JP2000246092A - Production of microchemical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To bond members having a recessed part on the surface and another member to form an integrated body which are completely contacted with each other, without a minute space being closed by an adhesive in the production of a microchemical device, in which a space to be a passage and others is formed, by bonding/integrating the members. SOLUTION: A surface in which the recessed part of a member 1 is formed is contacted with a member 2 through a composition containing an energy ray curable compound. After a part excluding the recessed part formed in the member 1 is irradiated with energy rays to cure the composition, and the uncured composition in a space formed between the recessed part of the member 1 and the member 2 is removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a microchemical device, that is, a microchannel, a reaction tube, a reaction vessel,
Microreaction devices (microreactors) for chemical, biochemical, physical chemistry, etc., with integrated structures such as electrophoresis columns, chromatographic columns, and membrane separation mechanisms, and integrated DNs
The present invention relates to a method for producing a micro-analysis device such as an A-analysis device, a micro-electrophoresis device, a micro-chromatography device, a micro-membrane separation device, and a micro-concentration device. The present invention relates to a method for manufacturing a fine chemical device having a space in a capillary shape or another shape, which is formed by bonding and integrating the above member using an energy ray-curable resin.

[0002]

2. Description of the Related Art There are known microchemical devices in which a concave portion is formed on a substrate made of silicon, quartz, glass, polymer, or the like by an etching method or the like to form a liquid flow path or a gel channel for separation (for example, M. McCormick, etc., "Analytical Chemistry", 2nd
(Page 626, Vol. 69, 1997). It is known that a cover such as a glass plate is used in close contact with the surface by screws or the like for the purpose of preventing evaporation of liquid during operation and transporting liquid by pressurization. Have been.

[0003]

However, it is quite difficult to completely adhere the substrate and the cover in close contact, and the liquid tends to leak from the flow path to the space between the substrate and the cover.

On the other hand, when these two members are bonded with an adhesive, the adhesive tends to enter the space formed by the concave portion formed on the substrate and the cover, and tends to close the space. It was difficult to form a space. When the space is in the form of a thin capillary, its formation is particularly difficult.

[0005] The problem to be solved by the present invention is a method for forming a minute space between two or more members, and the two or more members are formed without closing such a minute space. It is to provide a method of bonding and integrating.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for solving the above-mentioned problems, and as a result, using an energy ray-curable composition containing an energy ray-curable compound as an adhesive, The member having the concave portion and the other member are contacted with the energy ray-curable composition interposed therebetween, and the portion excluding the concave portion is irradiated with energy rays to cure the irradiated portion of the energy ray-curable composition, and then the concave portion and the other portions are exposed. By removing the uncured energy-ray-curable composition in the space formed by the member or by sandwiching the energy-ray-curable composition between a member having a concave portion on the surface and another member bonded to the member. In a state where the energy beam is irradiated on a part of the portion other than the concave portion, or without irradiation, the energy ray-curable composition in the space formed by the concave portion and another member Remove After, the method of curing by irradiation with energy ray, and can be bonded without occluding the recess and other small space formed by the member heading,
The present invention has been completed.

That is, in order to solve the above-mentioned problem, the present invention provides a method for bonding a member (A) having a concave portion having a depth of 1 to 3000 μm on the surface thereof with another member (B). A method for manufacturing a microchemical device having a space formed between a concave portion of (A) and a member (B), wherein the surface of the member (A) where the concave portion is formed and the member (B) are energy-curable. The composition (C) containing the compound is brought into contact with the composition (C), and the composition (C) is cured by irradiating the composition (C) with energy rays at a portion other than the concave portion formed on the member (A).
A method for manufacturing a microchemical device, comprising removing an uncured composition (C) existing in a space formed between a concave portion of a member (A) and a member (B) (hereinafter referred to as “the present invention”). 1).

In order to solve the above-mentioned problems, the present invention provides a method for forming a member (A) by bonding a member (A) having a concave portion with a depth of 1 to 3000 μm on the surface thereof and another member (B). A) a method for manufacturing a microchemical device having a space formed by the concave portion and the member (B), wherein the surface of the member (A) having the concave portion and the member (B) contain an energy ray-curable compound; The composition (C) is cured by irradiating a part of the part (A) excluding the concave part formed on the member (A) with an energy beam, thereby curing the composition (C) and the concave part of the member (A). After removing the uncured energy ray-curable composition (C) existing in the space formed between the substrate and the member (B), the uncured portion around the concave portion is irradiated with energy rays to be cured. A method for manufacturing a microchemical device comprising: A second manufacturing method of the present invention).

In order to solve the above-mentioned problems, the present invention provides: (III) a member (A) having a concave portion with a depth of 1 to 3000 μm on the surface and another member (B) by bonding the member (A); A) a method for manufacturing a microchemical device having a space formed by the concave portion and the member (B), wherein the surface of the member (A) having the concave portion and the member (B) contain an energy ray-curable compound; After the composition (C) is brought into contact with the composition (C), the composition (C) in the concave portion is removed, and then the composition (C) is cured by irradiating with energy rays. (Hereinafter, referred to as a second manufacturing method of the present invention).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The member (A) used in the production method of the present invention is impermeable to a liquid used for the microchemical device obtained by the present invention, and has a surface
It has a concave portion serving as a space for a microchemical device. The recess may itself be connected to the end of the member (A), that is, to the outside of the microchemical device to be manufactured, or may not be to the outside of the microchemical device. The depth of the recess is 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more. A microchemical device having a shallower recess becomes difficult to manufacture. The depth of the concave portion is 3000 μm or less, preferably 500 μm or less, and more preferably 100 μm or less. If it is deeper than this, the effect of the present invention is reduced.

The planar shape of the concave portion of the member (A) is arbitrary, but the width (or diameter) of the narrowest portion is preferably 1 μm or more, more preferably 5 μm or more, and 1 μm or more.
More preferably, it is 0 μm or more. If it is smaller than this, manufacturing becomes difficult. The width (or diameter) of the narrowest portion of the concave portion is preferably 3000 μm or less,
It is preferably at most 500 μm, more preferably at most 100 μm. If the width is wider than this, the effect of the present invention is reduced. The effect of the present invention can be particularly exhibited when the planar shape of the concave portion is a groove shape. The width of the groove is the same as the description of the width of the narrowest portion of the recess, and the depth of the groove is the same as the description of the depth of the recess. The cross-sectional shape of the concave portion (including the groove) is also arbitrary such as a square, a trapezoid, or a semicircle.

[0012] The surface of or inside the member (A) is connected to a concave portion and connected to another structure, for example, a connection port with the outside of the member, a reaction tank, a flow rate measuring section, a valve, a valve, a groove filled with gel, a separation, A film or the like may be formed.

[0013] The shape of the member (A) does not need to be particularly limited, and may take a shape according to the purpose of use. For example, sheet (including film and ribbon), plate, coating, rod,
It can be a tube, a molded product of other complicated shape, etc., but it is easy to mold and it is easy to irradiate energy rays, so that the surface to be adhered is a flat shape, especially a sheet or plate. Preferably, there is. The member (A) may be formed on a support. The material of the support in this case is arbitrary, for example, polymer, glass,
It may be ceramic, metal, semiconductor or the like. The shape of the support is also arbitrary, and may be, for example, a plate-like material, a sheet-like material, a coating film, a rod-like material, paper, cloth, nonwoven fabric, a porous body, an injection-molded product, and the like. It is possible to form a plurality of microchemical devices on one member (A), or it is possible to cut them after manufacturing to form a plurality of microchemical devices.

The material of the member (A) is not particularly limited as long as it can be bonded with the composition (C) containing the energy ray-curable compound used in the present invention. In the case where the energy ray used in the present invention is not transmitted, the energy ray used in the present invention needs to be transmitted. Materials usable as the material of the member (A) include, for example, polymers, glass, crystals such as quartz, ceramics, semiconductors such as silicon, metals, and the like. Among these, easy moldability, high productivity, Polymers are particularly preferred from the viewpoint of low cost and the like.

Examples of the polymer which can be used for the member (A) include styrene polymers such as polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, and polystyrene / acrylonitrile copolymer; porsulfone, polyethersulfone (Meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide polymers; polycarbonate polymers such as bisphenol A-based polycarbonate, bisphenol F-based polycarbonate and bisphenol Z-based polycarbonate; polyethylene, polypropylene, Poly
Polyolefin polymers such as 4-methylpentene-1; chlorine-containing polymers such as vinyl chloride and vinylidene chloride; cellulosic polymers such as cellulose acetate and methylcellulose; polyurethane polymers; polyamide polymers; polyimide polymers; Polyether or polythioether polymers such as dimethylphenylene oxide and polyphenylene sulfide; polyetherketone polymers such as polyetheretherketone; polyester polymers such as polyethylene terephthalate and polyarylate; epoxy resins; urea resins; Can be mentioned. Among these, styrene-based polymers, (meth) acrylic-based polymers, polycarbonate-based polymers, polysulfone-based polymers, and polyester-based polymers are preferable from the viewpoint of good adhesion.

The polymer used for the member (A) may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. From the viewpoint of productivity, the polymer used for the member (A) is preferably a thermoplastic polymer or an energy ray-curable crosslinked polymer. The member (A) may be composed of a polymer blend or a polymer alloy, or may be a laminate or other composite. Further, the member (A) may contain additives such as a modifying agent, a coloring agent, a filler, and a reinforcing material.

Examples of the modifier which can be contained in the member (A) include hydrophobizing agents (water repellents) such as silicone oil and fluorine-substituted hydrocarbons; water-soluble polymers, surfactants, silica gels and the like. And hydrophilic agents such as inorganic powders.

As the coloring agent which can be contained in the member (A), any dye or pigment, fluorescent dye or pigment,
UV absorbers.

The reinforcing material that can be contained in the member (A) includes, for example, inorganic powders such as clay, and organic and inorganic fibers.

The member (A) is made of a material having low adhesiveness, for example,
In the case of polyolefin, fluorine-based polymer, polyphenylene sulfide, polyether ether ketone, or the like, it is preferable to improve the adhesion by surface treatment of the bonding surface of the member (A) or use of a primer.

In the use of the microchemical device of the present invention, the surface of the groove of the member (A) is made hydrophilic for the purpose of improving the adhesiveness and suppressing the adsorption of solutes such as proteins to the device surface. It is also preferable to do so. The hydrophilic treatment is not limited to the surface of the groove, and other parts may be treated.

The member (B) used in the present invention is impermeable to the liquid to be used, and is adhered to the groove-formed surface of the member (A) so that the concave portion of the member (A) (B) If it is possible to form a space, its shape, material,
The structure, surface condition, and the like are arbitrary. For these,
This is the same as the case of the member (A) except that the concave portion does not need to be formed on the surface. The member (B) does not need to have a concave portion formed on the surface, but may have a concave portion or a structure other than the concave portion. When the member (A) does not transmit the energy ray used in the present invention, the member (B) needs to transmit the energy ray used in the present invention.

The energy ray-curable compound used in the present invention can be any compound such as a radical polymerizable polymer, an anionic polymerizable polymer, or a cationic polymerizable polymer as long as it can be cured to bond the member (A) to the member (B). It may be. The energy ray-curable compound is not limited to one that polymerizes in the absence of a polymerization initiator, and one that is polymerized by an energy beam only in the presence of a polymerization initiator can also be used.

As such an energy ray-curable compound, a compound having a polymerizable carbon-carbon double bond is preferable. Among them, a highly reactive (meth) acrylic compound or vinyl ether, and a photopolymerization initiator are preferable. A maleimide-based compound that cures even in the absence of is preferred. The energy ray-curable compound may be a monofunctional monomer and / or oligomer as long as it can be sufficiently cured and adhered. However, in order to obtain high adhesive strength, a cross-linkable polymerizable compound, for example, It is preferably a polyfunctional monomer and / or oligomer.

Examples of the (meth) acrylic monomer that can be used as the energy ray-curable compound include 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, neopentylglycol dihydroxydipivalate A) bifunctional monomers such as acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, and N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, Chi trimethylolethane tri (meth)
Trifunctional monomers such as acrylate, tris (acroxyethyl) isocyanurate and caprolactone-modified tris (acroxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylate A monofunctional monomer having another crosslinkable functional group such as 2-isocyanatoethyl methacrylate.

Further, as the energy ray-curable compound,
A polymerizable oligomer (also referred to as a prepolymer) can also be used, for example, having a weight average molecular weight of 500 to 50.
000. Examples of such a polymerizable oligomer include (meth) acrylate of epoxy resin, (meth) acrylate of polyether resin, (meth) acrylate of polybutadiene resin, and (meth) acryloyl at the molecular terminal. And a polyurethane resin having a group.

Examples of the maleimide-based energy ray-curable compound include 4,4′-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, , 2-Bismaleimide ethane, 1,6-Bismaleimide hexane, Triethylene glycol bismaleimide, N, N'-m-phenylenedimaleimide, m-Tolylene dimaleimide, N,
N'-1,4-phenylenedimaleimide, N, N'-diphenylmethane dimaleimide, N, N'-diphenylether dimaleimide, N, N'-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1 ,
4-diazoniabicyclo- [2,2,2] octane dichloride, 4,4'-isopropylidenediphenyl dicyanate N, N '-(methylenedi-p-phenylene)
Bifunctional maleimides such as dimaleimide; and maleimides having a maleimide group such as N- (9-acridinyl) maleimide and a polymerizable functional group other than the maleimide group. The maleimide-based monomer can also be copolymerized with a compound having a polymerizable carbon-carbon double bond, such as a vinyl monomer, a vinyl ether, or an acrylic monomer.

The composition (C) contains an energy ray-curable compound as an essential component, and may be composed of a single energy ray-curable compound, but may be a mixture of a plurality of types of energy ray-curable compounds. Can be For example, in order to impart sufficient hardness to a cured product of the energy ray-curable compound, the composition (C) preferably contains a polyfunctional monomer and / or oligomer. ) For the purpose of adjusting the viscosity, improving the adhesiveness, and imparting flexibility to the cured product.
Alternatively, it is also possible to mix oligomers.

Examples of the monofunctional (meth) acrylic monomer which can be mixed and used in the composition (C) include, for example, methyl methacrylate, 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 -Carboxyaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloysoxypropylhexahydrohydrogen phthalate, fluorine-substituted alkyl (meth) acrylate,
Chlorine-substituted alkyl (meth) acrylate, sodium sulfonic acid (meth) acrylate, sulfonic acid-2-
Methylpropane-2-acrylamide, (meth) acrylate containing phosphoric ester group, (meth) acrylate containing sulfonic ester group, (meth) acrylate containing silane group, (meth) acrylate containing ((di) alkyl) amino group, quaternary ((Di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl) acrylamide, (N, N-dialkyl) acrylamide, achloroyl morpholine, and the like.

Examples of the monofunctional maleimide monomer which can be mixed and used in the composition (C) include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide,
N-alkylmaleimides such as N-dodecylmaleimide; N-alicyclic maleimides such as N-cyclohexylmaleimide; N-benzylmaleimide; N-phenylmaleimide; N- (alkylphenyl) maleimide; N-dialkoxyphenylmaleimide; -(2-chlorophenyl) maleimide, 2,3-dichloro-N- (2,6-
Diethylphenyl) maleimide, 2,3-dichloro-N
N- (substituted or unsubstituted phenyl) maleimide such as-(2-ethyl-6-methylphenyl) maleimide; N-benzyl-2,3-dichloromaleimide, N- (4'-fluorophenyl) -2,3- A maleimide having a halogen such as dichloromaleimide; a maleimide having a hydroxyl group such as hydroxyphenylmaleimide; a maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide; and an alkoxy group such as N-methoxyphenylmaleimide. Having a maleimide;
Maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide; polycyclic aromatic maleimide such as N- (1-pyrenyl) maleimide; N- (dimethylamino-4-methyl-3-coumarinyl) maleimide And maleimides having a heterocyclic ring, such as N- (4-anilino-1-naphthyl) maleimide.

The preferred value of the viscosity of the composition (C) depends on the size of the space to be formed, and the smaller the space, the lower the viscosity. For example, when a space having a width (or diameter) of the order of 10 μm or less is formed, the thickness is preferably about 1000 mPa · s or less. For this purpose, it is preferable to mix the above monofunctional monomers.
Excessive viscosity of the composition (C) is not preferable because it tends to take time to remove the uncured composition.

In the composition (C), if necessary, other components such as a photopolymerization initiator, a solvent, a thickener, a modifier, and a coloring agent can be mixed and used.

The photopolymerization initiator which can be used as necessary in the composition (C) is active with respect to the energy rays used in the present invention and can polymerize the energy ray-curable compound. There is no particular limitation if it is
For example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator may be used. Examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone,
-Hydroxy-2-methyl-1-phenylpropane-1
Acetophenones such as -one; benzophenone, 4,
Ketones such as 4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether Benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; azides such as N-azidosulfonyl phenyl maleimide; Further, a polymerizable photopolymerization initiator such as a maleimide-based compound can be used.

The polymerizable photopolymerization initiator is exemplified as a monofunctional maleimide monomer which can be mixed and used in the composition (C), in addition to a polyfunctional monomer such as the polyfunctional maleimide exemplified as the energy ray-curable compound. It may be a simple monofunctional monomer.

When the photopolymerization initiator is mixed and used in the composition (C), the amount of the nonpolymerizable photopolymerization initiator may be set to 0.1.
The range is preferably from 005 to 20% by weight, particularly preferably from 0.01 to 2% by weight.

Examples of the thickener which can be mixed and used in the composition (C) as needed include, for example, a linear polymer which is soluble in an energy ray-curable compound and insoluble in a gel.

Examples of the modifier which can be mixed and used in the composition (C) as needed include, for example, silicone oil and fluorine-substituted hydrocarbon which function as a water repellent.

Examples of the coloring agent which can be mixed and contained in the composition (C) as needed include arbitrary dyes, pigments and fluorescent dyes.

In the first production method of the present invention, the surface of the member (A) where the concave portion is formed is brought into contact with the member (B) via the composition (C), and the concave portion formed on the member (A) is contacted. Is irradiated with energy rays to cure the energy ray-curable compound, and then the uncured composition present in the space formed between the concave portion of the member (A) and the member (B) ( By removing C), the member (A) and the member (B) are bonded to each other and a space is formed between the two members.

The method of contacting the member (B) with the surface of the member (A) in which the concave portions are formed via the composition (C) is arbitrary. For example, a method in which the composition (C) is applied to the member (A) and / or the member (B) and the composition (C) is applied to the member (A) or the member (B), and the composition (C) is placed and overlapped.
A method of spreading the composition (C) between the member (A) and the member (B), and narrowing the sheet-like member coated with the composition (C) on both surfaces between the member (A) and the member (B). A method of overlapping can be adopted.

When applying the energy ray-curable compound to the member (A) and / or the member (B), any coating method that can be applied on the member can be used. For example, a spin coating method, Roller coating method, casting method, dipping method, spray method, method using a bar coater,
Methods such as a method using an XY applicator, a screen printing method, a letterpress printing method, and a gravure printing method can be employed. The application site is arbitrary, and may be the entire surface where the member (A) and the member (B) are in contact or may be a partial surface, but is a region surrounding the periphery of a capillary formed after bonding. Is preferred. At this time, it may be applied to the concave portion of the member (A) or the surface other than the surface where each member contacts. The coating thickness is also arbitrary. When applying partially,
For example, when applying to the member (B) avoiding the position facing the concave portion of the member (A), it can be performed by a method using an XY applicator, various printing methods, or the like.

The member (A) and the member (B) are composed of the composition (C)
Is held in a state of being held. The site where the composition (C) is sandwiched may be the entire surface where the member (A) and the member (B) are in contact, or may be a part of the contact surface. It is preferably a portion surrounding the periphery of the capillary. When the member (A) and the member (B) are brought into contact with the composition (C) being held therebetween, the energy ray-curable compound may enter the concave portion of the member (A). Although the thickness of the composition (C) sandwiched between the member (A) and the member (B) is arbitrary, the thickness of the space formed by the concave portion of the member (A) and the member (B) after the bonding is determined. From the viewpoint of keeping the dimensions constant, it is preferably 300 μm or less.
More preferably, it is not more than μm. Of course, member (A)
When the composition and the member (B) are brought into contact with each other while holding the composition (C), the third member may be brought into contact with the composition (C) at the same time.

The member (A) and the member (B) sandwiching the composition (C) are irradiated with energy rays from outside the member (A) and / or the member (B) to portions other than the concave portions. The composition (C) is cured. The energy beam used for curing is a material capable of curing an energy ray-curable compound, and is a member (A) and / or a member (B).
Is transmitted. Examples of such energy rays include light rays such as ultraviolet rays, visible rays, and infrared rays; ionizing radiation such as X-rays and gamma rays; electron beams, ion beams,
Beta rays, particle beams such as heavy particle beams, and the like, UV and visible light are preferred from the viewpoint of handleability and curing speed,
Ultraviolet light is particularly preferred.

The method of irradiating an energy beam to a portion other than the concave portion is optional. For example, a method of irradiating an energy beam by photomasking the concave portion or a method of scanning with a laser beam or the like can be adopted. In the case of the photomasking method, it is also possible to divide the irradiation into a plurality of partial irradiations.

For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to perform the irradiation of the energy beam in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

After the composition (C) is cured by irradiation with energy rays, the uncured composition (C) in the space formed by the concave portions of the member (A) and the member (B) is removed. Remove from the opening to the outside. When the space is not open to the end of the member (A), that is, outside the microchemical device, a method such as drilling a hole in the member (A) and / or the member (B) at a position communicating with the space. Thereby, an opening can be formed. The openings are preferably at both ends of the space. The method of removing the uncured composition (C) is arbitrary, and for example, suction, extrusion with a fluid, extrusion with a plug, cleaning with a solvent that dissolves the composition (C), ultrasonic cleaning, and the like can be applied. . Fluids that can be used for extrusion can be gases, liquids, supercritical fluids, and the like. The liquid that can be used for extrusion may not dissolve the uncured composition (C). For solvent washing, circulation of the solvent, shaking in the presence of the solvent, and ultrasonic irradiation can be used. The above methods may be performed simultaneously or sequentially. For example, suction and extrusion may be performed simultaneously, or extrusion and cleaning may be performed by extruding with a solvent. Of these, suction and / or
Alternatively, it is preferable to perform washing with a solvent after extruding with a gas.

After removing the uncured composition (C), it is also preferable to irradiate energy rays again to completely cure the boundary between the cured part and the uncured part of the composition (C).

According to the second production method of the present invention, the member (A) is brought into contact with the member (B) via the composition (C) containing the energy ray-curable compound, (A) irradiating a part of the part excluding the concave part formed in (A) with an energy ray to cure the energy ray-curable compound,
After removing the uncured composition (C) existing in the space formed between the concave portion of the member (A) and the member (B), the uncured portion around the concave portion is irradiated with energy rays. This is a method in which the member (A) and the member (B) are adhered by curing, and a space is formed between the two members.

That is, in the second manufacturing method of the present invention, the member (A) and the member (B) are first partially adhered to fix the mutual positions of the members, and the concave portion of the member (A) and the member ( After removing the uncured composition (C) existing in the space formed between the member (B) and the uncured composition sandwiched between the member (B) and the surface other than the concave portion of the member (A). This is a method of irradiating the part with energy rays to cure it.

The thickness of the composition (C) sandwiched between the member (A) and the member (B) is preferably small. By making this thickness sufficiently smaller than the depth of the concave portion, the composition (C) held therebetween is left, and the composition formed in the space formed between the concave portion of the member (A) and the member (B) is formed. Only the composition (C) present can be selectively removed. The thickness of the composition (C) to be held is preferably 100 μm or less, more preferably 10 μm or less. If the thickness is larger than this, when removing the uncured composition (C) existing in the space formed between the concave portion of the member (A) and the member (B), the remaining portion other than the space is not removed. Part of the uncured composition (C) tends to be removed, which is not preferable.

The energy beam irradiation on a part of the member (A) excluding the concave portion is performed by partially bonding the member (A) and the member (B) to fix the mutual position of each member. is there. Therefore, as long as this object can be achieved, the irradiation site, shape, area, etc. are arbitrary, for example,
Can be a spot.

The method for removing the composition (C) is the first method according to the present invention.
Can be used, for example, by optimizing the cleaning time and the like, leaving the sandwiched composition (C) and leaving a gap between the concave portion of the member (A) and the member (B). Only the composition (C) existing in the space formed in the above can be selectively removed. Optimal conditions such as cleaning time
It can be determined by simple experiments in the system used.

The irradiation of the energy beam after removing the uncured composition (C) does not need to be applied only to the uncured portion, but may be applied to the entire member.

Other than this, for example, the member (A),
Member (B), composition (C), energy ray, coating method,
This is the same as in the first manufacturing method of the present invention.

The second manufacturing method of the present invention is the same as the first manufacturing method of the present invention.
Since the patterning accuracy of the energy beam irradiation may be lower than that of the manufacturing method of (1), there is an advantage that the manufacturing becomes easy.

According to the third production method of the present invention, the composition (C) of the concave portion is contacted with the member (B) in contact with the surface of the member (A) where the concave portion is formed via the composition (C). ) Is removed and the composition (C) is cured by irradiating it with energy rays to bond the member (A) and the member (B) and form a space between the two members. .

That is, in the third manufacturing method of the present invention, the member (A) and the member (B) are brought into contact with each other via the composition (C), and the mutual positions between the members are fixed by a clamp or the like. Removing the composition (C) existing in the space formed between the concave portion of the member (A) and the member (B), and then removing the surface of the member (A) other than the concave portion from the member (B). This is a method in which the uncured composition (C) sandwiched therebetween is cured by irradiating it with energy rays.

The thickness of the composition (C) sandwiched between the member (A) and the member (B) is the same as in the case of the second production method of the present invention.

The removal of the composition (C) is the same as in the second production method of the present invention.

The irradiation of the energy beam after removing the composition (C) does not need to be applied only to the portion where the composition (C) is present, but may be applied to the entire member. This is the same as the first manufacturing method of the present invention.

Other than this, for example, the member (A),
Member (B), composition (C), energy ray, coating method,
This is the same as in the first manufacturing method of the present invention.

The third manufacturing method of the present invention is the same as the first manufacturing method of the present invention.
In comparison with the manufacturing method of (1), the energy beam irradiation does not require patterning irradiation and can be performed on the entire surface, so that there is an advantage that manufacturing is easy.

[0063]

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

<Example 1> [Preparation of member (A)] On a surface of a flat plate having a thickness of 3 mm made of an acrylic resin ("Delpet 670N" manufactured by Asahi Kasei Corporation), 1,6-hexanediol di- Acrylate (“Kayarad HDDA” manufactured by Nippon Kayaku Co., Ltd.) 10
A mixture consisting of 0 parts and 0.02 part of an ultraviolet polymerization initiator 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) is applied using a 25 μm bar coater, and then the shape shown in FIG. 10 mW / cm ^{2 in} a nitrogen atmosphere using a light source unit for a multi-light 200 type exposure apparatus manufactured by Ushio Inc. via a photomask that blocks ultraviolet rays emitted to a portion to be the concave portion (2) of the above. Ultraviolet rays were irradiated for 10 seconds. After irradiating with ultraviolet light, the uncured material is washed and removed with ethanol, and then the acrylic resin plate is cut into a size of 2.5 cm × 2.5 cm. Member (A) on which (2) is formed [A-1]
(1) was produced.

[Preparation of Member (B)] A flat plate of the same acrylic resin as used in the member (A) was cut and cut into 2.5 cm ×
A 2.5 cm × 3 mm plate-shaped member (B) [B-1] was obtained.

[Preparation of Composition (C)] Glycerol acrylate methacrylate (“N
A composition (C) [C-1] consisting of 100 parts of K ester 701A) and 0.02 part of an ultraviolet polymerization initiator 1-hydroxycyclohexylphenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) was prepared.

[Adhesion] The composition (C) [C-1] was pipetted on the surface of the member (A) [A-1] (1) where the concave portion (2) was formed in a nitrogen gas atmosphere. About 0.1 cm ³ is placed, and the member (B) [B-1] (3) is brought into contact with it, and is clamped to about 100 kN while avoiding the recess (2).
The composition (C) [C-
1] was wiped off with filter paper. Using a light source unit for a multi-light 200 type exposure apparatus manufactured by Ushio Inc. for about 10 seconds from about 30 seconds after being clamped by the clamp, photomasking the concave portion (2) in FIG.
The composition (C) [C-1] in a portion other than the concave portion (2) is irradiated with ultraviolet light of W / cm ² to cure the member (A) [A-
1] (1) and the member (B) [B-1] (3) were bonded.

[Removal of Uncured Composition (C)] While introducing normal-pressure ethanol from the opening (4) in the space shown in FIG. 2, suction is performed from the other opening (not shown). The uncured composition filled in the space formed between the concave portion (2) of the member (A) [A-1] (1) and the member (B) [B-1] (3) At the same time as eliminating (C),
The composition (C) remaining in the space was removed by washing with ethanol to obtain a microchemical device [D-1] having the shape shown in FIG.

[Leakage test] Water colored with malachite green (manufactured by Wako Pure Chemical Industries, Ltd.) was supplied from the opening (4) of the obtained microchemical device [D-1] by 0.1MP.
A test was performed in which the sample was introduced at a water pressure of a and left for 1 hour with the other opening (not shown) closed. As a result, the member (A) [A-1] (1) and the member (B) [B
-1] Water leakage into the gap of (3) and the member (A) [A-
1] (1) and peeling of the member (B) [B-1] (3) were not observed.

[Cross Section Observation] The microchemical device [D-1] was broken at the temperature of liquid nitrogen, and the thickness of the cured product of the composition (C) at the bonded portion was measured to be about 7 μm.

<Example 2> [Preparation of microchemical device] In Example 1, instead of the method of photomasking the concave portion (2) and irradiating ultraviolet rays, the member (A) was moved from the four corners to the center. 5m in diameter centered on the 3mm inside
m was irradiated with ultraviolet light only at the four points (not shown). After irradiation with ultraviolet light, the clamp was removed, and the recesses and members of the members (A) [A-1] (1) were made in the same manner as in Example 1. (B) [B-1] The removal of the uncured composition (C) filling the space formed between (3) and the entire member laminated after the removal. A microchemical device [D-2] having the shape shown in FIG. 2 was produced in the same manner as in Example 1 except that ultraviolet light having the same intensity was irradiated in a nitrogen atmosphere for 20 seconds.

[Leakage Test] The microchemical device [D-2] obtained in Example 2 was evaluated by performing the same leakage test as in Example 1, and the same results as in Example 1 were obtained.

[Cross Section Observation] The microchemical device [D-2] obtained in Example 2 was evaluated by performing the same cross section observation as in Example 1. The results were the same as in Example 1.

<Example 3> [Preparation of microchemical device] In Example 1, before irradiation with ultraviolet rays, the members (A) [A-1] were fixed in the same manner as in Example 1 while being clamped. (1)
Of the uncured composition (C) filling the space formed between the concave portion (2) and the member (B) [B-1] (3), and after the removal, nitrogen 3 in the atmosphere
Example 1 except that two kw metal halide lamps were used to simultaneously irradiate 60 mw / cm ² of ultraviolet light for 10 seconds from both the front and back sides of the member fixed by the clamp, respectively.
In the same manner as in the above, a microchemical device [D-3] having the shape shown in FIG. 2 was produced.

[Leak Test] The microchemical device [D-3] obtained in Example 3 was evaluated by performing the same leak test as in Example 1, and the same result as in Example 1 was obtained.

[Cross Section Observation] The microchemical device [D-3] obtained in Example 3 was evaluated by performing the same cross section observation as in Example 1. The same results as in Example 1 were obtained.

<Example 4> [Preparation of microchemical device] In Example 1, glycerol acrylate methacrylate (“NK ester 701A” manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of the composition (C) [C-1]. 2) In the same manner as in Example 1 except that the composition (C) [C-4] consisting of 50 parts and 50 parts of N-cyclohexylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. A microchemical device [D-5] was produced.

[Leakage Test] The microchemical device [D-4] obtained in Example 4 was evaluated by performing the same leak test as in Example 1. The same results as in Example 1 were obtained.

[Cross Section Observation] The microchemical device [D-4] obtained in Example 4 was evaluated by performing the same cross section observation as in Example 1. The same results as in Example 1 were obtained.

<Example 5> [Preparation of microchemical device] In Example 2, composition (C) [C-4] used in Example 4 was used instead of composition (C) [C-1]. A microchemical device [D-5] having the shape shown in FIG. 2 was produced in the same manner as in Example 2 except that the above was used.

[Leak Test] The microchemical device [D-5] obtained in Example 5 was evaluated by performing the same leak test as in Example 1, and the same results as in Example 1 were obtained.

[Cross Section Observation] The microchemical device [D-5] obtained in Example 5 was evaluated by performing the same cross section observation as in Example 1. The same results as in Example 1 were obtained.

<Example 6> [Preparation of microchemical device] In Example 3, composition (C) [C-4] used in Example 4 was used instead of composition (C) [C-1]. A microchemical device [D-6] having the shape shown in FIG. 2 was produced in the same manner as in Example 3 except that was used.

[Leakage Test] The microchemical device [D-6] obtained in Example 6 was evaluated by performing the same leak test as in Example 1, and the same result as in Example 1 was obtained.

[Cross Section Observation] The microchemical device [D-6] obtained in Example 6 was evaluated by performing the same cross section observation as in Example 1. The same results as in Example 1 were obtained.

<Example 7> [Production of microchemical device] In Example 1, the material of the member (B) was changed to acrylic resin,
Except for using polystyrene ("Dick Styrene XC-520" manufactured by Dainippon Ink and Chemicals, Inc.),
A microchemical device [D-7] having the shape shown in FIG. 2 was produced in the same manner as in Example 1.

[Leakage Test] The microchemical device [D-7] obtained in Example 7 was evaluated by performing the same leak test as in Example 1, and the same result as in Example 1 was obtained.

[Cross Section Observation] The microchemical device [D-7] obtained in Example 7 was evaluated by performing the same cross section observation as in Example 1. The same results as in Example 1 were obtained.

[0089]

According to the manufacturing method of the present invention, the member having the concave portion and the other member can be completely brought into close contact with each other. A microchemical device that does not cause leakage of a liquid into the device can be manufactured. Further, according to the manufacturing method of the present invention, the space formed between the member in which the concave portion is formed and the other member is not closed by the adhesive, and has a minute or narrow space between the members. Microchemical devices can be manufactured.

[Brief description of the drawings]

FIG. 1 is a plan view of a member (A) used in an example when viewed from a direction perpendicular to a surface.

[Explanation of symbols]

 1 member (A) 2 recess

FIG. 2 is a bird's-eye view of the microchemical device manufactured in the example.

[Explanation of symbols]

 1 member (A) 3 member (B) 4 opening of space

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Claims (9)

[Claims] 1. A member (A) having a concave portion having a depth of 1 to 3000 μm on its surface and another member (B) are bonded to each other to form between the concave portion of the member (A) and the member (B). A method for producing a microchemical device having a defined space, comprising: contacting a surface of a member (A) having a concave portion with a member (B) via a composition (C) containing an energy ray-curable compound. After the composition (C) is cured by irradiating an energy beam to a portion excluding the concave portion formed in the member (A), a space formed between the concave portion of the member (A) and the member (B). A method for producing a microchemical device, comprising removing an uncured composition (C) present therein. 2. The method for manufacturing a microchemical device according to claim 1, wherein the concave portion has a groove shape having a width of 1 to 3000 μm. 3. The method for producing a microchemical device according to claim 1, wherein the energy ray-curable compound is an energy ray-curable compound having an acryloyl group or a maleimide group. 4. A space formed by a member (A) having a concave portion with a depth of 1 to 3000 μm on the surface and a concave portion of the member (A) and a member (B) by bonding another member (B). A method for producing a microchemical device comprising: contacting a surface of a member (A) with a concave portion formed thereon with a member (B) via a composition (C) containing an energy-ray-curable compound; The composition (C) is cured by irradiating a part of the part excluding the concave part formed in A) with an energy ray,
The uncured energy ray-curable composition (C) existing in the space formed between the concave portion of the member (A) and the member (B)
A method for manufacturing a microchemical device, comprising: irradiating an uncured portion around a concave portion with an energy ray after curing to cure the device. 5. The method for manufacturing a microchemical device according to claim 4, wherein the concave portion has a groove shape having a width of 1 to 3000 μm. 6. The method for producing a microchemical device according to claim 4, wherein the energy ray-curable compound is an energy ray-curable compound having an acryloyl group or a maleimide group. 7. A space formed by a member (A) having a concave portion having a depth of 1 to 3000 μm on the surface and a concave portion of the member (A) and a member (B) by bonding another member (B). A method for producing a microchemical device comprising: contacting a surface of a member (A) with a concave portion with a member (B) via a composition (C) containing an energy ray-curable compound; A method for producing a microchemical device, comprising: curing a composition (C) by irradiating an energy ray after removing the composition (C) in the concave portion. 8. The method for manufacturing a microchemical device according to claim 7, wherein the concave portion has a groove shape having a width of 1 to 3000 μm. 9. The method for producing a microchemical device according to claim 7, wherein the energy ray-curable compound is an energy ray-curable compound having an acryloyl group or a maleimide group.