JP2000248076A - Production of minute chemical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for sticking a member having a groove on the surface to the other member in a state in which the space therebetween adheres completely, without blocking the extremely fine groove. SOLUTION: This method for producing a minute chemical device having a capillary flow pass between a member A and a member B comprises coating a composition C containing a cross-linkable compound on the member B, bringing the surface b coated with the composition C on the member B in a semi- hardened state in which the composition C loses the fluidity and the unreacted polymerizable groups remains, into contact with the grooved surface (a) of the member A, having a groove with 1-1,000 μm width and 1-1,000 μm depth on the surface, and completely hardening the composition C in the state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a microchemical device, that is, a chemistry, biochemistry, physical chemistry in which a structure such as a microchannel, a reaction tank, an electrophoresis column, a membrane separation mechanism, etc. is formed in a member. For micro-reaction devices (micro-reactors), micro-analysis devices such as integrated DNA analysis devices, micro-electrophoresis devices, micro-chromatography devices, etc. The present invention relates to a micro-reaction device and a micro-analysis device having a capillary flow path formed by bonding and integrating.

[0002]

2. Description of the Related Art It is known that a thin groove is formed in a base material such as silicon, quartz, glass, or polymer by an etching method to form a liquid channel or a gel channel for separation (for example, R.M.・ McCormick et al., “Analytical Chemistry”, p. 2626, vol. 69, 1
997), it is known that a cover such as a glass plate is tightly attached to the surface by screws or the like for the purpose of preventing evaporation of liquid during operation.

[0003]

However, it is quite difficult to completely adhere the substrate and the cover to each other, and the liquid tends to leak between the substrate and the cover.

On the other hand, when these two members are bonded with an adhesive, if the groove formed in the base material is narrow, the adhesive tends to enter the groove and block the flow path.

[0005] The problem to be solved by the present invention is to provide a method for bonding a member having a groove on its surface and another member in a state in which they are completely adhered to each other, and for bonding without closing a very narrow groove. To provide.

[0006]

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 cross-linkable polymerizable compound, particularly an energy beam cross-linkable polymerizable compound, is used as an adhesive, and heat and energy rays are used. In the state of being semi-cured until the fluidity is lost by irradiation, it is contacted with other members to be bonded, and by using a method of completely curing in that state, it has been found that it is possible to bond without closing a very small groove,
The present invention has been completed.

That is, according to the present invention, in order to solve the above-mentioned problems, (I) the surface has a width of 1 to 1000 μm and a depth of 1 to 100 μm.
A method for manufacturing a microchemical device in which a member (A) having a groove of 0 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). Then, the composition (C) containing the cross-linkable polymerizable compound is applied to the member (B), and then the composition (C) containing the cross-linkable polymerizable compound loses its fluidity and has an unreacted polymerizable group. In the state where semi-cured to the extent that remains, the coated surface (b) made of the composition (C) containing the crosslinkable polymerizable compound of the member (B) and the grooved surface (a) of the member (A) And then bonding by completely curing the composition (C) containing the cross-linkable polymerizable compound in that state (hereinafter, referred to as a method for producing a microchemical device).
This is referred to as "the first manufacturing method of the present invention". )I will provide a.

In order to solve the above-mentioned problems, the present invention provides (II) a method of forming a surface having a width of 1 to 1000 μm and a depth of 1 to 100 μm.
A method for manufacturing a microchemical device in which a member (A) having a groove of 0 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). Then, on the surface (a) where the groove of the member (A) is formed,
The composition (C ') containing the cross-linkable polymerizable compound at a thickness of 1/10000 to 1/2 of the depth of the groove, and the composition (C) containing the cross-linkable polymerizable compound in the member (B), respectively. After coating, the composition (C) and the composition (C ′) containing the cross-linkable polymerizable compound lose their fluidity and are semi-cured to such an extent that unreacted polymerizable groups remain, and (A)
A coating surface (a ′) composed of the composition (C ′) containing the semi-cured cross-linkable polymerizable compound, and a coating composed of the composition (C) containing the semi-cured cross-linked polymerizable compound of the member (B) A surface of the microchemical device, which is brought into contact with the surface (b ′), and in this state, the composition (C) containing the crosslinkable polymerizable compound and the composition (C ′) are completely cured to be bonded to each other. A manufacturing method (hereinafter, referred to as a “second manufacturing method of the present invention”) is provided.

In order to solve the above-mentioned problems, the present invention provides: (III) a surface having a width of 1 to 1000 μm and a depth of 1 to 10 μm;
A method for manufacturing a microchemical device in which a member (A) having a groove of 00 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). Then, the composition (C) containing the cross-linkable polymerizable compound is applied to the member (B), and then the composition (C) containing the cross-linkable polymerizable compound loses its fluidity and has an unreacted polymerizable group. In the state where semi-cured to the extent that remains, the coated surface (b ″) of the composition (C) containing the crosslinkable polymerizable compound of the member (B) and the surface of the member (A) where the grooves are formed (a)
A composition (C ″) containing a cross-linkable polymerizable compound is applied to a thickness of 1/10000 to 1/10 of the depth of the groove, and the applied surface (a ″) is brought into contact with the composition. A method for producing a microchemical device, characterized in that a composition (C) containing a cross-linkable polymerizable compound and a composition (C ″) containing a cross-linkable polymerizable compound are completely cured so that they are bonded to each other (hereinafter, referred to as “ A third manufacturing method of the present invention ”).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The member (A) used in the production method of the present invention is impermeable to the liquid used in the microchemical device obtained by the present invention, and has a width of 1 to 3 on the surface.
It has a groove of 1000 μm and a depth of 1 to 1000 μm. The width of the groove is 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more. A microchemical device having a narrower groove becomes difficult to manufacture. The width of the groove is 1000 μm or less, and 300
μm or less, more preferably 100 μm or less. If the width of the groove is wider than this, the effect of the present invention is reduced. The depth of the groove is 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more. A microchemical device having a shallower groove becomes difficult to manufacture. The depth of the groove is also 1000 μm or less,
It is preferably 300 μm or less, more preferably 100 μm or less. If the groove is deeper than this, the effect of the present invention is reduced. The width / depth ratio of the groove is arbitrary, but is preferably in the range of 0.2 to 5, more preferably in the range of 0.5 to 2.0. The shape of the groove viewed from the top surface does not need to be a straight line, but may be any shape. Also, the cross-sectional shape of the groove is square,
Any shape such as a trapezoid or a semicircle may be used. Member (A)
Above, other structures connected to the groove, such as a reservoir,
A reaction tank, a flow rate measuring unit, a valve, a valve, a groove filled with gel, a separation membrane, and the like may be formed.

[0011] 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 also 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 adhered with a cross-linkable polymerizable compound. However, when an energy ray-curable compound is used as an adhesive,
When the member (B) described later does not transmit the energy ray used in the present invention, it must be able to transmit the energy ray used in the present invention. As a material that can be used as the material of the member (A), for example,
Examples thereof include polymers, crystals such as glass and quartz, semiconductors such as ceramic and silicon, and metals. Of these, polymers are particularly preferable from the viewpoints of easy moldability, high productivity, and low cost.

Examples of the polymer which can be used for the member (A) include styrene-based 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.

The modifier which can be contained in the member (A) includes, for example, 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 colorant that can be contained in the member (A), any dye or pigment, fluorescent dye or pigment,
UV absorbers.

Examples of the reinforcing material that can be contained in the member (A) include 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.

Further, in using the microchemical device of the present invention, 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 make the surface of the groove of the member (A) hydrophilic. 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). (B) Any shape, material, structure, surface condition, and the like can be used as long as a capillary-shaped flow path can be formed by the method. These are the same as in the case of the member (A), except that the grooves need not be formed on the surface. The member (B) does not need to have a groove formed on the surface, but may have a groove or a structure other than the groove. The member (B)
When the energy ray-curable compound is used as an adhesive and the member (A) does not transmit the energy ray used in the present invention, the energy ray used in the present invention is transmitted. Needs to be

The crosslinkable polymerizable compound used in the present invention is not particularly limited as long as it can form a crosslinked polymer by crosslink polymerization. Examples thereof include an epoxy adhesive, a urethane adhesive, a phenol adhesive, and a urea adhesive. Thermosetting compounds such as adhesives; water-crosslinkable adhesives such as silicone-based adhesives;
Energy ray-curable compounds and the like. Among these, an energy ray-curable compound is preferable because of its high polymerization rate. The energy ray-curable compound may be any compound such as a radical polymerizable compound, an anionic polymerizable compound, and a cationic polymerizable compound. 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, and among them, a highly reactive (meth) acrylic compound, vinyl ethers, and the absence of a photopolymerization initiator are preferable. A maleimide-based compound that cures even below is preferred.

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 And hexafunctional monomers as described above.

Also, 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.

These energy ray-curable compounds can be used alone or as a mixture of two or more.

The composition containing the energy ray-curable compound may be mixed with a monofunctional monomer, for example, a monofunctional (meth) acrylic monomer, for the purpose of increasing adhesiveness.

Examples of the maleimide-based crosslinkable polymerizable compound include 4,4′-methylenebis (N-phenylmaleimide) and 2,3-bis (2,4,5-trimethyl-
3-thienyl) maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, triethylene glycol bismaleimide, N, N'-m-phenylenedimaleimide, m-tolylenedimaleimide, N, N'-
1,4-phenylenedimaleimide, N, N'-diphenylmethane dimaleimide, N, N'-diphenylether dimaleimide, N, N'-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4- Bifunctional maleimides such as diazoniabicyclo- [2,2,2] octane dichloride, 4,4'-isopropylidenediphenyl dicyanate.N, N '-(methylenedi-p-phenylene) dimaleimide; N- (9-acridinyl) And maleimides having a maleimide group such as maleimide and a polymerizable functional group other than the maleimide group. Maleimide monomers include vinyl monomers, vinyl ethers, and polymerizable carbons such as acrylic monomers.
It can be copolymerized with a compound having a carbon double bond.

Composition (C) containing cross-linkable polymerizable compound
Contains a cross-linkable polymerizable compound as an essential component, and may be a mixture of a plurality of types of cross-linkable polymerizable compounds. For example, in order for the cured product of the energy ray-curable compound to be a crosslinked polymer, the composition (C) needs to contain a polyfunctional monomer and / or oligomer. It is also possible to mix monomers and / or oligomers.

Composition (C) containing crosslinkable polymerizable compound
Examples of the monofunctional (meth) acrylic monomer that can be mixed and used in the above 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-acryloysoxypropyl hexahexahydrohydrate Zhen phthalate, fluorine-substituted alkyl (meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sodium sulfonate 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) acrylamide, (N, N-
Dialkyl) acrylamide, achloroyl morpholine, and the like.

Composition (C) containing crosslinkable polymerizable compound
Examples of the monofunctional maleimide-based monomer which can be mixed and used include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide; N-alicyclic rings such as N-cyclohexylmaleimide Group maleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide, 2,3
N- (substituted or unsubstituted phenyl) maleimide such as -dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide; N-benzyl -2,3-dichloromaleimide, N- (4'-fluorophenyl) -2,3
Maleimide having a halogen such as dichloromaleimide; maleimide having a hydroxyl group such as hydroxyphenylmaleimide; maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide; and alkoxy group such as N-methoxyphenylmaleimide. 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, N- (4-anilino-1)
And maleimides having a heterocyclic ring such as -naphthyl) maleimide.

Composition (C) containing crosslinkable polymerizable compound
If necessary, other components such as a photopolymerization initiator, a solvent, a thickener, a modifier, and a colorant can be mixed and used.

Composition (C) containing a crosslinkable polymerizable compound
The photopolymerization initiator, which can be mixed and used as required, is particularly limited as long as it is active with respect to the energy ray used in the present invention and can polymerize the energy ray-curable compound. However, for example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator may be used. As such a photopolymerization initiator, for example, p-tert-butyltrichloroacetophenone, 2,2
2'-diethoxyacetophenone, 2-hydroxy-2
Acetophenones such as -methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone,
Ketones such as 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, for example, a monofunctional maleimide monomer exemplified as a monofunctional maleimide monomer which can be mixed and used in the composition (C), in addition to a polyfunctional monomer such as a polyfunctional maleimide exemplified as an energy ray-curable compound. It may be a functional monomer.

Composition (C) containing a crosslinkable polymerizable compound
When a non-polymerizable photopolymerization initiator is used by mixing with a photopolymerization initiator, the amount used is preferably in the range of 0.005 to 20% by weight, and particularly preferably in the range of 0.01 to 2% by weight.

Composition (C) containing crosslinkable polymerizable compound
Examples of the thickener that can be mixed and used as necessary include a linear polymer that is soluble in a crosslinkable polymerizable compound and insoluble in a gel.

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

Composition (C) containing crosslinkable polymerizable compound
Examples of the colorant that can be mixed and used as needed include arbitrary dyes, pigments, and fluorescent dyes.

In the first production method of the present invention, the composition (C) containing the crosslinkable polymerizable compound is applied to the member (B), and then the composition (C) containing the crosslinkable polymerizable compound is applied to the fluidity. And the unreacted polymerizable group remains and is semi-cured to the extent that adhesiveness is not lost, and the member (B) is coated with the crosslinked polymerizable compound-containing composition (C).
(b) is brought into contact with the grooved surface (a) of the member (A), and in this state, the composition (C) containing the crosslinkable polymerizable compound is completely cured, whereby the member (A) and the member (A) (B).

As a method for applying the crosslinkable polymerizable compound to the member (B), any coating method that can be applied on the member (B) can be used. For example, spin coating, roller coating, casting, etc. Methods, a dipping method, a spray method, a method using a bar coater, a method using an XY applicator, a screen printing method, a letterpress printing method, a gravure printing method, and the like. The application site is arbitrary and may be the entire surface of the member (B) in contact with the member (A) or may be a partial surface, but may be a site surrounding the capillary formed after bonding. preferable. The coating may be applied to a surface of the member (B) other than the surface in contact with the member (A). The coating thickness is also arbitrary. When applying partially,
For example, in the case where the coating is performed while avoiding the position facing the groove of the member (A), it can be performed by a method using an XY applicator, various printing methods, or the like.

The uncured coating of the cross-linkable polymerizable compound may be heated, humidified, irradiated with energy rays, or the like, depending on the type of the cross-linkable polymerizable compound, so that the unreacted polymerizable reactive group has a temperature above the gel point. Semi-cured to the extent that it remains. The gel point means that cross-linking polymerization proceeds in the coating film, and the entire coating film
A reaction point at which a network-like polymer having an unreacted crosslinked polymerizable compound inserted in the network is formed. When the polymerization reaction has passed the gel point, the coating film loses fluidity.

In the manufacturing method of the present invention, the member (B)
Is laminated with the member (A) in a state where the fluidity of the coating film of the cross-linkable polymerizable compound applied to the film is lost. This can prevent the crosslinkable polymerizable compound from entering the groove of the member (A). On the other hand, if the polymerization proceeds too much and the amount of unreacted polymerizable reactive groups becomes too small, the coating film loses flexibility and the adhesiveness is reduced, and the adhesion to the member (A) tends to be incomplete. A suitable degree of semi-curing can be determined by simple experiments in the system used.

The semi-cured coating film may show tackiness in some cases, but in the present invention, it is not necessary to show tackiness. The adhesive strength of the semi-cured coating film largely depends on the chemical structure of the crosslinkable polymerizable compound, but is independent of the adhesive strength and the adhesive strength. Generally speaking, the tackiness of cross-linked semi-cured coatings tends to be low.

Composition (C) containing a crosslinkable polymerizable compound
After semi-curing of the coating film composed of, the coated surface of the member (B) is brought into contact with the grooved surface of the member (A), and further cured in that state, whereby the crosslinked polymerizable compound is completely cured.
The term “complete curing” as used herein refers to curing to the extent that a sufficient adhesive force is generated, and it is not always necessary to completely eliminate the crosslinkable polymerizable group. When the crosslinkable polymerizable compound is an energy ray-curable compound, the bonding surface between the member (A) and the member (B) is irradiated with energy rays from outside the member (A) and / or the member (B). To cure.

The energy rays that can be used for the semi-curing and the complete curing are those that can cure the crosslinkable polymerizable compound, and the energy rays that can be used for the complete curing include the member (A) And / or through the member (B). Examples of such energy rays include light rays such as ultraviolet rays, visible light rays, and infrared rays;
Ionizing radiations such as X-rays and gamma rays; and electron beams, ion beams, beta rays, heavy particle beams and the like, but ultraviolet rays and visible lights are preferred from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferred. For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to perform the irradiation of the energy rays in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere. The energy beam used for semi-curing and the energy beam used for complete curing need not be the same.

According to the second manufacturing method of the present invention, the surface (a) where the groove of the member (A) is formed has a thickness of 1/10000 of the depth of the groove.
A composition (C ′) containing the cross-linkable polymerizable compound and a composition (C) containing the cross-linkable polymerizable compound are applied to the member (B) to a thickness of ２, respectively. In a state in which the composition (C) and the composition (C ′) to be contained lose fluidity and are semi-cured to the extent that unreacted polymerizable groups remain, semi-cured cross-linked polymerization of the member (A) A coating surface (a ′) composed of a composition (C ′) containing a reactive compound,
The composition (C) containing the crosslinked polymerizable compound and the composition in that state are brought into contact with the coated surface (b ′) of the composition (C) containing the semi-cured crosslinked polymerizable compound of the member (B) and in that state This is a method in which the object (C ′) is completely cured so as to be bonded.

That is, in the second production method of the present invention, the composition (C ′) containing the crosslinked polymerizable compound having a specific thickness was applied to the member (A), and the coating was semi-cured. Thereafter, the second embodiment is different from the first production method of the present invention in that the film is adhered to the member (B) in which the coating film is also semi-cured.

The amount of the composition (C ') applied to the member (A) is determined by the amount of the composition (C) on the member (B) if there is no coating film of the composition (C) on the member (B). It may be very thin such that a gap is formed or adhesion is incomplete, and its thickness is 1 / 10,000 or more of the depth of the groove. Of course, when the depth of the groove is as shallow as about 1 μm, for example, 1/1
A value greater than 0000 may be a practical lower limit. However, the coating film does not necessarily need to completely cover the surface of the member (A) other than the concave portions, and may have a molecular gap, for example. If the thickness is smaller than this, there is no difference in effect from the first manufacturing method of the present invention. The thickness of the coating film composed of the composition (C ′) applied to the member (A) is １ ／ or less of the groove depth, preferably 1/10 or less, and is 1/100 or less. Is more preferred. If the thickness is larger than this, when the composition (C ′) is applied, the composition (C ′) fills the groove, and the capillary formed between the member (A) and the member (B) tends to be closed. Not preferred.

The crosslinkable polymerizable compound constituting the composition (C ′) can be selected from the group described as the crosslinkable polymerizable compound that can be used in the first production method of the present invention. The composition (C ′) is the same as the composition (C) used in the first production method of the present invention. The composition (C ′) may be the same as or different from the composition (C), but if different, it is necessary that the composition (C ′) can adhere to each other, and the crosslinkable polymerizable compound contained in each of them Are preferably polymerizable with each other, and are more preferably cured by the same curing method. The composition (C ′) is preferably the same as the composition (C). In order to apply thinly, it is also preferable that the composition (C ′) contains a volatile solvent. The method for applying the composition (C ′), the method for curing the composition (C ′), and the like are the same as those described for the composition (C) in the first production method of the present invention. When the composition (C ′) contains a volatile solvent, the solvent needs to be removed before or after semi-curing and before bonding to the member (A). Regarding other parts, for example, regarding the member (A), the member (B), the composition (C), the energy ray, the coating method, the semi-curing or curing method, and the like, the first production of the present invention Similar to the method.

The second manufacturing method of the present invention is the same as the first manufacturing method of the present invention.
Compared with microchemical devices obtained by the manufacturing method of
It is easy to increase the adhesive strength and can be used at a high fluid pressure. Further, as compared with the first production method of the present invention, the allowable range of the degree of semi-curing of the coating film of the composition (C) is widened, and the production is easy.

In the third production method of the present invention, the composition (C) containing the crosslinkable polymerizable compound is applied to the member (B), and then the composition (C) containing the crosslinkable polymerizable compound is applied to the fluidity. And the coated surface (b ") of the composition (C) containing the cross-linkable polymerizable compound of the member (B), in a state of being semi-cured to the extent that unreacted polymerizable groups remain, and On the surface (a) where the groove of the member (A) is formed, 1/1000 of the depth of the groove
A composition (C ″) containing a cross-linkable polymerizable compound is applied to a thickness of 1/10, and the coated surface (a ″) is brought into contact with the composition (C ″). )) And the composition (C ″) containing the cross-linkable polymerizable compound are completely cured to bond the composition.

That is, in the third production method of the present invention, the coating of the composition (C ″) containing the crosslinkable polymerizable compound applied to the member (A) is bonded to the member (B) without semi-curing. This is different from the second manufacturing method of the present invention.

The amount of the composition (C ″) applied to the member (A) is determined by the amount of the composition (C ″) between the member (A) and the member (B) unless there is a coating film composed of the composition (C) on the member (B). The thickness of the groove may be as small as 1 / 10,000 or more of the depth of the groove, and the depth of the groove may be as shallow as, for example, about 1 μm. Sometimes 1/10
A value greater than 000 may be a practical lower limit. However, the coating does not necessarily have to completely cover the surface of the member (A) other than the concave portions, and may have, for example, a molecular gap. If the thickness is smaller than this, there is no difference in effect from the first manufacturing method of the present invention. The thickness of the coating film is 1/10 or less, preferably 1/30 or less, more preferably 1/100 or less of the depth of the groove. When the thickness is larger than this, when the member (A) and the member (B) are brought into contact, the composition (C ″) flows to fill the groove, and the capillary formed between the member (A) and the member (B) is formed. It is not preferable because it tends to be blocked.

The crosslinkable polymerizable compound constituting the composition (C ″) can be selected from the group described as the crosslinkable polymerizable compound that can be used in the first production method of the present invention. Is the same as the composition (C) used in the first production method of the present invention. The composition (C ″) may be the same as or different from the composition (C), but if different, it is necessary that the composition (C ″) can adhere to each other, and the crosslinkable polymerizable compound contained in each Are preferably polymerizable with each other, and more preferably contain the same crosslinkable polymerizable compound.The composition (C ″) is also preferably the same as the composition (C). In order to apply the composition thinly, the composition (C ") preferably contains a volatile solvent. The method for applying the composition (C") and the method for curing the composition (C ") are described below. This is the same as that described for the composition (C) in the first production method of the present invention.If the composition (C ″) contains a volatile solvent, the composition before bonding to the member (A) is used. It is necessary to remove the solvent. Other parts, for example,
Items relating to the member (A), the member (B), and the composition (C);
Regarding the energy beam, the coating method, the curing method, and the like, they are the same as those of the first manufacturing method of the present invention.

The third manufacturing method of the present invention is the first manufacturing method of the present invention.
Compared with microchemical devices obtained by the manufacturing method of
It is easy to increase the adhesive strength and can be used at a high fluid pressure. Further, as compared with the first production method of the present invention, the allowable range of the degree of semi-curing of the coating film of the composition (C) is widened, and the production is easy.

[0054]

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)] A 1,6-hexanedioldiamine was placed on the surface of a 3 mm-thick flat plate made of an acrylic resin ("Delpet 670N" manufactured by Asahi Kasei Corporation). Acrylate (“Kayarad HDDA” manufactured by Nippon Kayaku Co., Ltd.) 10
A mixture consisting of 0 parts and 2 parts of an ultraviolet polymerization initiator 1-hydroxycyclohexylphenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) was applied using a 25 μm bar coater. Next, using a light source unit for a multi-light 200 type exposure apparatus manufactured by Ushio Inc., through a photomask for blocking ultraviolet rays irradiated to a portion to be the groove (2) having the shape shown in FIG. Ultraviolet rays of 10 mW / cm ² were irradiated for 10 seconds in a nitrogen atmosphere. After UV irradiation, wash and remove uncured material with ethanol,
The acrylic resin plate was cut into 2.5 cm x 2.5 cm,
(A) [A-1] (1) in which a groove (2) having a width of 25 μm and a depth of 26 μm having the shape shown in FIG.

[Preparation of Member (B)] The same acrylic resin flat plate 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)] 100 parts of ethylene oxide-modified bisphenol A diacrylate ("BPE-4" manufactured by Daiichi Kogyo Co., Ltd.) and 1-hydroxycyclohexyl phenyl ketone (UV initiator) (Ciba Geigy) "Irgacure 184") 0.02
A composition (C) [C-1] consisting of 3 parts by weight was prepared.

[Adhesion] Using a coating roller, the composition (C) [C-1] was applied to one entire surface of the member (B) [B-1] (3) measuring 2.5 cm × 2.5 cm. Is applied to a thickness of about 30 μm, and irradiated with ultraviolet light of 10 mW / cm ² for 1 second in a nitrogen gas atmosphere (oxygen concentration of about 2%) using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc. And semi-cured.

In a nitrogen gas atmosphere (oxygen concentration: about 2%), the coating surface of the member (B) [B-1] (3) obtained by semi-curing the coating film and the member (A) [A-1] (1) is laminated so that the surface on which the groove is formed is in contact with the surface, and about 100 mm is clamped.
Approximately 3 seconds from the point of sandwiching with the force of kN, and simultaneously irradiating 60 mW / cm ² of ultraviolet light from both the front and back sides simultaneously using two 3 kW metal halide lamps for 10 seconds, the composition (C) [ C-1] was cured and bonded to obtain a microchemical device [D-1] having the shape shown in FIG.

A microchemical device [D-1 '] was obtained in the same manner except that ultraviolet irradiation was started about 60 seconds after the clamp.

For confirmation, the coating was separately scraped off from the member (B) [B-1] in which the coating was semi-cured. As a result, the coating was gel-like and did not show fluidity. .

[Distribution and Leakage Test] Water colored with malachite green (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced from the capillary opening (4) of the obtained microchemical device [D-1]. No obstruction was observed. Next, a test was performed in which the capillary was allowed to stand still for 1 hour in a state where a water pressure of 0.1 MPa was applied, and the members (A) [A-1] and (B) [B-
No leakage of water into the gap of [1] and separation of the member (A) [A-1] from the member (B) [B-1] were observed.

Further, a microchemical device [D-1 ']
The same was true for. That is, it was confirmed that the semi-cured composition (C) [C-1] did not flow to block the capillary.

<Example 2> [Preparation of microchemical device]
As the composition (C ′) [C′-2], the composition (C) [C
Using the 5% ethanol solution of [-1], and spraying the composition [C'-2] on the entire surface of the member (A) [A-1] where the grooves are formed, and hot air at 40 ° C. for 15 minutes. The ethanol was removed by drying, and the member (A) [A-2] on which the solvent-removed coating film of the composition (C ') [C'-2] was formed was irradiated with ultraviolet rays for 1 second in a nitrogen gas atmosphere. After being irradiated and semi-cured, and then subjected to bonding,
In the same manner as in Example 1, the fine chemical device [D-
2] was produced.

For confirmation, the composition (C) was separately prepared.
Member (A) on which the solvent-removed coating film of [C'-2] is formed
[A-2] was irradiated with ultraviolet rays for 10 seconds in a nitrogen gas atmosphere and completely cured. The cross section of the cured product was observed with a scanning electron microscope, and the coating thickness was measured to be about 1.3 μm.
Met.

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

<Example 3> [Preparation of microchemical device]
Same as Example 2 except that the member (A) [A-2] on which the solvent-removed coating film of the composition (C ') [C'-2] was formed was used for adhesion without irradiating ultraviolet rays. Thus, a microchemical device [D-3] was produced.

For confirmation, the composition (C ′) was prepared separately.
Member (A) coated with the dried product of [C′-2] [A-
2] was irradiated with ultraviolet rays in nitrogen gas for 10 seconds and completely cured, and the cross section was observed with a scanning electron microscope.
The measured coating thickness was about 1.3 μm.

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

<Example 4> [Preparation of microchemical device]
As composition (C) [C-4], a bisphenol A type epoxy ("Epiclon 857" manufactured by Dainippon Ink and Chemicals, Inc.) and an amine type curing agent ("Epiclon B1170" manufactured by Dainippon Ink and Chemicals, Inc.) -70 ") (viscosity at 20 ° C. of 1100 mPa · s)], and instead of ultraviolet irradiation, the mixture was allowed to stand at 25 ° C. for 60 minutes to be semi-cured. 40
Microchemical device [D-4] in the same manner as in Example 1 except that it was left at 30 ° C. for 30 minutes to completely cure.
Was prepared.

For confirmation, when the coating film was separately scraped from the member [B-4] in which the coating film was semi-cured, the coating film was gel-like and did not show fluidity.

[Distribution and Leakage Test] The microchemical device [D-4] obtained in Example 4 was evaluated by performing the same test as in Example 1, and the same result as in Example 1 was obtained.

[Example 5] [Production of microchemical device] In Example 1, 4-ethylene oxide-modified bisphenol A diacrylate (manufactured by Daiichi Kogyo Co., Ltd.) was used in place of composition (C) [C-1]. "BPE-4") and a microchemical device [D-5] in the same manner as in Example 1 except that a composition (C) consisting of 50 parts of N-cyclohexylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. ] Was produced.

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

[Example 6] [Preparation of microchemical device] In Example 1, instead of acrylic resin, polycarbonate (Mitsubishi Engineering Plastics Co., Ltd. “Iupilon S-2000”) was used as the material of the member (B). Is used in the same manner as in Example 1 except that the microchemical device [D
-6].

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

[Example 7] [Preparation of microchemical device] In Example 1, polysulfone ("Udel P-1700" manufactured by Amoco) was used as the material of member (B) instead of acrylic resin. Except for the above, a microchemical device [D-7] was produced in the same manner as in Example 1.

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

[Example 8] [Preparation of microchemical device] In Example 1, instead of acrylic resin, polyether sulfone (“Victrex 200P” manufactured by Sumitomo Chemical Co., Ltd.) was used as the material of the member (B). ) Was prepared in the same manner as in Example 1 except that the microchemical device [D-8] was used.

[Distribution and Leakage Test] The microchemical device [D-8] obtained in Example 8 was evaluated by performing the same test as in Example 1, and the same result as in Example 1 was obtained.

[Example 9] [Preparation of microchemical device] In Example 1, polystyrene ("Dick Styrene XC-" manufactured by Dainippon Ink and Chemicals, Inc.) was used as the material of the member (B) instead of acrylic resin. 520 "), except that a microchemical device [D-9] was produced in the same manner as in Example 1.

[Distribution and Leakage Test] The microchemical device [D-9] obtained in Example 9 was evaluated by performing the same tests as in Example 1, and the same results as in Example 1 were obtained.

[Example 10] [Preparation of microchemical device] As a material for the member (B), a polyarylate resin ("U-Polymer U-100" manufactured by Unitika Ltd.) was used in place of the acrylic resin. In the same manner as in Example 1, a microchemical device [D-10] was produced.

[Distribution and Leakage Test] The microchemical device [D-10] obtained in Example 10 was evaluated by performing the same test as in Example 1, and the same result as in Example 1 was obtained.

[Comparative Example 1] [Preparation of microchemical device] A microchemical device [D-C1] was prepared in the same manner as in Example 1 except that semi-curing was not performed.

[Distribution and Leakage Test] The microchemical device [D-C1] obtained in Comparative Example 1 was evaluated by performing the same test as in Example 1. As a result, the capillary was closed.

[Comparative Example 2] [Preparation of microchemical device] A microchemical device [D-C2] was prepared in the same manner as in Example 4, except that semi-curing was not performed.

[Distribution and Leakage Test] The microchemical device [D-C2] obtained in Comparative Example 2 was evaluated by performing the same test as in Example 1. As a result, the capillary was closed.

[Comparative Example 3] [Preparation of microchemical device]
Instead of the composition (C) [C-1], the composition (C) [C-
A 5% ethanol solution of the composition [C-1] was used as [C3], and the composition (C) was applied by spraying the composition (C) [C-C3] at 40 ° C. for 15 minutes. Removing ethanol by hot air drying,
A microchemical device [D-C3] was produced in the same manner as in Example 1, except that the coating film composed of the composition (C) was not semi-cured.

For confirmation, the composition (C) was separately prepared.
Member (B) on which the solvent-removed coating film of [C-C3] is formed
[B-C3] was irradiated with ultraviolet rays for 10 seconds to be completely cured, and the cross section thereof was observed with a scanning electron microscope. The coating thickness was measured to be about 1.4 μm.

[Distribution and Leakage Test] The microchemical device [D-C3] obtained in Comparative Example 3 was evaluated by performing the same test as in Example 1. As a result, no blockage of the capillary was observed. Penetrated between the member (A) [A-C3] and the member (B) [B-C3] and leaked to the outside. From this result, it can be seen that when the coating thickness is reduced as in Comparative Example 3 in order to prevent the capillary from being blocked, the adhesion is incomplete and leakage is likely to occur.

[0092]

According to the manufacturing method of the present invention, the member in which the groove is formed and the other member can be completely adhered to each other. A microchemical device that does not occur can be manufactured. Also,
According to the manufacturing method of the present invention, it is possible to manufacture a microchemical device that is not blocked by an adhesive even when a flow path is narrow. Further, the method for producing a microchemical device of the present invention has an advantage that, when an energy beam crosslinkable polymerizable compound is used as an adhesive, bonding can be performed in a very short time and productivity is high.

[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 groove

FIG. 2 is an overhead view of the microchemical device manufactured in the example.

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/06 C08L 33/06 67/00 67/00 69/00 69/00 81/06 81/06 101 / 16 101/00 F term (reference) 4F071 AA22B AA33B AA43B AA50B AA64B AC10A AC19A AF01A AF07A AF13A CA01 CB02 CB04 CC03 CC04 CD03 4J002 AA011 AA021 BG072 BG132 4J011 QA03 QA08 QA01 QA01 QA08 QA01 QA13 MA10 PA18 PA32

Claims (12)

[Claims] 1. A surface having a width of 1 to 1000 μm and a depth of 1 to 1
A method for manufacturing a microchemical device in which a member (A) having a groove of 000 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). The composition (C) containing the cross-linkable polymerizable compound in the member (B)
The composition (C) containing the cross-linkable polymerizable compound is then semi-cured to the extent that the composition (C) loses fluidity and unreacted polymerizable groups remain, and then the cross-linking polymerization of the member (B) is performed. The coating surface (b) made of the composition (C) containing the reactive compound is brought into contact with the grooved surface (a) of the member (A), and in that state, the composition (C) containing the crosslinkable polymerizable compound A method for producing a microchemical device, wherein the adhesive is adhered by completely curing the same. 2. The production of a microchemical device according to claim 1, wherein the crosslinkable polymerizable compound is an energy ray-curable crosslinkable polymerizable compound, and the semi-curing and curing of the composition (C) are performed by energy ray irradiation. Method. 3. The method for producing a microchemical device according to claim 2, wherein the crosslinkable polymerizable compound is a crosslinkable polymerizable compound having an acryloyl group or a maleimide group. 4. The member (A) and the member (B) are:
Styrene polymer, (meth) acrylic polymer, polycarbonate polymer, polysulfone polymer,
4. The method for producing a microchemical device according to claim 1, wherein the device is formed of a polymer selected from the group consisting of polyester-based polymers. 5. A surface having a width of 1 to 1000 μm and a depth of 1 to 1
A method for manufacturing a microchemical device in which a member (A) having a groove of 000 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). The surface (a) of the member (A) where the groove is formed has a depth of 1 /
A composition (C ′) containing a crosslinkable polymerizable compound is applied to a thickness of 10,000 to さ に, and a composition (C) containing a crosslinkable polymerizable compound is applied to a member (B). Composition (C) and composition (C ′) containing compound
Is coated with the composition (C ′) containing the semi-cured cross-linkable polymerizable compound of the member (A) in a state where the fluidity is lost and semi-cured to the extent that unreacted polymerizable groups remain. surface
(a ') and the coated surface (b') of the composition (C) containing the semi-cured crosslinked polymerizable compound of the member (B),
A method for producing a microchemical device, wherein the composition (C) and the composition (C ′) containing the crosslinkable polymerizable compound are completely cured in this state so as to be adhered. 6. The cross-linkable polymerizable compound is an energy-ray-curable cross-linkable polymerizable compound, and the semi-curing and curing of the composition (C) and the composition (C ′) are performed by energy beam irradiation. A manufacturing method of the microchemical device according to the above. 7. The method for producing a microchemical device according to claim 6, wherein the crosslinkable polymerizable compound is a crosslinkable polymerizable compound having an acryloyl group or a maleimide group. 8. The member (A) and the member (B) are each
Styrene polymer, (meth) acrylic polymer, polycarbonate polymer, polysulfone polymer,
8. The method for producing a microchemical device according to claim 5, wherein the device is formed of a polymer selected from the group consisting of polyester-based polymers. 9. A surface having a width of 1 to 1000 μm and a depth of 1 to 1
A method for manufacturing a microchemical device in which a member (A) having a groove of 000 μm and another member (B) are bonded to form a capillary-like flow path between the member (A) and the member (B). The composition (C) containing the cross-linkable polymerizable compound in the member (B)
The composition (C) containing the cross-linkable polymerizable compound is then semi-cured to the extent that the composition (C) loses fluidity and unreacted polymerizable groups remain, and then the cross-linking polymerization of the member (B) is performed. Coated surface (b ") composed of composition (C) containing a hydrophilic compound
And a composition (C ″) containing a crosslinkable polymerizable compound in a thickness of 1/10000 to 1/10 of the depth of the groove is applied to the grooved surface (a) of the member (A). The composition (C) containing the cross-linkable polymerizable compound and the composition (C ") containing the cross-linkable polymerizable compound in the state of contact with the coating surface (a")
A method for producing a microchemical device, comprising bonding by completely curing the device. 10. The crosslinkable polymerizable compound is an energy ray-curable crosslinkable polymerizable compound, and the semi-curing of the composition (C) and the curing of the composition (C) and the composition (C ″) are performed with energy. The method for manufacturing a microchemical device according to claim 9, wherein the method is performed by irradiation with a line. 11. The method for producing a microchemical device according to claim 10, wherein the crosslinkable polymerizable compound is a crosslinkable polymerizable compound having an acryloyl group or a maleimide group. 12. The member (A) and the member (B) are each formed of a polymer selected from the group consisting of a styrene-based polymer, a (meth) acryl-based polymer, a polycarbonate-based polymer, a polysulfone-based polymer, and a polyester-based polymer. The method for producing a microchemical device according to claim 9, 10 or 11.