JP2000288381A - Manufacture of microchemical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make both members attachable to each other in a completely tight condition to be bonded together without blocking up grooves by forming a coat film having the grooves of an energy curable compound on one of the members and making the other member attach tightly to the surface of the coat and at the same time, irradiating the compound with an energy beam to cure it. SOLUTION: Two members 1, 4 are bonded together interposing a composition 2 containing a crosslinking polymerizable energy radiation-curable compound to be held between the members 1, 4. In addition, a capillary space 5 is formed as a defect of the cured product between both members 1, 4 and thus a microchemical device is obtained. In this case, the composition 2 is applied to the member 1 in the thickness range of 5-1,000 μm, and the part other than the grooves 3 is irradiated with an energy beam to cure the composition 2. At the same time, the uncured composition 2 is removed to form the grooves 5-1,000 μm deep and 5-3,000 μm wide on the surface of the member 1, and further, the member 1 is irradiated with the energy beam in such a state that the member 4 is tightly attached to the member 1. Consequently, the composition 2 is cured and bonded with the members 1, 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a chemical, biochemical, and physical device in which a structure such as a microchannel, a reaction tank, an electrophoresis column, and a membrane separation mechanism is formed in a microchemical device, that is, a member. Micro-reaction devices such as chemical
Reactor), and methods for manufacturing microanalytical devices such as integrated DNA analysis devices, microelectrophoresis devices, and microchromatography devices. More specifically, a member having a groove on its surface and another member are tightly fixed or bonded and integrated. The present invention relates to a method for manufacturing a micro-reaction device or a micro-analysis device having a capillary-shaped flow path formed by the above-described method.

[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, 1997, Vol. 69, 2626
It has been known that a cover such as a glass plate is used in contact with the surface by screwing or the like for the purpose of preventing the liquid from evaporating during the 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 enters the groove and tends to close 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) an energy ray-curable energy ray in a semi-cured state is formed on a member by an energy ray patterning method. A coating film having a groove of the curable compound is formed, and (i) another member is brought into close contact with the coating film, and (ii) the energy ray-curable compound is (Iii) Alternatively, apply a very thin energy ray-curable compound, and apply another thin member that has been semi-cured by energy beam irradiation. By contacting and (c) irradiating energy rays in that state to completely cure these semi-cured or uncured energy ray-curable compounds, no gap is created between both members, and It found that can adhere without closing the Ku narrow groove, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides (I) a cured product of a composition (C) containing a crosslinkable polymerizable energy ray-curable compound between a member (A) and a member (B). Are adhered or adhered in a state of being sandwiched by the member, and the member (A) and the member (B)
(A) a composition (C) containing a cross-linkable polymerizable energy ray-curable compound in a member (A) having a thickness of 5 To 1000 μm,
(B) Irradiation of energy rays to a portion other than a portion of the coating film to form a groove having a width of 5 to 3000 μm, the composition (C) loses fluidity, and unreacted polymerizable groups remain. (C) By removing the uncured composition (C) in the unirradiated portion, a groove having a depth of 5 to 1000 μm and a width of 5 to 3000 μm is formed on the surface of the member (A). ) Contacting the member (B) with the groove forming surface of the member (A);
In this state, a method for manufacturing a microchemical device in which the composition (C) and the composition (C ′) are completely cured and irradiated by irradiating energy rays from outside the member (A) and / or the member (B). I will provide a.

In order to solve the above-mentioned problems, the present invention provides (II) a method as described in the above (I), wherein the member (B)
A composition comprising a cross-linkable polymerizable energy ray-curable compound in a thickness of 1/10000 to 1/10 of the applied thickness of the composition (C) to the member (A) on the surface to be brought into contact with the member (A). (C ') is applied, and thereafter a method for manufacturing a microchemical device is provided, in which the coating surface of the member (B) is brought into contact with the groove forming surface of the member (A).

Further, the present invention solves the above-mentioned problems. (III) In the method described in the above (I), the surface of the member (B) to be brought into contact with the member (A) has a composition for the member (A). A composition (C ″) containing a crosslinkable polymerizable energy ray-curable compound is applied to a thickness of 1/10000 to 1/2 of the applied thickness of the product (C), and the composition is irradiated with energy rays.
The composition (C ″) loses fluidity and is semi-cured to the extent that unreacted polymerizable groups remain, and then the coating surface of the member (B) is brought into contact with the groove-forming surface of the member (A). Provided is a method for manufacturing a microchemical device.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The member (A) used in the production method of the present invention does not transmit the composition (C) used in the present invention,
If it is possible to form a coating film on the surface,
There is no particular limitation.

The shape of the member (A) does not need to be particularly limited, and may be a shape according to the purpose of use, such as a sheet (including a film and a ribbon), a plate, a coating, a rod, a tube, and others. Although it may be a shape such as a molded product having a complicated shape, at least one surface is formed by applying a composition (C) containing an energy ray-curable compound thereon and easily patterning and irradiating the energy ray. It is preferably a flat shape, and particularly preferably a sheet shape or a plate shape. The member (A) may be formed on a support that is removed or not removed after the manufacture of the device. In the case of a sheet or plate, the thickness is preferably in the range of 0.1 to 10 mm, and 0.3 to 5 mm
Is particularly preferred.

A plurality of microchemical devices can be formed on one member (A).
These can be cut into a plurality of microchemical devices.

The material of the member (A) is not particularly limited,
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. It is preferable that the material of the member (A) can be adhered with an energy ray-curable compound. 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.

When the member (A) is formed on a support, a material that can be used as the member (A) can be used as a material for the support. The shape of the support is also arbitrary and may be the same as the shape that can be used as the member (A), and may be, for example, paper, cloth, nonwoven fabric, or a porous body.

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. 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) is, for example, a hydrophobizing agent (water repellent) such as silicone oil or fluorine-substituted hydrocarbon; a water-soluble polymer, a surfactant, or an inorganic agent such as silica gel. And a hydrophilizing agent such as a powder.

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.

When the member (A) is made of a material having low adhesiveness, for example, polyolefin, fluoropolymer, polyphenylene sulfide, polyetheretherketone, etc., the surface treatment of the bonding surface of the member (A) and the use of a primer can be used. It is preferable to improve the adhesiveness.

In the use of the microchemical device obtained by the manufacturing method of the present invention, the surface of the member (A) is used for the purpose of improving the adhesiveness and suppressing the adsorption of solutes such as proteins to the device surface. Is also preferably hydrophilized.

The member (B) adheres or adheres to a layer of a semi-cured product of the composition (C) formed on the surface of the member (A),
Between the member (A) and the member (B), it is necessary that a capillary-shaped flow path can be formed as a defective portion of the semi-cured product of the composition (C). For other points, for example, The shape, material, structure, surface condition and the like are the same as those of the member (A). The member (B) is the member (A)
Is not able to transmit the energy ray used in the present invention, it is necessary to transmit the energy ray used in the present invention.

The energy ray-curable compound used in the present invention may be any compound such as a radical polymerizable compound, an anionic polymerizable compound and a cationic polymerizable compound. Energy ray-curable compounds are not limited to those that polymerize in the absence of a polymerization initiator,
Those which polymerize with energy rays 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.

As the (meth) acrylic monomer which can be preferably used as the energy ray-curable compound, for example, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, 2,2 '
-Bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, neopentylglycol hydroxy (dipivalate) di (meth) acrylate, Bifunctional monomers such as cyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acroxy Trifunctional monomers such as ethyl) isocyanurate and caprolactone-modified tris (acroxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; dipe Data hexa (meth) acrylate such as 6-functional monomers, and the like.

Further, as the energy ray-curable compound,
Polymerizable oligomers (called prepolymers) 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 compounds can be used alone or in combination of two or more. It is also possible to mix a monofunctional monomer, for example, a monofunctional (meth) acrylic monomer, for the purpose of increasing the adhesiveness.

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-Tolylenedimaleimide, 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) containing the energy ray-curable compound contains the energy ray-curable compound as an essential component, and may be a mixture of plural kinds of energy ray-curable compounds. For example, in order to obtain a cured product of the energy ray-curable compound as a crosslinked polymer for the purpose of obtaining high strength and hardness, the composition (C) preferably contains a polyfunctional monomer and / or oligomer. However, it is also possible to mix monofunctional monomers and / or oligomers.

Examples of usable monofunctional (meth) acrylic monomers include, for example, methyl methacrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, and 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-phenoxy Propyl 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 hexahexahydrohydrogen Phthalate, fluorine-substituted alkyl (meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sodium sulfonic acid (meth) acrylate, 2-methylpropane sulfonic acid
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 M, and the like.

Examples of usable monofunctional maleimide monomers include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-dodecylmaleimide; and N-alkylmaleimides such as N-cyclohexylmaleimide. Alicyclic maleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide;
2,3-dichloro-N- (2,6-diethylphenyl)
Maleimide, 2,3-dichloro-N- (2-ethyl-6
N- (substituted or unsubstituted phenyl) maleimides such as -methylphenyl) maleimide; N-benzyl-2,3-dichloromaleimide, N- (4'-fluorophenyl)-
Maleimide having a halogen such as 2,3-dichloromaleimide; maleimide having a hydroxyl group such as hydroxyphenylmaleimide; maleimide having a carboxy group such as N- (4-carboxy-3-hydroxyphenyl) maleimide; and N-methoxyphenylmaleimide. Maleimide having an alkoxy group such as maleimide having an alkoxy group; 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, maleimide having a heterocyclic ring of N- (4-anilino-1-naphthyl) maleimide, and the like.

In the composition (C), other components can be mixed and used as required. Other components include, for example, a photopolymerization initiator, a solvent, a thickener, a modifier, and a colorant.

The photopolymerization initiator is not 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. 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 can be mixed and used in the composition (C), for example, in addition to a polyfunctional monomer such as a polyfunctional maleimide exemplified as a preferably usable energy ray-curable compound. A monofunctional monomer as exemplified as the monofunctional maleimide-based monomer may be used.

The amount of the photopolymerization initiator added to the composition (C) is preferably in the range of 0.01 to 20% by weight, and more preferably in the range of 0.5 to 10% by weight in the case of a non-polymerizable photopolymerization initiator. Is particularly preferred.

Examples of the thickener which can be added to the composition (C) include a linear polymer soluble in an energy ray-curable compound such as polysulfone and polyvinylpyrrolidone.

Examples of the modifier that can be used in the composition (C) include hydrophobic agents such as silicone oil and fluorine-substituted hydrocarbons; surfactants, hydrophilic polymers, and affinity powders such as silica gel. And a hydrophilizing agent.

As the colorant that can be contained in the composition (C), any dye, pigment, or fluorescent dye can be used.

In the first production method of the present invention, first, a composition (C) containing an energy ray-curable compound is applied to a member (A) so as to have a thickness of 5 to 1000 μm. Irradiating an energy ray to a portion other than a portion of the coating film to form a groove having a width of 5 to 3000 μm until the composition (C) loses fluidity and unreacted polymerizable groups remain. By semi-curing and removing the uncured composition (C) in the unirradiated portion, a groove having a depth of 5 to 1000 μm and a width of 5 to 3000 μm is formed on the surface of the member (A), and the member (B) is formed thereon. ), The composition (C) is completely cured by irradiating an energy beam from the outside of the member (A) and / or the member (B) in this state.

As a method for applying the energy ray-curable compound to the member (A), any coating method that can be applied on the member (A) can be used. For example, a spin coating method, a roller coating method, a flow coating method, or the like can be used. Examples include a drawing method, 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, and a gravure printing method. The application site is arbitrary, and may be the entire surface of the member (A) in contact with the member (B) or may be partial, but may be a site including the side surface of the capillary formed after bonding. is necessary. The coating may be applied to a surface of the member (A) other than the surface in contact with the member (B). The coating thickness is also arbitrary. In the case of partial application, it can be carried out by a method using an XY applicator or various printing methods.

The coating thickness of the composition (C) on the member (A) is 5 μm or more, preferably 10 μm or more.
More preferably, it is not less than μm. If it is thinner than this, it will be difficult to adhere, and leakage to the space tends to occur.
The coating thickness is 1000 μm or less and 300 μm
Or less, more preferably 100 μm or less. If the thickness is larger than this, the effect of the present invention is reduced. The coating thickness does not need to be uniform over the entire coating portion, but it is necessary that the member (B) be in a shape that allows close contact. For example, when the member (B) is a flexible sheet, the thickness may have a gentle slope, or the member (B)
May have irregularities corresponding thereto if it has a surface having irregularities. However, a plate-like member (B)
When is used, the thickness is preferably uniform.

A portion of the coating film of the composition (C) other than a portion to be formed as a groove is irradiated with energy rays, and the coating film at the irradiated portion is
It is semi-cured to the extent of the gel point or higher and to the extent that unreacted polymerizable reactive groups remain. The gel point is a reaction point at which cross-linking polymerization proceeds in a coating film and a network-like polymer in which an unreacted energy-ray-curable compound is occluded in the network is formed throughout the coating film. After passing the gel point, the coating loses fluidity. In the production method of the present invention, the member (A) is laminated with the member (B) in a state where the fluidity of the coating film of the energy ray-curable compound is lost. Thereby, the coating film of the composition (C) and the member (B) can be adhered. On the other hand, if the polymerization proceeds too much and the number of unreacted polymerizable reactive groups becomes too small, the coating film loses flexibility,
The adhesion with the member (B) tends to be incomplete. The degree of semi-curing can be controlled by the amount of irradiation of the energy beam, and the suitable degree can be determined by a simple experiment in the system used. In addition, although the coating film in a semi-cured state may show adhesiveness, in the present invention, it is not always necessary to show adhesiveness.

The energy ray used for the semi-curing is one that can cure the energy ray-curable compound. Examples of such energy rays include rays such as ultraviolet rays, visible rays, and infrared rays; ionizing radiation such as X-rays and gamma rays; and particle rays such as electron rays, ion beams, beta rays, and heavy ion rays. Ultraviolet rays and visible light are preferred from the viewpoint of curing speed, and ultraviolet rays are particularly preferred. For the purpose of speeding up the curing speed and performing semi-curing completely,
It is preferable that the irradiation of the energy beam is performed 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.

Photolithography can be used as a method of irradiating an energy beam except for a portion to be a groove. For example, a method of irradiating the coating film of the composition (C) with an energy ray by covering a portion to be a groove, or a method of scanning an energy ray beam such as a laser beam and irradiating only a necessary portion can be adopted. Energy beam irradiation is preferably performed from a direction perpendicular to the coating film of the composition (C), but is not necessarily limited thereto. Irradiation is preferably performed from the coating film surface, but may be performed through the member (A).

The width of the groove formed in the semi-cured coating film of the composition (C) is 5 μm or more, preferably 10 μm or more, and more preferably 3 μm or more.
More preferably, it is 0 μm or more. A microchemical device having a narrower groove becomes difficult to manufacture. The width of the groove is 3000 μm or less, preferably 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 substantially equal to the thickness of the applied composition (C). 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. The cross-sectional shape of the groove is also arbitrary such as a square, a trapezoid, and a semicircle. On the member (A), other structures such as a liquid 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 by being connected to the groove. . The width of the portion not irradiated with the energy beam does not always coincide with the width of the formed groove. The width of the groove may be wider or narrower than the width that cannot compete with irradiation, depending on the amount of irradiation of the energy beam, the concentration of the energy beam material, and the concentration of the composition (C). However, the relationship between the width of the portion not irradiated with the energy beam and the width of the formed groove can be known by a simple experiment in the system used.

Next, the uncured composition (C) in the unirradiated portion is removed. The removing method is optional, and for example, methods such as blowing off with compressed air or the like, absorption with a filter paper or the like, rinsing with a liquid flow of a non-solvent such as water, solvent washing, and volatilization can be used. Of these, washing with a non-solvent liquid stream and solvent washing are preferred.

After removing the uncured portion of the uncured composition (C), the member (B) is brought into contact with the surface of the semi-cured coating film of the member (A). The composition (C) is completely cured by irradiating energy rays from outside the member (B). The term “complete curing” as used herein refers to curing to such an extent that sufficient hardness is obtained, and it is not always necessary to completely eliminate the polymerizable group.

In the obtained microchemical device, a capillary-shaped space is formed between the defective portion of the cured product made of the composition (C) and the members (A) and (B). The space may communicate outside the device,
You do not need to contact them. In the latter case, it is possible to communicate with the outside of the device by separately drilling a hole with a drill or the like.

The obtained microchemical device can be used as it is when the members are firmly adhered to each other.
It is also possible to use it fixed by a clamp or other methods.

According to the second production method of the present invention, the surface of the member (B) to be brought into contact with the member (A) has a groove formed of a semi-cured coating film of the composition (C) on the member (A). 1/100 of depth
The composition (C ′) containing the energy ray-curable compound is applied to a thickness of 00 to 1/10, and then the composition of the member (B) is applied to the surface of the member (A) to which the composition (C) is applied. C ′) The application surfaces are brought into contact with each other, and the composition (C) and the composition (C ′) that have been semi-cured in that state are completely cured. That is, the second production method of the present invention is different from the first production method of the present invention in that a composition (C ′) containing a specific thickness of the energy ray-curable compound is applied to the member (B). .

The amount of the composition (C ') applied to the member (B) is determined by setting a gap between the member (A) and the member (B) if there is no coating of the composition (C) on the member (A). It may be as thin as possible or cause incomplete bonding, and its thickness is at least 1 / 10,000 of the depth of the groove. Of course, when the depth of the groove is very shallow, for example, about 5 μm, a value larger than 1/10000 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 a molecular gap, for example. That is, the thickness may be a value calculated from the amount of application. 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 is 1/10 of the groove depth
Or less, preferably 1/30 or less,
More preferably, it is 100 or less. If the thickness is larger than this, when bonding, the composition (C ′) fills the grooves and tends to close the capillaries formed between the members (A) and (B).

The composition (C ') used in the present invention is the same as the composition (C) used in the present invention. The energy ray-curable compound constituting the composition (C ′) can be selected from the group described as the energy ray-curable compound that can be 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 be bonded to each other, and the energy ray curability contained in each Preferably, the compound is copolymerizable. The composition (C ′) is preferably the same as the composition (C). Moreover, 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 is volatilized and removed before bonding to the member (A). Removal need not be complete.

Other parts, for example, members (A), members (B), compositions (C), methods of forming grooves,
Regarding the energy rays, the application method, the semi-curing and the curing method, and the like, the same is as in the case of 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.
Compared to 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.

The third production method according to the present invention is directed to a method for producing a member (B)
A composition (C) containing an energy ray-curable compound in a thickness of 1/10000 to 1/2 of the depth of the groove formed by the semi-cured coating film of the composition (C) on the member (A) )), And irradiating the coating film with an energy ray to semi-harden the coating film to such an extent that the coating film loses fluidity and the polymerizable group remains, and the coated surface and the member (A) Semi-cured composition of (C)
And the member (A) and / or
Alternatively, the composition (C) and the composition (C ″) are bonded by irradiating energy rays through the member (B) to completely cure the composition (C ″). )) Is different from the second production method of the present invention in that the coating film of the composition (C ″) containing the energy ray-curable compound applied to the member (A) is adhered to the member (A) in a semi-cured state.

The amount of the composition (C ″) applied to the member (B) is determined by setting a gap between the member (A) and the member (B) if there is no coating of the composition (C) on the member (A). The thickness may be as thin as possible or may be incomplete, and the thickness may be 1 / 10,000 or more of the depth of the groove, of course, when the depth of the groove is as shallow as about 5 μm, for example, 1 / 10,000. A larger value may be a practical lower limit, but the coating does not necessarily have to completely cover the surface of the member (A) other than the concave portions, and for example, even if there is a molecular gap. In other words, the above-mentioned thickness may be a value calculated from the coating amount, and if it is smaller than this, there is no difference in effect from the first manufacturing method of the present invention. / 2 or less, preferably 1/10 or less, and 1/3
More preferably, it is 0 or less. If the thickness is larger than this, when bonding, the composition (C ") tends to fill the groove and close the capillary formed between the member (A) and the member (B).

The composition (C ″) used in the present invention is the same as the composition (C) used in the present invention. The energy ray-curable compound constituting the composition (C ″) is the same as that of the present invention. Can be selected from the group described as the energy ray-curable compound that can be used in the first production method. 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, The compound is preferably copolymerizable, and the composition (C ″) is preferably the same as the composition (C). Moreover, 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 is volatilized and removed before bonding with the member (A), and the removal may not be complete. Regarding the member (A), the member (B), the composition (C), the groove forming method, the energy ray, the coating method, the semi-curing or curing method, and the like, Same as in the case.

The third manufacturing method of the present invention is the same as the first manufacturing method of the present invention.
Compared to 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.

[0060]

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)] As member (A) [A-1], 1
A flat plate having a thickness of 3 mm made of an acrylic resin of 0 cm × 10 cm (“Delpet 670N” manufactured by Asahi Kasei Corporation) was used.

[Preparation of composition (C)] 100 parts of 1,6-hexanediol diacrylate ("Kayarad HDDA" manufactured by Nippon Kayaku Co., Ltd.) and ultraviolet polymerization initiator 1-
2 parts of hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) were mixed, and
Composition (C) [C-1] was prepared.

[Preparation of Composition (C) Semi-cured Coating Film] The composition (C) was applied to the member (A) [A-1] using a 25 μm bar coater, and then the composition shown in FIG. Of the groove (3) is irradiated with ultraviolet rays of 10 mW / cm ² for 10 seconds in a nitrogen atmosphere using a light source unit for a Multilight 200 type exposure apparatus manufactured by Ushio Inc. Then, the uncured composition (C) is removed, and the member (A) [A-1] is cut into 2.5 cm × 2.5 cm to obtain a member (A) [ A-
1] A member having a semi-cured coating film of the composition (C) in which a groove (3) having a width of 25 μm and a depth of 26 μm was formed on the surface of (1) was prepared.

[Preparation of Member (B)] Member (A) [A-
[1] A plate of the same acrylic resin as used as [1] was cut, and a 2.5 cm × 2.5 cm × 3 mm plate-like member (B) [B]
-1].

[Adhesion] In a nitrogen gas atmosphere, the surface of the member (A) [A-1] (1) coated with the composition (C) is laminated and contacted with the member (B) (4), and clamped. At about 10
3k after 10 seconds from about 3 seconds after sandwiching with force of 0kN
Using two metal halide lamps, simultaneously irradiating 60 mw / cm ² of ultraviolet rays from both sides of the front and back sides, the semi-cured coating film (2) of the composition (C) is cured and bonded, and FIG. 1 and FIG. 2, the member (A) [A-
1] Openings (6, 6 ') to the outside of the device are defined as defective portions of the composition (C) cured product (3) sandwiched between (1) and the member (B) [B-1] (4). Chemical device having a capillary space (5) formed therein [D-
1] was obtained.

A microchemical device [D-1 '] was obtained in the same manner except that ultraviolet light was irradiated about 60 seconds after being clamped.

For confirmation, the coating was separately scraped off while the coating was semi-cured. The coating was gel-like and did not show fluidity.

[Distribution and Leakage Test] A distribution and leakage test was performed while the obtained microchemical device [D-1] was clamped. When water colored with malachite green (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced from the capillary opening (6) shown in FIG. 2, no blockage of the capillary-like space (5) was observed. Next, a test was performed in which the capillary-shaped space (5) was allowed to stand still for 1 hour in a state where a water pressure of 0.1 MPa was applied, and the member (A) [A-1] (1) was removed from the capillary-shaped space (5). ) And the member (B) [B-1] (4), and the member (A) [A-1] (1) and the member (B) [B-1] (4)
No peeling was 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 capillaries.

<Example 2> [Preparation of microchemical device]
4 Ethylene oxide-modified bisphenol A diacrylate (“BPE-4” manufactured by Daiichi Kogyo Co., Ltd.) 100
Part, and 2 parts of an ultraviolet polymerization initiator 1-hydroxycyclohexylphenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) and 1900 parts of ethanol to prepare a composition (C ′) [C′-2]. The composition (C ′) [C′-2] is sprayed on one entire surface of the member (B), and the resultant is dried with hot air at 40 ° C. for 15 minutes to remove ethanol. Example 1 except that the layer was brought into contact with the film-forming surface of (1) and laminated and adhered.
In the same manner as in the above, a microchemical device [D-2] was produced.

For confirmation, the composition (C) was separately prepared.
Member (B) on which the solvent-removed coating film of [C'-2] is formed
[B-2] was completely cured by irradiating it with ultraviolet light, was broken at the temperature of liquid nitrogen, and its cross section was observed with a scanning electron microscope. As a result, the average coating thickness was about 1.8 μm.

[Distribution and Leakage Test] The same test as in Example 1 was performed on the microchemical device [D-2] without being clamped by the clamp, and the same result as in Example 1 was obtained.

<Embodiment 3> [Production of microchemical device]
The member (B) [B-2] on which the solvent-removed coating film of the composition (C ') [C'-2] was formed was irradiated with ultraviolet rays for one second to be semi-cured, and then subjected to bonding. A microchemical device [D-3] was produced in the same manner as in Example 2 except for the above.

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

<Example 4> [Preparation of microchemical device] In Example 1, instead of the composition (C) [C-1], tetramethylene glycol (average molecular weight: 250) maleimide capriate (European Patent No. Microchemical device [D] was prepared in the same manner as in Example 1 except that composition (C) [C-5] was used as composition (C) [C-5].
-4].

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

<Example 5> [Preparation of microchemical device]
Instead of the composition (C) [C-1], tetramethylene glycol (average molecular weight: 250) maleimide capriate (synthesized by the method described in European Patent Publication No. 788482) was used as the composition (C) [C-5]. And a mixture of 5 parts of tetramethylene glycol (average molecular weight: 250) maleimide capryate and 95 parts of ethanol instead of the composition (C ') [C'-1]. Except having used as [C'-5], it carried out similarly to Example 2, and carried out the microchemical device [D-5].
Was prepared.

[Distribution and Leakage Test] The same test as in Example 1 was performed on the microchemical device [D-5], and the same result as in Example 1 was obtained.

<Example 6> [Preparation of microchemical device]
Instead of the composition (C) [C-1], tetramethylene glycol (average molecular weight: 250) maleimide capryate (synthesized by the method described in European Patent Publication No. 788482) was used as the composition (C) [C-6]. And a mixture of 5 parts of tetramethylene glycol (average molecular weight: 250) maleimide capriate and 95 parts of ethanol instead of the composition (C ′) [C′-1] was used as the composition (C ″). A microchemical device [D-6] was obtained in the same manner as in Example 3 except that the microchemical device [D-6] was used.
Was prepared.

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

[Example 7] [Preparation of microchemical device] In Example 1, polycarbonate ("Iupilon S-2000" manufactured by Mitsubishi Engineering-Plastics Corporation) was used instead of acrylic resin as the material of the member (B). Except that the microchemical device [D] was used in the same manner as in Example 1.
-7].

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

[Example 8] [Preparation of microchemical device] Except for using polysulfone ("Udel P-1700" manufactured by Amoco) in place of acrylic resin as the material of member (B) in Example 1. Produced a microchemical device [D-8] in the same manner as in Example 1.

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

[Example 9] [Preparation of microchemical device] Polyether sulfone ("Victrex 200" manufactured by Sumitomo Chemical Co., Ltd.) was used as the material of the member (B) instead of acrylic resin.
P "), except that a microchemical device [D-9] was produced in the same manner as in Example 1.

[Distribution and Leakage Test] The same test as in Example 1 was performed on the microchemical device [D-9], and the same result as in Example 1 was obtained.

[Example 10] [Preparation of microchemical device] Polystyrene (Dick Styrene XC-52 manufactured by Dainippon Ink and Chemicals, Inc.) was used instead of acrylic resin as the material of member (B).
0 ”), except that a microchemical device [D-10] was produced in the same manner as in Example 1.

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

[Example 11] [Preparation of microchemical device] As a material for the member (B), a polyarylate resin ("U-Polymer U-100" manufactured by Unitika Ltd.) was used instead of the acrylic resin. In the same manner as in Example 1, a microchemical device [D-11] was manufactured.

[Distribution and Leakage Test] The same test as in Example 1 was performed on the microchemical device [D-11], and the same result as in Example 1 was obtained.

Comparative Example 1 In this comparative example, the composition (C)
When the coating film was laminated with the member (B) in a completely cured state instead of a semi-cured state, the adhesion was incomplete.

[Production of microchemical device] Example 1
In the same manner as in Example 1, except that the coating film composed of the composition (C) was irradiated with photomasked ultraviolet rays for 10 seconds and the coating film was completely cured, the microchemical device [D-C3] was used. Was prepared.

[Distribution and Leakage Test] When a test similar to that of Example 1 was performed with the obtained device sandwiched between clamps, no blockage of the capillary was observed. -C3] and the member (B) [B-C3], and leaked to the outside. That is, it can be seen that when the composition (C) coating film is laminated in a completely cured state, the adhesion is incomplete and leakage tends to occur.

[0094]

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 and fixed or adhered to each other. The present invention can provide a microchemical device that does not cause liquid leakage. Further, according to the manufacturing method of the present invention, it is possible to provide a microchemical device which 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 bonding can be performed in a very short time and productivity is high.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a plan view of a microchemical device manufactured in an example as viewed from a direction perpendicular to the surface.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Member (A) 2 Cured product of composition (C) 3 Groove 4 Member (B) 5 Capillary 6 Capillary opening 6 ′ Capillary opening

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

[Explanation of symbols]

 Reference Signs List 1 member (A) 2 cured product of composition (C) 4 member (B) 6 opening of capillary

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C12N 15/09 G01N 30/60 D G01N 27/447 C12N 15/00 A 30/60 G01N 27/26 331E F Term (Reference) 4B024 AA11 AA19 CA01 HA11 4B029 AA07 AA23 BB20 FA15 4G075 AA23 AA30 AA70 CA32 CA33 4J011 QA03 QA06 QA12 QA13 QA15 QA17 QA19 QA22 QA32 QA34 QA39 QB04 QB14 QB14 SAB01 UA01 FA151 FA171 FA191 FA231 FA261 FA281 FA291 JB07 LA01 LA06 MA10 MA11 PA18 PA20 PA32 PA41

Claims (3)

[Claims] 1. A cured product of a composition (C) containing a crosslinkable polymerizable energy ray-curable compound is adhered or adhered to a member (A) and a member (B) while being sandwiched between the members. A method of manufacturing a microchemical device in which a capillary space is formed between a member (A) and a member (B) as a defective portion of the cured product, wherein (a) the member (A) is crosslinked. The composition (C) containing the polymerizable energy ray-curable compound has a thickness of 5 to 1000 μm.
(B) irradiating an energy ray to a portion other than a portion of the coating film to be formed into a groove having a width of 5 to 3000 μm to obtain a composition (C)
Is semi-cured to the extent that it loses fluidity and unreacted polymerizable groups remain. (C) Removing the uncured portion of the uncured composition (C) causes the surface of the member (A) to become Depth 5 to 1000μ
m, a groove having a width of 5 to 3000 μm is formed. (d) The member (B) is brought into contact with the groove forming surface of the member (A), and energy is supplied from the outside of the member (A) and / or the member (B) in that state. A method for producing a microchemical device, wherein the composition (C) and the composition (C ′) are completely cured and bonded by irradiating a line. 2. The method according to claim 1, wherein the surface of the member (B) to be brought into contact with the member (A) has a thickness of 1/1 of the thickness of the composition (C) applied to the member (A).
A composition (C ') containing a crosslinkable polymerizable energy ray-curable compound is applied to a thickness of 0000 to 1/10, and then the coated surface of the member (B) is coated on the groove-formed surface of the member (A). 2. The method for producing a microchemical device according to claim 1, wherein the device is brought into contact. 3. The coating of the composition (C) on the surface of the member (B) which is to be brought into contact with the member (A) is 1/1 of the coating thickness of the composition (C) on the member (A)
A composition (C ″) containing a crosslinkable polymerizable energy ray-curable compound is applied to a thickness of 0000 to １ ／ and irradiated with energy rays, whereby the composition (C ″) loses fluidity. ,
And semi-cured to the extent that unreacted polymerizable groups remain,
2. The method for manufacturing a microchemical device according to claim 1, wherein the application surface of the member (B) is brought into contact with the groove forming surface of the member (A).