer (p) used in this wet method
The solvent (s) and the solvent (n) may be the same as those shown in the above UV wet method. Further, as in the case of the first to third preferred methods described above, the other additives described in the above-mentioned production method can be added to the film-forming solution (g), if necessary.

The porous shape may be a three-dimensional mesh shape (sponge shape), an agglomerated particle shape, or a complicated shape having macro voids. The present wet method usually forms a heterogeneous film (asymmetric film) having a dense layer on the opposite surface of the coated support, but an isotropic film is also possible. In this wet method, it is easy to form a porous body having a pore size of about reverse osmosis membrane to microfiltration membrane, and a gas separation membrane having a non-porous dense layer can also be formed. By this wet method, for example, a porous portion having a dense layer having a pore diameter of 0.0005 to 2 μm can be formed.

The area of the porous portion formed in step (I) of the present invention is arbitrary, but is preferably 1 × 10 ^−10.
m ² to 1 × 10 ⁻⁴ m ² , and more preferably 2.
5 is a ^{× 10 -9 m 2 ~1 × 10} -5 m 2. If it is less than these ranges, the performance of the porous part (for example, filtration performance) will decrease, and if it exceeds these ranges, the device will become large, the merit as a microdevice will decrease, and the amount of fluid required will also increase. Not preferable.

In the microfluidic device manufactured by the manufacturing method of the present invention, the ratio (ratio) of the porous portion to the area of the first member is not particularly limited, but a porous membrane device of a normal size (for example, , Filtration filter), which is extremely small, and is preferably 1 × 10 ^{−8 to} 3 × 1.
0 ⁻² , and more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² . If it is 1 × 10 × ⁻⁸ or more, the merit as a microfluidic device is further increased, and if it is 3 × 10 ^{−2 or} less, the production of a fine porous portion is easier.

The pore size of the pores of the porous part is, as described above,
Although it can be arbitrarily set depending on the production method and the application, when used as a filtration membrane, for example, 1 nm to 30 μm is preferable,
More preferably, it is 10 nm to 10 μm. Further, the pore diameter may be uniform or may have a distribution in the thickness direction of the porous portion.

For example, the pore size distribution in which the pore size of the pores gradually decreases or increases from the surface of the porous part to the opposite surface, or the pore size gradually decreases from both surfaces of the porous part toward the center. Or, there may be a larger pore size distribution. Alternatively, the surface of the porous portion has a so-called dense layer having a pore size much smaller than other portions in the thickness direction (for example, several nm or less) and a thickness of about several nm to several μm. The pores may have a so-called asymmetric structure that gradually increases toward the opposite surface.
Alternatively, it may have a porous layer having a dense layer as described above on both surfaces and having a pore size distribution inside both surfaces.

The pore structure of the porous portion is not particularly limited. For example, when viewed from the surface and the thickness direction,
It may have a mesh-like structure or, for example, a diameter of 0.
It may have a structure in which fine particles of 1 μm to several μm are fused to each other, or may have a structure in which a large number of capillary pores penetrating from the surface to the opposite surface are arranged.

The second member used in the manufacturing method of the present invention is
It has a defective portion which becomes a flow path reaching the surface. The defect portion reaching the surface means a groove formed on the surface of the member, a hole formed in the member, a cavity provided inside the member, a part of which is opened on the surface of the member, or a composite structure thereof. The defective portion which becomes a flow channel means a defective portion which becomes a capillary flow channel by the defective portion itself of the second member or by being laminated with the first member.

The shape of the defective portion which serves as a flow passage through the member is, for example, a round hole, a square hole, a slit shape, a cone shape, a pyramid shape,
Barrels, screw holes, cuts (normally, the cross-sectional area is zero, and the deformation of the surrounding area creates a flow path with a finite cross-sectional area), and the defective parts with complicated shapes that change the cross-sectional area and direction. obtain. The concave portion that forms a concave flow path on the surface of the member may be a concave portion such as a cone, a pyramid, a trapezoid, an inverted trapezoid, a cone or a pyramid, or a groove that forms a flow path. A defective portion penetrating the member may be provided so as to communicate with the concave portion of the surface. The defective portion opened to the surface of the member that is connected to the defective portion inside the member is, for example, a capillary defective portion having both ends or one end opened, a cavity having an opening having an area smaller than the area as viewed from the surface, and the like. obtain.

The second member may be provided with a plurality of defect portions independent of each other. These defective portions may be defective portions that serve as a flow path reaching the surface, or may be other defective portions. Examples of other defect parts include, for example,
Examples include a development path for chromatography or electrophoresis, a detection section, an installation space for an absorber, a space used as a sensor embedding section, and a mark for alignment.

The method for producing the second member and the method for producing the defective portion of the second member are arbitrary. For example, injection molding, melt replica method, solution casting method, and photolithography using an active energy ray-curable composition. A cast molding method using an energy ray-curable composition, a micro-stereolithography method,
Cutting and cutting with a blade, drilling, punching, laser drilling, sandblasting, etc. can be used. Also,
The second member may be a structure in which a plurality of layered members are laminated and fixed.

Of these, photolithography using an active energy ray-curable composition as the second member forming material is preferable because it is easy to form fine and complicated defects and the productivity is high. The composition (x) can be used as the active energy ray-curable composition. However, it is not necessary to use the same composition as the composition (x) used as the first member forming material. A method of patterning and irradiating the composition (x) coating film of the second member forming material with an active energy ray in order to provide a defective portion which will be a flow path reaching the surface is also used in the formation of the first member in the step (I). Then, it is the same as in the case of forming a defect in the coating film of the composition (x) formed on the coated support. It is also preferable to form the internal cavity of the member by stacking and fixing a plurality of composition (x) layers having a defective portion.

The outer shape of the second member is not particularly limited, and may have a shape according to the purpose of use. For example, sheet shape (including film, ribbon, etc., the same applies below), plate shape,
It may be a paint film, rod, tube, or other complicated shaped product, but it should be fixed because it is easy to mold and the preliminary (incomplete) cured coating film of the first member is easily laminated and fixed. The surface is preferably flat or quadric, and particularly preferably sheet or plate. Further, the size of the fixing portion of the second member to the first member does not necessarily have to be the same as that of the first member.

The material of the second member is not particularly limited as long as it can be fixed to the first member by the manufacturing method of the present invention. Examples of materials that can be used as the material of the second member include polymers; crystals such as glass and quartz; ceramics; semiconductors such as silicon; carbon; metals and the like. A polymer is particularly preferable in terms of productivity, low cost, and the like.

The second member may be formed on a support. The material of the support in this case is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor or the like. The shape of the support is also arbitrary, and may be, for example, a plate-shaped material, a sheet-shaped material, a coating film, a rod-shaped material, a paper, a cloth, a non-woven fabric, a porous material, an injection molded product, or the like. The support may be integrated with the present microfluidic device or may be removed after formation. It is possible to form a plurality of microfluidic devices on one first member, or to cut these into a plurality of microfluidic devices after manufacturing.

The polymer used for the second member may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. good. From the viewpoint of productivity, the polymer used for the second member is preferably a thermoplastic polymer or an energy ray-curable crosslinked polymer.

The polymers usable for the second member are the same as those mentioned as the polymers usable for the coating support. You may contain the additive which can be added to a coating support body.

Further, in using the microfluidic device of the present invention, in addition to the purpose of improving the adhesiveness, the adsorption of solutes such as proteins to the device surface is suppressed, and the surface of the second member and the first member. It is also preferable to make the porous portion of the member hydrophilic.

The cross-sectional area of the formed capillary channel is preferably 1 × 10 ⁻¹² m ² to 1 × 10 ⁻⁶ m ² , and more preferably 1 × 10 ⁻¹⁰ m ^{2 to} 2.5 × 10 ^{−. 5} m ²
Is. The width and height of the cross section of the flow path are both preferably 1
μm to 1000 μm, more preferably 10 μm
Is about 500 μm. If the cross section of the flow channel is smaller than these dimensions, it becomes difficult to manufacture, and if it exceeds this range, the characteristics as a microdevice are reduced. The microfluidic device manufactured by the present invention has a flow path having a cross-sectional area in this range, so that reaction / analysis time can be shortened, synthesis / analysis can be performed with a small amount of sample, small amount of waste, and improvement of temperature control accuracy. The characteristics of the microfluidic device such as, are exhibited.

The width / height ratio of the flow path cross section can be arbitrarily set according to the use and purpose, but is generally preferably 0.5 to 10, and more preferably 0.7 to 5. The cross-sectional shape of the flow path is arbitrary such as a rectangle (including a rectangle with rounded corners; the same applies hereinafter), a trapezoid, a circle, a semicircle, and a slit. The width of the channels need not be constant. The flow path may or may not be connected to the outside of the microfluidic device manufactured by the present invention, and other structures inside the device, such as a liquid storage tank, a waste liquid absorption unit, and a pressure You may contact the tank, decompression tank, etc.

The shape of the flow channel as seen from the outside of the microfluidic device, for example, the shape as seen from the direction perpendicular to the surface of the formed microfluidic device on the side of the first member is straight, branched or comb-shaped depending on the purpose of use. It may be curved, spiral, zigzag, or any other shape. The flow path is a capillary space in which a fluid flows, or a capillary space in which pressure is transmitted through the fluid. In addition to a flow path for merely transferring a fluid, a reaction field,
It may be used as a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, or the like. The porous part of the first member is connected to the flow channel, but in addition to that, connected to the flow channel,
In addition to the membrane separation mechanism, for example, a liquid storage tank, a reaction tank, a waste liquid absorption section, a connection port to the outside of the device, etc. may be formed.

The first member formed on the coated support is superposed on the second member with the porous portion and at least a part of the opening of the defective portion serving as a flow path reaching the surface to the member surface. So that they are laminated and fixed. This step is referred to as "step (II)".

The lamination and fixing of the first member and the second member may be in a form according to the use and purpose, and need not necessarily be the entire surface. The porous portion of the first member may be overlapped so as to communicate with the defective portion that serves as a flow path reaching the surface of the second member.

For example, the area of the porous portion may be larger than that of the defective portion opened on the surface of the second member, and the porous portion may be overlapped so as to cover the entire opening of the defective portion of the second member, or a part thereof may overlap. May be layered as The area of the porous portion may be smaller than that of the defective portion on the surface of the second member, and the porous portion may be overlapped with a part of the opening portion of the defective portion of the second member. In the case where the porous portion of the first member is formed, for example, by the preferable second to fourth methods described above, the adhesive force between the cured coating film portion and the porous portion of the composition (x) is relatively weak. Can occur.

In such a case, the area of the porous portion is made larger than that of the opening of the defective portion on the surface of the second member so that the entire opening of the defective portion of the second member is covered, or a part thereof overlaps. It is preferable to stack them in such a manner that the pressure resistance of filtration can be increased.

In the present invention, "laminating" includes not only direct laminating but also laminating via an adhesive.
The first member and the second member are fixed to each other by adhesion using an adhesive,
It may be fusion (fusion), polymerization or cross-linking through the laminated surface, or fusion by partial dissolution with a solvent. Among these fixing methods, a method of directly laminating a semi-cured (incompletely cured) first member and preferably a semi-cured second member, and further adhering by further curing in that state, is an adhesion method. This is preferable because there is no risk of blocking the porous part or the defective part with the agent. The curing performed at this time may be energy ray curing by irradiation with active energy rays or heat curing by heating, and in the case of irradiation with active energy rays, it may be the same as that used for semi-curing or different. It may be one.

When an adhesive is used, the adhesive is optional, for example, an energy ray-curable adhesive, an epoxy-based thermosetting adhesive, a melt-type adhesive, a solvent-type adhesive, a cyanoacrylate. Moisture-curable adhesives, etc. can be used, but energy ray-curable adhesives are preferred because of high productivity. The energy ray-curable adhesive can be selected and used from those shown as the composition (x) used in the present invention. However, the adhesive does not have to have the same composition as the composition (x) used for the first member or the second member.

The adhesive also has a viscosity of 1000 mPa / s.
The above is preferable. By using an adhesive having such a high viscosity, when the adhesive is cured in a state where the first member and the second member are laminated, the adhesive layer has tackiness, and therefore it is necessary to maintain the compressed state. In addition, the possibility of blocking the porous portion with an adhesive is also reduced. Also, with the adhesive slightly cured to increase the viscosity,
It is also preferable that they are laminated or adhered as a gel.

The part where the adhesive fixes the two members does not block the defective portion which becomes the flow path reaching the surface formed on the second member, and the defective portion is unnecessary outside the device. As long as it is not in contact with the other defective portion, its position and shape are arbitrary, but it is preferable that it is the entire surface other than the defective portion. The adhesive may coat the inside of the defective portion or the portion of the porous portion facing the defective portion as long as it does not block the defective portion of the second member.

The thickness of the adhesive layer is optional as long as the flow path portion of the defective portion that reaches the surface is not blocked. However, in view of the constitution of the present invention, compared with the first member and the second member. Is preferably sufficiently thin, is preferably 1/5 or less of the thickness of the first member or the second member, more preferably 1/10 or less, most preferably 1/30 or less. preferable. The lower limit of the thickness of the adhesive layer is arbitrary as long as the first member is fixed to the second member, and it is not particularly limited, and it is difficult to measure when it is very thin. It can be as small as 5 nm.

In the present invention, since the first member is laminated on the second member while being aligned with the first member formed on the coating support, the first member is thin and flexible so that it cannot stand on its own. Even a portion can be accurately aligned without stretching, and in particular, it can be accurately aligned at a plurality of portions, and a minute structure can be easily manufactured.

After the step (II), the first member is transferred to the second member by removing the coating support from the first member fixed to the second member. This step is referred to as "step (III)". Any removal method can be used: peeling, decomposition, melting, dissolution,
It can be volatile or the like. Of these, removal by peeling is preferable because of high productivity.

Removal by peeling includes peeling by pulling, peeling by a blade, peeling using a liquid stream such as water stream, peeling using a gas stream such as compressed air, natural peeling or partial melting by immersion in water, heating or energy rays. Peeling due to modification of the support due to irradiation or the like and peeling due to swelling of the support due to water or the like are optional, and it is also preferable to change temperature conditions in order to facilitate peeling.

Further, by selecting a combination of the material of the coating support and the material of the first member, the material of the first member is adhesive in the uncured and semi-cured state, and the adhesive force is low after the complete curing. Peeling becomes easy by selecting the following combination.

In the production method of the present invention, step (III)
It is also preferable to carry out post-curing, if necessary, to completely cure any semi-cured members or adhesives.

After the transfer of the first member to the second member, a third member having a defective portion which serves as a flow path reaching the surface is provided on the first member and the porous member of the first member and the third member. It is also preferable to stack and fix members so that the defective portions of the members overlap. Although the fixing method is arbitrary, the same method as in the case of stacking and fixing the first member and the second member can be used. The shape of the third member can be similar to the second member. The shape and size of the defective portion are similar to those of the second member.

The third member is positioned so as to face the opening of the defective member which becomes the flow path reaching the surface of the second member, and the porous portion of the first member is separated. It is also preferable to stack and adhere to each other to form a channel or another space as a part thereof on the back side of the porous portion. By providing the third member, it is possible to manufacture a microfluidic device having independent flow paths on the raw solution side and the filtrate side.

The formed microfluidic device has perforations,
Post processing such as cutting is also possible. Further, since the entire microfluidic device of the present invention has a very small size, it is useful for producing a large number of members on one resin layer at the same time for production efficiency and positioning of each member with high precision. is there. That is, by producing a plurality of minute microfluidic devices on one exposure and development plate, it is possible to produce a large number of microfluidic devices at a time with good reproducibility and dimensional stability with high accuracy. it can.

According to the present invention, it is possible to accurately manufacture a microfluidic device having a high yield, high productivity, and a minute porous film portion. The manufacturing method of the present invention, it is easy to precisely align the film-shaped member having a minute porous portion formed thereon without causing deformation such as elongation and stacking it on another member, in particular, In the manufacturing of a structure that requires alignment in multiple parts, for example, a microfluidic device having multiple porous parts, or a microfluidic device in which the flow paths of both members are connected in multiple parts Demonstrate.

[0130]

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

[Activation of active energy rays] A light source unit for multi-light type 200 exposure apparatus manufactured by USHIO INC. Using a 200 W metal halide lamp as a light source was used.
Ultraviolet rays having an ultraviolet intensity of 5 m at 100 mW / cm ² were irradiated at room temperature in a nitrogen atmosphere unless otherwise specified.

[Example 1] In this example, an example in which the porous portion is manufactured by the "reaction-induced phase separation method" will be described. [Preparation of Composition (x)] As the polymerizable compound (a), 30 parts of a trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.), ω- 45 parts of alkyl diacrylate (“Sartomer C2000” manufactured by Somar Co., Ltd.) containing tetradecanediol diacrylate and ω-pentadecanediol diacrylate as main components, and nonylphenoxy polyethylene glycol (n = 17) acrylate ( "N-177E" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25 parts, 5 parts of 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba-Geigy) as a photopolymerization initiator, and 2,4 as a polymerization retarder. -Diphenyl-4-methyl-
Composition (x) 1 was prepared by mixing 0.1 part of 1-pentene (manufactured by Kanto Chemical Co., Inc.). The composition (x) 1
The ultraviolet cured product had a contact angle with water of 14 degrees.

[Preparation of film-forming solution (e)] 76 parts of "Unidic V-4263" (a trifunctional urethane acrylate oligomer manufactured by Dainippon Ink and Chemicals, Inc.) as a polymerizable compound (a), dicyclopentanil 19 parts of diacrylate (“R-684” manufactured by Nippon Kayaku Co., Ltd.),
Methoxynona ethylene glycol acrylate ("NK-ester AM-90 manufactured by Shin-Nakamura Chemical Co., Ltd."
G ") 5 parts," methyl decanoate "as poor solvent (r)
180 parts (manufactured by Wako Pure Chemical Industries, Ltd.), 3 parts acetone as a volatile good solvent, and 3 parts "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba-Geigy) as an ultraviolet polymerization initiator. The film-forming liquid (e) 1 was prepared by uniformly mixing.

[Step (I): Preparation of First Member] A coating support having a thickness of 30 μm and a corona discharge treatment on one side was used.
Axial stretched polypropylene film (manufactured by Nimura Chemical Co.,
OPP film), composition (x) 1 was applied using a bar coater of 127 μm, and through a photomask, ultraviolet rays were applied in the air to a portion other than the non-exposed portion having a circular shape with a diameter of 1 mm (FIG. 1). It is exposed to light for 10 seconds to be semi-cured, and the non-exposed portion is washed and removed with a 50% aqueous ethanol solution and dried under atmospheric pressure at 50 ° C. for 20 minutes to obtain a semi-cured state having a circular defect portion with a diameter of 1 mm. A composition (x) coating film was formed.

Next, the film-forming solution (e) is applied (filled) to the defective portion with a microsyringe so that the film-forming solution (e) is slightly raised from the surface of the coating film, and the film-forming solution (e) application part is applied in a nitrogen atmosphere. The composition is irradiated with ultraviolet rays for 40 seconds to cure, and the poor solvent (r) is washed off with n-hexane to form a cured product of the film-forming liquid (e) into a porous body, and a semi-cured composition ( x) A first member 1 having a porous film formed on the defective portion of the coating film was obtained.

[Preparation of Second Member] The composition (x) was applied to an acrylic plate (base material) having a size of 5 cm × 5 cm × thickness of 1 mm by using a bar coater having a thickness of 127 μm, and the composition was passed through a photomask to give a pattern shown in FIG. 1mm diameter circle and width 15 of the shape shown
The part other than the non-exposed part where the line of 0 μm and length of 30 mm is connected is exposed to ultraviolet light in the air for 10 seconds to be semi-cured, and the uncured composition (x) in the non-exposed part is 50%.
Of the base material and the composition (x) semi-cured resin layer, which has a concave defect portion having the shape shown in FIG. A second member was obtained.

[Step (II): Lamination and Adhesion of First Member and Second Member] Both members are overlapped so that the porous portion of the first member and the defective portion of the circular portion of the second member overlap. The whole was irradiated with ultraviolet rays for 15 seconds to be cured and fixed. [Step (III): Peeling and Removal of Coating Support] Next, the coating support is peeled from the first member with running water, the first member is formed into a resin layer and transferred to the second member, and the porous portion is removed. A microfluidic device having [# 1] was obtained.

[Formation of Other Structure] After that, a hole having a diameter of 0.5 mm was drilled from the first member side at the end of the linear defect (on the side opposite to the circular defect) by a drill,
An inflow portion was formed, and a luer fitting (not shown) was adhered to the inflow portion with an epoxy adhesive.

[Filtration test] Microfluidic device [#
[1] from a microsyringe connected to a lure fitting (not shown) at the inflow portion, resin fine particles having an average particle size of 10 μm (Micropearl SP manufactured by Sekisui Chemical Co., Ltd.)
When water in which -210) was dispersed was injected and a pressure of about 10 kPa was applied, only water permeated and flowed out from the porous portion. That is, the separation function as a filtration membrane was confirmed.

[Structure Observation] After completion of the filtration test, the microfluidic device [# 1] was washed, dried and destroyed, and the porous portion was observed with a scanning electron microscope (SEM). As a gap between the aggregated particles having a diameter of about 0.3 μm, pores having a pore diameter of about 0.1 μm were observed, and pores of about 0.3 μm were observed on the side where the second member was bonded. Further, in the cross section, a dense layer was formed on the surface side of the microfluidic device, and a porous body of about 0.3 μm was formed from the dense layer to the adhesion side. Moreover, the thickness of the first member and the thickness of the resin layer of the second member were about 100 μm.

[Embodiment 2] In this embodiment, the porous portion is made to have "U".
An example of manufacturing by the “V wet method” will be described. [Preparation of film-forming liquid (f)] As the polymerizable monomer (a),
2 parts of diethylene oxide modified bisphenol A diacrylate (“New Frontier BPE-4” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), methoxynonaethylene glycol acrylate (“NK-ester AM-90G” manufactured by Shin Nakamura Chemical Co., Ltd.) 5 parts, polysulfone as chain polymer (p) [“Udel Polysulfone P1700” manufactured by Amoco Performance Products Inc.] 18 parts, and N, N as solvent (s)
67 parts of dimethylacetamide and 5 parts of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba-Geigy) as a photopolymerization initiator were uniformly mixed to obtain a film-forming solution (f).

[Step (I): Fabrication of First Member] Example 1
In the same manner as in (1), the same semi-cured coating film as shown in FIG. 1 having a defect portion was prepared on the coated support. Then, using a syringe to the defective portion,
The film-forming solution (f) is applied (filled) to the extent that it slightly rises from the surface of the coating film, and a part of the solvent is volatilized by leaving it to stand in a nitrogen atmosphere for about 5 seconds. The film forming solution (f) was pre-cured by irradiating only the coating film portion with ultraviolet rays for 40 seconds to obtain a transparent gel in which fluidity was lost. Then
When the whole coating support was placed in water used as the solvent (n), the gel film-forming solution (f) became milky white and solidified. Then, wash the porous part in this order with ethanol and water,
It was freeze-dried to form the first member on the coated support.

[Step (II): Lamination and Fixation of First Member and Second Member] Trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.) 4 parts, alkyl diacrylate containing ω-tetradecanediol diacrylate and ω-pentadecanediol diacrylate as main components (“Sartomer C2000” manufactured by Somar Corporation)
1 part, ethanol 95 parts, and 1-as a photopolymerization initiator
An active energy ray curable adhesive solution obtained by uniformly mixing 0.2 parts of hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) was spin-coated on the surface of the same second member as used in Example 1. And then dried with hot air at 50 ° C. for 15 minutes, then the both members are overlapped so that the porous portion of the first member and the circular defect portion of the second member overlap each other, and ultraviolet rays are irradiated for 4 seconds to bond them. The agent was cured to bond the first member and the second member.

[Step (III): Separation of Coating Support] After that, the coating support was separated from the first member by running water, and the first member was transferred to the second member. [Formation of Other Structure] At the end of the linear defect (opposite to the circular defect), a hole having a diameter of 0.5 mm is drilled from the first member side to form an inflow part, and A luer fitting (not shown) was adhered on the top to obtain a microfluidic device [# 2].

[Filtration Test] Microfluidic Device [#
2] is connected to a luer fitting (not shown) at the inflow portion, and a bovine serum albumin aqueous solution (concentration Co = 500 mg / L, pH 7) is injected,
When a pressure of Pa was applied, it was confirmed that the liquid permeated and flowed out from the porous portion. The concentration (Ct) of bovine serum albumin in the liquid that had permeated and flowed out from the porous layer was measured by an ultraviolet-visible spectrophotometer, and the albumin inhibition rate (R (%) = (1-Ct / C
The omission rate was 90% when o) × 100) was determined. That is, the separation function as an ultrafiltration membrane was confirmed.

[Structure Observation] After completion of the filtration test, the microfluidic device [# 2] was washed, dried and destroyed, and the porous portion was observed by SEM. The pores having a diameter of not more than 05 μm were recognized, and the pores having a diameter of about 1 μm were observed on the surface side of the microfluidic device. Further, in the cross section, a dense layer is formed on the adhesive side to the second member, and a porous portion of about 1 μm and macro voids of about 50 μm were observed in the porous portion extending outward from the dense layer. The thickness of the first member and the resin layer of the second member is about 1
The thickness of the adhesive was 00 μm, and the thickness of the adhesive was about 2.5 μm.

[Embodiment 3] In this embodiment, an example in which the porous portion is manufactured by the "wet method" will be described. [Preparation of film-forming solution (g)] 18 parts of polyamide (“Conex” manufactured by Teijin Limited) as a chain polymer (p) and 82 parts of N, N-dimethylacetamide as a solvent were uniformly mixed, A film forming solution (g) 3 was obtained.

[Step (I): Preparation of First Member] Example 1
In the same manner as in (1), the same semi-cured coating film as shown in FIG. 1 having a defect portion was prepared on the coated support. Then, using a syringe to the defective portion,
The film-forming solution (g) is applied (filled) to the extent that it slightly rises from the surface of the coating film, and a part of the solvent is volatilized by standing in the air for about 5 seconds, and then the solvent (n ), The film-forming solution (g) became milky white and solidified. Then, it was washed with water and freeze-dried to form a semi-cured coating-like first member on the coated support.

[Step (II): Lamination and Fixation of First Member and Second Member] The porous portion of the first member in the semi-cured state and the circular portion of the same second member as used in Example 1. Were overlapped with each other so as to be overlapped with each other, and were irradiated with ultraviolet rays for 15 seconds to be cured and fixed.

[Step (III): Peeling of Coating Support] Next, the coating support is peeled from the first member with running water, the first member is transferred to the second member, and a micro-pore having a porous portion is formed. A fluidic device [# 3] was obtained. [Formation of Other Structure] After that, at the end of the linear defective portion (the side opposite to the circular defective portion), a hole having a diameter of 0.5 mm is drilled from the first member side to form an inflow portion,
A lure fitting (not shown) was adhered thereon.

[Filtration test] Microfluidic device [#
[3] A microsyringe is connected to the lure fitting (not shown) at the inflow portion, and a bovine serum albumin aqueous solution (concentration Co = 500 mg / L, pH 7) is injected, and 50 k
When a pressure of Pa was applied, it was confirmed that the liquid permeated and flowed out from the porous portion. The concentration (Ct) of bovine serum albumin in the liquid permeated from the porous layer was measured by an ultraviolet-visible spectrophotometer, and the albumin inhibition rate (R (%) = (1-Ct / Co) x1
The rejection rate was 96% when 00) was obtained. That is,
The separation function as an ultrafiltration membrane was confirmed.

[Structure Observation] After completion of the filtration test, the microfluidic device [# 3] was washed, dried and destroyed, and the porous portion was observed by SEM. No pore having a resolution of 0.007 μm or more was recognized, and a pore of about 1 μm was observed on the surface side of the microfluidic device. In addition, in the cross section, a dense layer is formed on the adhesive side to the second member, and beyond that,
A porous portion of about 1 μm and macrovoids of about 150 μm were observed therein, and the thickness of the first member and the resin layer of the second member were about 100 μm.

[Embodiment 4] In this embodiment, an example in which the porous portion is manufactured by the "energy ray lithographic method" will be described.

[Step (I): Preparation of First Member] As a coating support (not shown), a biaxially stretched polypropylene film having a thickness of 30 μm and treated on one side with corona discharge (OPP film manufactured by Nimura Chemical Co., Ltd.) ) Is coated with the composition (x) using a 50 μm bar coater, and is passed through a photomask to obtain 10 mm × 10 mm as shown in FIG.
In the range of, a portion other than a large number of circular non-exposed portions with a diameter of 10 μm arranged at a pitch (center-to-center distance) of 20 μm is exposed to ultraviolet light in the air for 7 seconds to be semi-cured,
The non-exposed area is washed away with a 50% aqueous ethanol solution and then removed.
Drying with hot air at 0 ° C. for 20 minutes, a semi-cured coating film (5) having a porous part (11) as shown in FIG. 4 was prepared on a coating support (not shown). One member (5) was used.

[Step (II): Fabrication of Second Member] Thickness 1 m
m acrylic plate substrate (1) was coated with the same composition (x) as used in Example 1 using a 127 μm bar coater, and a circle with a diameter of 1 mm and a width of 1 were applied through a photomask.
Ultraviolet rays were applied in the air to the portion other than the non-exposed portion having the shape shown in FIG. 2, which was connected to a line of 50 μm and a length of 30 mm.
It is exposed to light for 2 seconds to be semi-cured, and the uncured composition (x) in the non-irradiated portion is washed and removed with a 50% ethanol aqueous solution and dried with hot air at 50 ° C. for 20 minutes, as shown in FIG. A semi-cured coating film (3) having a defect (12) was formed.

On the other hand, as a coating support (not shown), a 30 μm thick biaxially stretched polypropylene film (OPP film manufactured by Nimura Chemical Co., Ltd.) having one surface subjected to corona discharge treatment was used. The composition (x) used in Example 1 was applied using a coater, and a portion other than the circular unexposed portion having a diameter of 1 mm as shown in FIG. 1 was exposed to ultraviolet light in air for 10 seconds through a photomask. The composition is exposed to light to be semi-cured, and the composition (x) in the non-irradiated area is washed off with a 50% aqueous ethanol solution and then heated at 50 ° C. for 20 minutes.
Drying was carried out with hot air to form a semi-cured coating film (4) having a defect (13) as shown in FIG.

Then, the circular defect portion (13) of the coating film (4) formed on the coating support (not shown) and the coating film (3) formed on the base material (2). Of the coating film (4) are overlapped with each other so that the circular portions of the defective portion (12) of the coating film are overlapped with each other, and ultraviolet rays are irradiated for 10 seconds to cure both members. The OPP film (not shown) is peeled off with a water stream, and the base material (2), coating film (3) and coating film (4)
A second member (14) was obtained by stacking in this order.

[Step (II): Lamination and Fixation of First Member and Second Member] The porous portion (11) of the semi-cured first member (5) and the defective portion of the second member (14) Both members were overlapped so that (13) overlapped, and active energy rays were irradiated for 10 seconds to bond both members. [Step (III): Peeling off coated support] Next, a coated support (not shown) is peeled off from the first member (5) with a water stream, and the first member (5) is turned into a second member (14). It was transcribed.

[Production of Third Member] The second member (14)
In exactly the same manner as in the above, the base material (2) of the second member, the coating film (3), the coating film (4), the defective portion (12), the defective portion (13).
The same as the second member (14), which has a base material (2 ′), a coating film (3 ′), a coating film (4 ′), a defective portion (12 ′), and a defective portion (13 ′) respectively corresponding to Three parts (15) were made.

[Lamination and Fixation of Third Member] A circular defective portion of the third member (15) is provided on the first member (5) side of the laminated body of the first member (5) and the second member (14). (13 ') separates the porous part (11) of the first member (5) from the second member (1).
The third member was superposed so as to overlap the circular defect portion (13) of 4), and while being pressed, it was irradiated with ultraviolet rays for 30 seconds to be completely cured and fixed, thereby obtaining a microfluidic device [# 4].

[Formation of Other Structure] After that, at the end portion on the opposite side of the circular portion of the defective portion (12), the base material (2) of the second member is drilled to form a hole having a diameter of 0.5 mm and flow in. The part (1) is formed, and the base material (2 ′) of the third member is drilled into the base material (2 ′) at the end opposite to the circular portion of the defect portion (12 ′) to flow out with a hole having a diameter of 0.5 mm. A part (1 ') was formed, and a luer fitting (not shown) was adhered on each part.

[Filtration test] Microfluidic device [#
4] A microsyringe is connected to the lure fitting (not shown) of the inflow portion 1 of 4], and resin fine particles having an average particle diameter of 25 μm (Micropearl SP- manufactured by Sekisui Chemical Co., Ltd.
When water in which 225) was dispersed was injected and a pressure of about 5 kPa was applied, only water permeated the porous layer and flowed out from the outflow portion 2. That is, the separation function as a filtration membrane was confirmed.

[Structure Observation] After completion of the filtration test, the microfluidic device [# 4] was washed, dried and destroyed, and the porous portion was observed by SEM. As a result, the pore size on the side of adhesion to the second member was 11 μm. A mortar-shaped pore having a pore diameter of about 16 μm on the third member side was observed. The thickness of the first member (5), the resin layer (4) and the resin layer (4 ′) was about 30 μm, and the thickness of the resin layer (3) and the resin layer (3 ′) was about 100 μm.

[0164]

INDUSTRIAL APPLICABILITY According to the present invention, a film-like member having a minute porous portion in a part thereof or a very thin and flexible film-like member having a porous portion can be manufactured by an industrially stable method with high accuracy. It is possible to provide a method for manufacturing a microfluidic device having a porous portion by well stacking and fixing it on another member.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a plan view of a first member used in Examples 1, 2 and 3 and second and third members used in Example 4 as seen from a direction perpendicular to a surface.

FIG. 2 is a plan view of the second member used in Examples 1, 2 and 3, the resin layer 1 of the second member and the resin layer 3 of the third member used in Example 4, as viewed from a direction perpendicular to the surface. It is a schematic diagram of a figure.

FIG. 3 shows the porous portion (first member) used in Example 4,
It is a schematic diagram of the top view seen from the direction perpendicular to the surface.

FIG. 4 is an exploded perspective view of the microfluidic device manufactured in Example 4.

[Explanation of symbols]

1 Holes made in the base material 2, inflow part 1'hole formed in the base material 2 ', outflow portion 2 Base materials that make up the second member 2'Substrate constituting the third member 3, 4 Coating film and resin layer constituting the second member 3 ', 4'Coating film and resin layer constituting the third member 5 Paint film, resin layer, and first member to be the first member 11 Porous part of the first member 12, 12 ', 13, 13' defect 14 Second member 15 Third member

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D006 GA02 GA06 HA41 MA03 MA06                       MA22 MA25 MC37X MC38                       MC40 MC58 NA42 NA50 PA01                       PB12 PB52                 4D019 AA03 BA13 BB08 BB09 CA10                       CB06                 4G075 AA02 BA10 BB01 BB05 BC10                       CA32 CA33 CA34 CA38 CA39                       DA02 EE12 FA02 FB02 FB04                       FB06 FB12

Claims (10)

[Claims] 1. An active energy ray-curable composition (x) containing an active energy ray-polymerizable compound (a) is coated on a coated support, and at least a part of the member is coated with a surface of the member. Step (I) of forming a first member composed of a cured or semi-cured coating film having a porous portion having pores reaching the back surface, the above-mentioned defect of the second member having a defect portion serving as a flow path reaching the front surface A step (II) of stacking and fixing the porous part of the first member so as to overlap with at least a part of the part, and removing the coating support from the first member to make the first member a second member. A method for producing a microfluidic device having a flow path and a porous portion connected to the flow path, which comprises the step (III) of transferring. 2. The step (I) applies the composition (x) to a coated support to form an uncured coating film, and forms an uncured coating film on portions other than the portions to be pores. Irradiation with active energy rays to form a cured or semi-cured coating film, and then the uncured composition (x) in the non-irradiated portion is removed to obtain a cured or semi-cured film having a porous portion composed of a large number of pores. The method for producing a microfluidic device according to claim 1, wherein the first member in the form of a coating film is formed on the coated support. 3. A portion to be formed as a porous portion in the step (I) by applying the composition (x) to a coated support to form an uncured coating film of the composition (x). The uncured coating film other than the above is irradiated with an active energy ray to form a cured or semi-cured coating film of the composition (x), and then the uncured composition of the non-irradiated portion from the cured or semi-cured coating film. Of the active energy ray-polymerizable compound (b) and the compound (b) in the portion where the composition (x) is removed.
After coating the active energy ray-curable film-forming liquid (e) containing the poor solvent (r), the film-forming liquid (e) is irradiated with active energy rays to polymerize the compound (b). The first member comprising a polymer, and the polymer and the poor solvent (r) are phase-separated to form a first member having a porous portion having a large number of pores on a coated support. A method for manufacturing the described microfluidic device. 4. A part to be formed as a porous part in the step (I), by applying the composition (x) to a coated support to form an uncured coating film of the composition (x). The uncured coating film other than the above is irradiated with an active energy ray to form a cured or semi-cured coating film of the composition (x), and then the uncured composition of the non-irradiated portion from the cured or semi-cured coating film. The substance (x) is removed, and then the chain polymer (p), the active energy ray-polymerizable compound (m), and the chain polymer are added to the portion where the composition (x) is removed. (P) and the compound (m)
After forming a film-forming solution (f) by applying a film-forming solution (f) containing a solvent (s) that dissolves the compound (m) and does not dissolve the polymer formed by polymerizing the compound (m). The film-forming liquid (f) coating film is irradiated with active energy rays to pre-cure the film-forming liquid (f) coating film, and the film-forming liquid (f) is pre-cured.
The coating film is brought into contact with a solvent (n) which is miscible with the solvent (s) but does not dissolve the chain polymer (p), whereby the chain polymer (p) is aggregated and deposited in a porous state to form a large number of pores. The method for producing a microfluidic device according to claim 1, wherein the first member having a porous portion made of is formed on the coated support. 5. A portion to be formed as a porous portion in the step (I), by coating the composition (x) on a coated support to form an uncured coating film of the composition (x). The uncured coating film other than the above is irradiated with an active energy ray to form a cured or semi-cured coating film of the composition (x), and then the uncured portion of the non-irradiated portion of the cured or semi-cured coating film is uncured. The composition (x) is removed, and then, in the portion where the composition (x) is removed,
After forming a film-forming solution (g) by applying a film-forming solution (g) containing a chain-like polymer (p) and a solvent (s) that dissolves the chain-like polymer (p) The film-forming liquid (g) coating film is brought into contact with a solvent (n) which is miscible with the solvent (s) but does not dissolve the chain polymer (p) to make the chain polymer (p) porous. The method for producing a microfluidic device according to claim 1, wherein the first member having a porous portion having a large number of pores is formed on the coated support by coagulating and depositing. 6. The curing or semi-cured coating film formation of the composition (x) in the step (I) is a semi-cured coating film formation, and the first member and the second member in the step (II) are formed. The method for producing a microfluidic device according to claim 1, wherein the fixing is fixing by irradiating the composition (x) with a semi-cured coating film by irradiating with active energy rays while the both members are in contact with each other. 7. An active energy ray-curable composition (x) containing an active energy ray-polymerizable compound (a) as an adhesive for fixing the first member and the second member in the step (II). The method for producing a microfluidic device according to claim 1, wherein the adhesive is applied to two members, the first member is laminated on the adhesive application surface, and the adhesive is cured by irradiation with active energy rays. 8. A porous member of the first member, wherein a third member having a defective portion serving as a flow path reaching a surface is provided on at least a part of the defective portion of the second member. The method for manufacturing a microfluidic device according to claim 1, further comprising a step of stacking and adhering the third member so that the defective portions of the third member overlap each other. 9. The pores of the porous portion have a pore size of 0.001 to 10
The microfluidic device manufacturing method according to claim 1, wherein the microfluidic device has a thickness of μm. 10. The method for producing a microfluidic device according to claim 1, wherein the pore diameter of the porous portion is nonuniform in the thickness direction of the first member.