JP2002086399A - Micro-device having lamination structure and manufacturing method for it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a micro-device having a capillary cavity, particularly to the manufacturing method for a micro-device having complicated passages formed in three-dimensions, and to provide a micro- device in which plural resin layers are stacked and the capillary cavities are communicated with each other through the respective layers having multi- function such as a passage, a reaction vessel, a diaphragm type valve and a valve structure. SOLUTION: According to this manufacturing method for the micro-device having a cavity inside, a coat having a defective part is formed of energy line curable composition on a support, the coat is stacked on another member to remove the support, and the coat is cured by again applying active energy line to be bonded to the member. The micro-device has a lamination structure where one or more cured resin coats having the defective part are stacked on the member having the defective part penetrating the member or recessed in the surface, and at least two or more defective parts in the member are connected to form a cavity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a microfluidic device having a microfluidic channel therein, a microreaction device (microreactor) used in a wide range of fields such as chemistry, biochemistry or physical chemistry, Useful as an integrated DNA analysis device, microelectrophoresis device, microchromatography device, has a microcavity inside, such as a channel, a reaction tank, an electrophoresis column, a membrane separation mechanism, and a sensor in a member The present invention relates to a method for manufacturing a microdevice such as a microanalytical device having a structure, and a microdevice obtained by the method.

More specifically, the present invention has a laminated structure having an active energy ray-curable resin layer, wherein the active energy ray-curable resin layer has a resin defect in the layer, and a plurality of resin layers are formed. A micro device which is laminated, has a thin capillary channel which penetrates through each layer and communicates with each other, and further has a space to be a reaction layer, a diaphragm valve and a valve structure.

Further, the microdevice of the present invention is an active energy ray-curable resin containing a hydrophobic active energy ray-polymerizable compound (a) and an amphiphilic polymerizable compound (b) copolymerizable therewith. It is a micro device consisting of layers and hardly adsorbing biological components.

Further, according to the present invention, an active energy ray-curable resin layer having a resin defective portion formed by patterning exposure and development is prepared by forming an active energy ray-curable resin layer on a coated support. And laminated with other members,
The present invention relates to a method for manufacturing a micro device, in which an active energy ray is again applied to adhere and cure with another member, and the coated support is removed before, after, or during another active energy ray irradiation.

[0005]

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 a polymer by an etching method to form a liquid channel or a gel channel for separation (for example, M. McCormick et al., "Analytical Chemistry", p. 2626, vol. 69, 1
997), it is known that a cover such as a glass plate is fixed by screwing, fusing, bonding or the like for the purpose of preventing evaporation of liquid during operation.

However, in the case of close contact by screwing or the like, the liquid tends to leak between the laminated base materials or between the base material and the cover, and fusion and bonding require a long time. It was extremely poor productivity. Further, it is difficult to form a micro device having a multilayer structure in which a flow path and other voids are formed in three or more continuous layers with such a material and a manufacturing method. Fabricating stacked microdevices has been quite difficult.

[0007] "Science"
In a magazine (Vol. 288, p. 113, 2000), a member made of silicon rubber having a groove on the surface is formed by a casting method.
A method of forming a three-dimensionally intersecting capillary flow path by sandwiching and bonding a silicone rubber sheet between two members is described.

However, these two flow paths are independent flow paths, and it has not been possible to form a thin capillary flow path penetrating through each layer and communicating with each other. In particular, it is impossible to industrially manufacture a multi-layered micro device composed of thin layers that cannot be self-sustained with a flexible material, and to produce a micro device capable of performing complicated reaction and analysis processes. I couldn't do that. Further, silicon rubber has drawbacks in that its application is limited due to the large amount of adsorption of biochemical substances, and that it takes a long time to cure the silicone rubber, resulting in extremely low productivity.

On the other hand, a microdevice formed of an active energy ray-curable resin is brought into contact with another member in a state where the active energy ray-curable resin is semi-cured, and is irradiated again with active energy rays in that state. By using a method of completely curing the adhesive, it is possible to adhere without using an adhesive, and it is possible to produce the product with extremely high productivity.

However, even with this method, it is industrially difficult to laminate a large number of films each having a defective portion so as not to be self-supporting, while aligning the positions of the minute defective portions. In particular, when the defective portion of the resin layer has a long linear shape, a curved shape, a large number of linear shapes, and the like, it becomes more difficult to handle the film, and the capillary flows penetrating through such a layer and communicating with each other. There was no known way to form a road. Further, there has been no known microdevice in which three or more layers of a film made of an active energy ray-curable resin having a defective portion and each of which is too thin to be self-supporting are laminated with the positions of the minute defective portions aligned.

[0011]

An object of the present invention is to provide a method for manufacturing a micro device having a fine capillary cavity formed as a defect in a very thin layer which is easily broken, and particularly to a three-dimensional method. Providing a highly productive manufacturing method of a micro device having a complicated flow path formed in, and a plurality of resin layers are laminated, and fine capillary cavities penetrate each layer and communicate with each other, An object of the present invention is to provide a multifunctional microdevice having a three-dimensionally crossing fine capillary channel, a space to be a reaction tank, a diaphragm valve, a valve structure, and the like.

[0012]

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 semi-cured coating having a defective portion, comprising an active energy ray-curable composition, is formed on a coated support. Forming a film, removing the support by laminating the semi-cured coating film to another member, before or after removing the support, or re-irradiating active energy rays before and after removing the support The present inventors have found that a microdevice having a cavity formed therein, particularly a microdevice in which a plurality of layers are continuously laminated can be easily manufactured by curing the coating film and bonding the coating film to the other member. Was completed.

That is, the present invention comprises at least one resin layer (X) having a defective portion, comprising the following steps, wherein the resin layer is laminated with another member or another resin layer (X). And a method for manufacturing a micro device having a laminated structure, in which a defective portion forms a cavity.

(I) A step of forming an uncured coating film by applying an active energy ray-curable composition (x) containing an active energy ray-polymerizable compound (a) to a coated support. , (I
i) Irradiation of active energy rays to the uncured coating film other than the portion to be formed as a defective portion to make the uncured coating film of the irradiated portion non-flowable or hardly flowable and an unreacted active energy ray-polymerizable functional group Is semi-cured to the extent that it remains, a step (ii) of forming a semi-cured coating film,

(Iii) removing the uncured composition (x) in the non-irradiated portion from the semi-cured coating film to obtain a semi-cured coating film having a defective portion of the coating film (iii), (iv) a defective portion Step (iv) of forming a resin layer (X) by laminating a semi-cured coating film having another on the other member (J),

(V) Step of transferring the resin layer (X) to the member (J) by removing the coated support from the resin layer (X)
(v), and (vi) after the step (iv) and before the step (v), or after the step (v), or before and after the step (v), the semi-cured resin layer (X ) Is irradiated with an active energy ray to further cure the resin layer (X), and the resin layer (X) is bonded to the member (J) (vi).

According to the present invention, the removal of the coated support in the step (v) is the dissolution of the coated support, or the step (vi) is a step
Before (v), the method of manufacturing a microdevice in which the removal of the coated support in step (v) is peeling, and steps (i) and (i)
i), (iii), (iv), and (v), or after performing step (i),
After performing (ii), (iii), (iv), (v), and (vi), or after performing steps (i), (ii), (iii), (iv), (vi), and (v) ) In this order, and then the member (J) on which the resin layer (x) is laminated is subjected to the step (i).
Using the member (J) in (v), by repeating the steps (i) to (v) or the steps (i) to (vi), a plurality of resin layers (X) are laminated, a method for manufacturing a micro device. I will provide a.

According to the present invention, a plurality of resin layers (X) are laminated so that at least a part of their defective portions are overlapped with each other to form a cavity in which the defective portions of the plurality of resin layers (X) are connected in a laminate. To provide a method for manufacturing a micro device for forming the same. The present invention provides a member (J) having a defective portion penetrating the member, or a member having a concave defect portion on the surface, or a member having a defective portion penetrating the member and a concave defect portion on the surface. The member (J) and the resin layer (X) such that at least a part of the defective portion of the member (J) and the defective portion of the resin layer (X) partially overlap.
And a method for manufacturing a microdevice, wherein a cavity in which a defective portion of the member (J) and a defective portion of the resin layer (X) are connected to each other is formed in the laminate by laminating them.

The present invention relates to the above-mentioned (1) between step (i) and step (ii), between step (ii) and step (iii), and between step (iii) and step (i).
During one or more steps selected from v) and (iv), a part of the resin layer (X) is irradiated with an active energy ray to perform a step (iv).
In the resin layer (X), a portion that is not adhered even if it is in contact with another member or the resin layer is formed by performing partial curing to cure the irradiated portion to such an extent that the irradiated portion does not adhere to another member. A method for manufacturing a microdevice.

In the present invention, the irradiation of the active energy ray in the above step (ii) is performed in a shape for forming a valve, and the resin layer is formed.
Provided is a method for manufacturing a microdevice, in which a structure serving as a valve is provided in a part of (X), and a part to be partially cured is a part serving as a valve in the resin layer (X).

According to the present invention, the above-mentioned active energy ray-curable composition (x) comprises a hydrophobic active energy ray-polymerizable compound (a) wherein the homopolymer exhibits a contact angle with water of 60 ° or more,
Provided is a method for producing a microdevice, which contains an amphiphilic polymerizable compound (b) copolymerizable therewith.

The present invention further provides a member having a defective portion penetrating the member or a member having a concave defective portion on the surface.
Or a member (J ′)｝ selected from a member having a defect portion penetrating the member and a concave defect portion on the surface, and a defect portion in a part of the layer, and the minimum width of the defect portion is 1 to 1000 μm. Is,
One or more layers of an active energy ray-curable resin layer (X ′);
部 材 A member having a defective portion penetrating the member, a member having a concave defect portion on the surface, or a member selected from a member having a defective portion penetrating the member and a concave defect portion on the surface (K ′)｝
Are provided, and at least two or more defective portions in the member are connected to form a cavity.

The present invention provides the above-mentioned member (J '), resin layer (X'),
And one or more members selected from the member (K ′) and a microdevice having one or more linear cavities provided in a direction parallel to the stacking surface of the members, or a part of the cavities is a fluid flow. Provided is a microdevice in which a plurality of flow paths or branched flow paths formed in different resin layers (X ′) are three-dimensionally crossing each other across the resin layer (X ′).

The present invention provides the above-mentioned member (J '), resin layer (X'),
And a microdevice having a portion which is in contact with, but not adhered to, another member laminated adjacent to a part of one or more members selected from the member (K ′).

According to the present invention, at least a part of one layer of the resin layer (X ') is provided with a structure serving as a valve by making a part of a peripheral part a defective part, and is laminated adjacently. And a part in contact with, but not adhered to, another member is a valve.

According to the present invention, at least one member selected from a member (J ′), a resin layer (X ′), and a member (K ′) includes a member whose one side is a diaphragm and a member whose other side is a defect. It is directly laminated with other members having, the cavity is formed by laminating the defective portion, and the other member laminated on the back surface of the member that becomes the diaphragm has an inflow port or an outflow port into the cavity, or both. Each hole-shaped defective portion, at least one of the inflow port and the outflow port is formed on the facing surface of the diaphragm with the member interposed therebetween, and the periphery thereof is not in contact with the diaphragm,
A micro device capable of closing a channel by deforming a diaphragm to contact at least one of the inlet and the outlet.

The present invention relates to a microdevice containing an amphiphilic active energy ray-polymerizable compound copolymerizable with an active energy ray-polymerizable compound, a member having a defective portion penetrating a member, or a concave surface on the surface. A member having a defective part, or a member selected from a defective part penetrating the member and a member having a concave defective part on the surface (J ′)｝, and having a defective part in a part of the layer; One or more layers of the active energy ray-curable resin layer (X ′) having a minimum width of 1 to 1000 μm, and a member (K ″) that forms a diaphragm without a defective portion are laminated, and the member (K ′ ') Has a portion that is in contact with but not adhered to another member that is adjacently laminated, and that portion is a diaphragm portion, at least in the member (J') and the resin layer (X '). Two or more missing parts are connected to form a cavity,
Provided are a micro device having a laminated structure, and a micro device manufactured by the above-described manufacturing method of the present invention.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The manufacturing method of the present invention relates to a method for forming a resin layer having a resin defect [hereinafter referred to as a “resin layer”
(X) ") alone, or two or more resin layers (X) having flow paths of the same or different shapes are laminated and bonded to another member, and the resin layer (X) is formed of another member or Other resin layer (X)
And a method for manufacturing a microdevice in which the defective portion forms a cavity by being laminated.

The coated support used in the production method of the present invention is coated with an active energy ray-curable composition (x) (hereinafter sometimes simply referred to as “composition (x)”). It can be processed and can be removed after the composition (x) is cured. In the present invention,
The coating shall include casting, and the coating shall include casting.

The shape of the coating support does not need to be particularly limited, and may take a shape according to the purpose of use. For example, sheet (including film, ribbon, and belt), plate,
Roll-shaped (coating, semi-curing, laminating, peeling, etc. are performed during one round of the roll, using a large roll as a coating support), and moldings and molds of other complicated shapes However, from the viewpoint that the active energy ray-curable composition (x) is easily applied thereon, and the active energy ray is easily irradiated, the surface to be adhered has a flat shape or a quadratic curved shape. It is particularly preferable that the sheet is a flexible sheet. Further, from the viewpoint of productivity, it is also preferable to be in the form of a roll.

The coated support may be printed with squares, drawings, alignment symbols and the like. The material of the coating support is
There is no particular limitation as long as the above conditions are satisfied. Examples thereof include polymer; glass; crystal such as quartz; ceramic; semiconductor such as silicon; metal; paper, nonwoven fabric, and woven fabric. Among them, polymers and metals are particularly preferred.

The polymer used for the coating support may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. Is also good.
From the viewpoint of productivity, the polymer used for the coating support is preferably a thermoplastic polymer or an active energy ray-curable polymer.

When the removal of the coating support is due to peeling by mechanical force, it is difficult to dissolve in many types of active energy ray-curable compositions (x), and Polyolefin polymers, chlorine-containing polymers, fluorine-containing polymers, polythioether-based polymers, polyetherketone-based polymers, and polyester-based polymers are preferably used as those easily peelable.

When the removal of the coating support is due to dissolution, for example, a water-soluble resin such as polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, acrylic acid copolymer; a polyether group such as polyethylene glycol group; A lower alcohol-soluble resin containing a hydroxyl group or the like; an alkali-soluble resin such as a carboxyl group, a phosphoric acid group or a sulfone group-containing resin; and an acid-soluble resin such as an amino group or a quaternary ammonium salt-containing resin are preferably used.

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

The coated support, whether a polymer or other material, may be surface-treated. The surface treatment is intended to prevent dissolution by the composition (x), the purpose of facilitating the release of the composition (x) from the cured product,
A composition for improving the wettability of the composition (x), a composition for preventing the penetration of the composition (x), and the like can be used.

The surface treatment method of the coated support is optional.
For example, corona treatment, plasma treatment, flame treatment, acid or alkali treatment, sulfonation treatment, fluorination treatment, primer treatment with silane coupling agent, etc., surface graft polymerization, application of surfactant or release agent, rubbing and Physical treatments such as sandblasting may be used.

When the active energy ray-curable composition (x) is thinly coated thereon, the coated support is wettable by the composition (x) or has a low repelling force. It is preferred that That is, the contact angle with the composition (x) to be used is preferably 90 ° or less, more preferably 45 ° or less, further preferably 25 ° or less, and most preferably 0 °. preferable.

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

However, it is necessary to adjust the degree of the treatment so that the cured active energy ray-curable composition (x) does not adhere so strongly that the cured active energy ray-curable composition (x) cannot be peeled off. As a surface treatment method for improving wettability, for example, corona discharge treatment, plasma treatment, acid or alkali treatment, sulfonation treatment, primer treatment,
The application of a surfactant is preferred.

On the other hand, when the coated support is formed of a material having good adhesion and from which the cured product of the active energy ray-curable composition (x) is difficult to peel, a fluorine treatment, a fluorine-based or silicon Surface treatment such as application of a system release agent, introduction of a hydrophilic group or a hydrophobic group by a surface grafting method, and the like are preferable. Also,
When the coating support is a porous body such as paper, nonwoven fabric, or woven fabric, the surface of the coating should be made non-porous by treatment with a fluorine compound or coating to prevent intrusion of the composition (x). Is preferred. Control of wettability can also be performed by selecting a modifier to be blended with the coated support, in addition to the surface treatment.

Examples of the modifying agent that can be contained in the coating support include a hydrophobizing agent (water repellent) such as silicone oil and fluorine-substituted hydrocarbon; a water-soluble polymer, a surfactant, and silica gel. And a plasticizer such as dioctyl phthalate. Examples of the colorant that can be contained in the coating support include arbitrary dyes and pigments, fluorescent dyes and pigments, and ultraviolet absorbers. Examples of the reinforcing material that can be contained in the coated support include inorganic powders such as clay, and organic and inorganic fibers and woven fabrics.

The active energy ray-polymerizable compound (a) (hereinafter may be simply referred to as “compound (a)”) used in the present invention is a radical compound as long as it is polymerized and cured by an active energy ray. Any polymerizable, anionic or cationic polymerizable polymer may be used. Compound (a) is
Not only those that polymerize in the absence of a polymerization initiator but also those that polymerize by active energy rays only in the presence of a polymerization initiator can be used.

The compound (a) is preferably an addition polymerizable compound because of its high polymerization rate, and is preferably a compound having a polymerizable carbon-carbon double bond as an active energy ray polymerizable functional group. Preferred are highly reactive (meth) acrylic compounds and vinyl ethers, and maleimide compounds which cure even in the absence of a photopolymerization initiator.

Further, the compound (a) is preferably a compound which polymerizes to form a crosslinked polymer in view of high shape retention in a semi-cured state and high strength after curing. Therefore, a compound having two or more polymerizable carbon-carbon double bonds in one molecule (hereinafter, “a compound having two or more polymerizable carbon-carbon double bonds in one molecule” is referred to as “multiple”. Is sometimes referred to as “functional”).

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

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

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

Examples of the maleimide type compound (a) include 4,4'-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 2-bismaleimide ethane,
1,6-bismaleimidehexane, triethyleneglycolbismaleimide, 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.

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

The monofunctional (meth) acrylic monomer includes, 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-acryloyloxypropyl hexahexahydrohydrogen phthalate, fluorine-substituted alkyl (meth) acrylate,

Chlorine-substituted alkyl (meth) acrylate,
Sodium sulfonic acid (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, phosphoric ester group-containing (meth) acrylate, sulfonic 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 can be mentioned.

Examples of the monofunctional maleimide monomer include N-methylmaleimide, N-ethylmaleimide,
N-alkylmaleimides such as N-butylmaleimide and N-dodecylmaleimide; N-alicyclic maleimides such as N-cyclohexylmaleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-di Alkoxyphenylmaleimide, N- (2-chlorophenyl) maleimide,

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

Maleimide having an alkoxyl 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 A maleimide having a heterocyclic ring such as N- (dimethylamino-4-methyl-3-coumarinyl) maleimide and N- (4-anilino-1-naphthyl) maleimide;

When the amphiphilic compound (b) described below is added to the composition (x), it is preferable to use the hydrophobic compound (a) as the compound (a). The hydrophobic compound (a) refers to a compound whose homopolymer exhibits a contact angle with water of 60 ° or more. As the hydrophobic compound (a), any of the compounds exemplified above as the compound (a) can be selected and used, but most of the exemplified compounds are the hydrophobic compounds (a).

The composition (x) is a resin which becomes a cured resin upon irradiation with active energy rays.
(a) is contained. The composition (x) may contain the compound (a) alone, or may be a mixture of plural kinds of the compounds (a). Other components can be added to the composition (x) as needed. Other components that can be added to the composition (x) include a compound copolymerizable with the compound (a), an active energy ray polymerization initiator, a polymerization retarder, a polymerization inhibitor, a thickener, a modifier, and coloring. Agents and solvents.

The compound that can be added to the composition (x) and is copolymerizable with the compound (a) may be an amphiphilic compound, a hydrophilic compound, a hydrophobic compound, or the like. The hydrophilic compound copolymerizable with the compound (a), which can be added to the composition (x), has a hydrophilic group in the molecule and gives a hydrophilic polymer.

Such compounds include, for example, vinylpyrrolidone; N-substituted or unsubstituted "acrylamide;
Acrylic acid; polyethylene glycol group-containing (meth) acrylate; hydroxyl group-containing (meth) acrylate; amino group-containing (meth) acrylate; carboxyl group-containing (meth) acrylate; phosphoric acid group-containing (meth) acrylate;
Sulfone group-containing (meth) acrylates and the like can be mentioned.

The hydrophobic compound copolymerizable with the compound (a), which can be added to the composition (x), has a hydrophobic group in the molecule and gives a hydrophobic polymer. Examples of such a compound include an alkyl (meth) acrylate; a fluorine-containing (meth) acrylate; a (alkyl-substituted) siloxane group-containing (meth) acrylate, and the like.

An amphiphilic compound copolymerizable with the compound (a) [hereinafter referred to as “amphiphilic compound (b)” or simply “compound ( b)]] is preferably a compound having one or more polymerizable carbon-carbon unsaturated bonds in one molecule. The amphiphilic compound (b) does not need to be a homopolymer of a crosslinked polymer, but may be a compound of a crosslinked polymer.

The amphiphilic compound (b) is uniformly compatible with the hydrophobic compound (a). "Compatible" in this case means that there is no macroscopic phase separation,
A state where micelles are formed and dispersed stably is also included.

The amphiphilic compound referred to in the present invention refers to a compound having a hydrophilic group and a hydrophobic group in a molecule and being compatible with both water and a hydrophobic solvent. Even in this case,
Compatibility means that no macroscopic phase separation occurs, and also includes a state where micelles are formed and dispersed stably. The amphiphilic compound (b) has a solubility in water of 0.5% by weight or more at 0 ° C. and a solubility in cyclohexane / toluene = 5: 1 (weight ratio) mixed solvent at 25 ° C. of 2%.
It is preferably at least 5% by weight.

The solubility mentioned here, for example, the solubility is 0.
The content of 5% by weight or more means that at least 0.5% by weight of the compound is soluble, and although 0.5% by weight of the compound is not soluble in the solvent, only a small amount of the compound is contained in the compound. Does not include those in which the solvent is soluble. Solubility in water, or cyclohexane: toluene =
When a compound having at least one of solubility in a 5: 1 (weight ratio) mixed solvent lower than these values is used, it is difficult to satisfy both high surface hydrophilicity and high water resistance.

When the amphiphilic compound (b) has a nonionic hydrophilic group, particularly a polyether-based hydrophilic group,
The balance between hydrophilicity and hydrophobicity is preferably in the range of 10 to 16 as HLB (HLB) value of griffin, more preferably in the range of 11 to 15. Outside this range, it is difficult to obtain a molded article having high hydrophilicity and excellent water resistance, or the combination and mixing ratio of the compounds for obtaining the molded article are extremely limited, and the performance of the molded article is poor. It tends to be stable.

The hydrophilic group possessed by the amphiphilic compound (b) is optional, for example, a cationic group such as an amino group, a quaternary ammonium group or a phosphonium group; an anion such as a sulfone group, a phosphate group or a carbonyl group. Groups; polyether groups such as hydroxyl groups and polyethylene glycol groups; nonionic groups such as amide groups; and zwitterionic groups such as amino acid groups. As the hydrophilic group, preferred are polyether groups,
Particularly preferred are compounds having a polyethylene glycol chain having 6 to 20 repetitions.

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

The amphiphilic compound (b) has a polyethylene glycol chain having a repeating number of 6 to 20 as a hydrophilic group,
Further, it is preferable that the compound has an alkyl group or an alkylene group having 6 to 20 carbon atoms as a hydrophobic group.
More preferably used amphiphilic compound (b),
The compound represented by the general formula (1) can be mentioned.

Formula (1) CH₂= CR¹COO (R²O)_n-Φ-R³ (Where R¹Is hydrogen, halogen atom or lower alkyl group
And R²Represents an alkylene group having 1 to 3 carbon atoms.
N is an integer of 6 to 20, φ is a phenylene group, R ³Is charcoal
Represents an alkyl group having a prime number of 6 to 20)

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

The relationship between the number n and the number of carbon atoms in R ³ is preferably in the range of 10 to 16 as HLB value of griffin, and particularly preferably in the range of 11 to 15. Among these amphiphilic compounds (b), nonylphenoxypolyethylene glycol (n = 8)
To 17) (meth) acrylate and nonylphenoxypolypropylene glycol (n = 8 to 17) (meth) acrylate are particularly preferred.

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

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, benzoin methyl ether,
Benzoin ethers such as 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.

When the photopolymerization initiator is mixed and used in the composition (x), the amount of the nonpolymerizable photopolymerization initiator is 0.0
The range is preferably from 0.5 to 20% by weight, and from 0.1 to 5% by weight.
Is particularly preferred. Photopolymerization initiator is polymerizable,
For example, a polyfunctional or monofunctional maleimide monomer exemplified as the active energy ray polymerizable compound (a) may be used. The amount used in this case is not limited to the above.

The polymerization retarder that can be added to the composition (x) includes, for example, an active energy ray polymerizable compound.
When (a) is an acryloyl group-containing compound, styrene, α-methylstyrene, α-phenylstyrene, p-
Octylstyrene, p- (4-pentylcyclohexyl) styrene, p-phenylstyrene, p- (p-ethoxyphenyl) phenylstyrene, 2,4-diphenyl-4-methyl-1-pentene, 4,4'-divinylbiphenyl And vinyl monomers having a lower polymerization rate than the active energy ray-polymerizable compound (a) used, such as 2-vinylnaphthalene.

Examples of the polymerization inhibitor that can be added to the composition (x) include, for example, an active energy ray polymerizable compound.
When (a) is a polymerizable carbon-carbon double bond-containing compound, hydroquinone derivatives such as hydroquinone and methoxyhydroquinone; butylhydroxytoluene, ter
Hindant phenols such as t-butylphenol and dioctylphenol are exemplified.

When a light beam is used as the active energy ray, it is preferable to use a polymerization retarder and / or a polymerization inhibitor together with a photopolymerization initiator in order to improve the patterning accuracy. Examples of the thickener that can be added to the composition (x) include a chain polymer such as polystyrene.

The modifier which can be added to the composition (x) includes, for example, hydrophobic compounds such as silicone oil and fluorine-substituted hydrocarbon which function as a water repellent and a release agent;
Water-soluble polymers such as polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol that function as hydrophilizing agents and adsorption inhibitors; nonionic, anionic, cationic, and the like that function as wetting improvers, release agents, and adsorption inhibitors Surfactants. Examples of the colorant that can be mixed and used in the composition (x) as needed include arbitrary dyes and pigments, fluorescent dyes, and ultraviolet absorbers.

The solvent that can be added to the composition (x) is arbitrary as long as it dissolves each component of the composition (x) to form a uniform solution. Is preferred. When the viscosity of the composition (x) is high, particularly when the composition (x) is applied thinly, it is preferable to add a solvent to the composition (x). The solvent is volatilized and removed after coating or in any subsequent step.

In the production method of the present invention, the composition (x) is applied on a coating support to form an uncured coating film. This step is referred to as “step (i)”. The thickness of the coating is arbitrary,
It is preferably at least 5 μm, more preferably at least 5 μm, even more preferably at least 10 μm. If it is thinner than this, manufacturing becomes difficult.

The thickness of the coating film is preferably 1000 μm or less, more preferably 400 μm or less, and 2 μm or less.
More preferably, it is not more than 00 μm. If the thickness is larger than this, the effect of the present invention is reduced. Although the thickness of the coating film slightly changes due to shrinkage at the time of curing, etc., it generally matches the thickness of the layer to be the resin layer (X). The coating site is arbitrary, and may be the entire surface or the partial surface of the coating support. Conversely, the coating may be applied to portions other than the portion to be laminated with the member (J) described later.

As a method for applying the composition (x) to the coated support, any coating method that can be applied on the coated support can be used. For example, a spin coating method, a roller coating method, and the like can be used. Method, casting method, dipping method, spray method, bar coater method, XY applicator method, screen printing method, letterpress printing method, gravure printing method, extrusion from a nozzle and casting. When the composition (x) is applied particularly thinly, a method in which a solvent is added to the composition (x) and then the solvent is volatilized may be adopted.

The uncured coating material of the composition (x) is irradiated with active energy rays except for a portion to be a defective portion, so that the irradiated portion of the composition (x) is semi-cured. The active energy ray non-irradiated part of (x) is left as an uncured part (hereinafter,
This operation is called “patterning exposure” or simply “exposure”
In some cases). This step is referred to as a step (ii) of forming a semi-cured coating film. The irradiation angle is arbitrary and does not necessarily have to be perpendicular to the coating film surface.

The term “semi-cured” as used herein means that the composition (x) becomes non-flowable or hardly flowable and is an unreacted active energy ray-polymerizable functional group which can be polymerized by further irradiation with active energy rays. It refers to curing to the extent that the groups remain. The method of semi-curing the composition (x) includes irradiating an active energy ray at a dose insufficient for completely curing the composition (x), or irradiating at a temperature lower than the re-irradiation temperature described below, or both. Preferably, the method is a combination of methods.

If the irradiation dose of the active energy ray is too small and the degree of curing is insufficient, the selectivity becomes insufficient when removing the uncured part, so that a defective portion of a desired shape is not formed. In the step of adhering to the member (J), when the member (J) has a concave portion on the surface, the composition (x) enters the concave portion, closes the concave portion, or changes the cross-sectional area of the concave portion. Not preferred to bring.

On the other hand, when the irradiation amount is excessive and the degree of curing is excessive, the semi-cured coating film loses flexibility and the adhesiveness is reduced, so that the adhesion to the member (J) tends to be incomplete. A suitable degree of semi-curing can be suitably determined by a simple experiment in the system used.

The shape of the pattern in the patterning exposure, that is, the shape of the portion to be a defect can be arbitrarily set according to the purpose of use. For example, a communication path, an inflow / outflow port, a storage tank, a reaction tank, a liquid-liquid contact section, a development path for chromatography and electrophoresis, a detection section, and a part of a valve structure; a portion around a valve; , A space used as a pressure detecting portion, etc .; all or a part of a hollow defective portion used as a space used as a sensor embedded portion, etc.

When the shape to be the defective portion is linear in the plane of the coating film, it may be a straight line, zigzag, spiral, horseshoe or other shapes. When used as a liquid storage tank or a reaction tank, the shape may be circular or rectangular. Further, the shape to be the defective portion may be a minute through hole connecting the front and back of the coating layer. The defective portion may or may not communicate with the outer peripheral portion of the coating film, that is, the outer peripheral portion of the micro device.

When the deficient portion is linear when viewed from the coating film surface, the deficient portion, that is, the uncured portion preferably has a width of 1 to 1000 μm. The width is preferably 1 μm or more, and 5 μm
More preferably, it is 10 μm or more. A microdevice having an uncured portion with a smaller width becomes difficult to manufacture. Uncured part width is 1000μ
m, preferably 500 μm or less, more preferably 200 μm or less.

When the width of the uncured portion is wider than the above, the effect of the present invention is reduced. The width / depth ratio of the groove is arbitrary,
The range is preferably from 10 to 10, more preferably from 0.5 to 5. The size of the uncured portion formed by exposure is not necessarily the same as the size of the active energy ray non-irradiated portion,
It may be larger or smaller than the dimension of the non-irradiated portion of the active energy ray.

Types and irradiation doses of active energy rays, compounds
It may vary depending on the reactivity of (a), the type and amount of the active energy ray polymerization initiator, and the amounts of the polymerization inhibitor and the retarder added. However, the degree of change is not so large, and is at most about 1/2 to 2 times. The cross-sectional shape of the uncured portion may be any shape such as a rectangle (including a rounded rectangle), a trapezoid (including a rounded trapezoid), and a semicircle.

The active energy rays that can be used in the present invention include: rays such as ultraviolet rays, visible rays, infrared rays, laser rays, and radiation; ionizing radiation such as X-rays, gamma rays, and radiation; electron rays, ion beams, and beta rays. ,
A particle beam such as a heavy particle beam is exemplified. Among these,
Ultraviolet light and visible light are preferred in terms of handleability and curing speed, and ultraviolet light is particularly preferred. For the purpose of accelerating the curing speed and performing the curing completely, it is preferable to carry out the irradiation of the active energy ray in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere.

The method of irradiating the active energy ray to a part other than the part to be a defect part is arbitrary. For example, masking and irradiating an unnecessary part or scanning with a beam of an active energy ray such as a laser. Photolithography techniques can be used.

In the production method of the present invention, after exposure, the uncured portion of the uncured composition (x) is removed to form a defective portion of the resin (hereinafter, this operation is sometimes referred to as "development"). This step is referred to as “step (iii)”. The method of removing the uncured composition (x) is optional.For example, methods such as blowing off with compressed air, absorbing with filter paper, rinsing with a non-solvent liquid stream such as water, solvent washing, volatilization, decomposition, etc. Available.

Among them, washing with a non-solvent liquid stream or solvent washing is preferred. Composition (x) by development
The uncured part becomes a defective part. The shape of the formed defect
The dimensions are almost the same as the shape and dimensions of the uncured portion of the composition (x), but do not completely match. For example, in the case of blowing off with compressed air or the like and rinsing with a non-solvent liquid stream, the width of the defective portion tends to be narrower than in solvent cleaning, and the uncured composition (x) in the non-irradiated portion is completely removed. In some cases, the bottom of the defective portion may be rounded, or the bottom of the defective portion may not reach the surface of the coated support.

In the case where a part of the resin layer (X) of the micro device manufactured by the present invention which is in contact with the member (J) but is not adhered is formed, the step (i) and the step (i) (ii)
, Between steps (ii) and (iii), and between steps (iii) and
(iv) during one or more steps selected from
When selectively irradiating a part of the coating film to be the resin layer (X) with an active energy ray and stacking it with another member in the step (iv), the irradiated portion does not adhere to other members. Partial curing is performed to cure to. This step is referred to as "step (ii ')".

That is, when the step (ii ′) is performed between the step (i) and the step (ii), the uncured coating film to be the resin layer (X) is partially cured, and then the defective portion is removed. It is semi-cured except for the part where it becomes. When carried out between the step (ii) and the step (iii), the coating film to be the resin layer (X) is partially cured in a state where the uncured portion and the semi-cured portion are present, and thereafter, the defective portion To form

When the step is carried out between the step (iii) and the step (iv), a part of the semi-cured coating film having the defective portion is partially cured. Step (ii ′) is substantially the same as steps (i), (ii), and (i).
It may be substantially simultaneous with ii), or may be performed in a plurality of stages. The active energy rays used in the step (ii ′) are the same as those in the step (ii) of semi-curing the coating film.

The same applies to the case where a structure in which a part of the resin layer (X) is in contact with the member (K) but is not bonded is formed.
That is, when a part of the resin layer (X) is provided with a part that is not bonded to both the member (J) and the member (K), the same method as described above can be used.

However, if a part of the resin layer (X) is bonded to the member (J) and not bonded to the member (K), the step of performing partial curing is a (iv) and step (between vI, step (iv) and step (vi), step (v) and step (between step (vi) and step of laminating the member (K), step It can be formed by the same method as described above, except between any arbitrary steps between the step of laminating (v) and the member (K).

After the step (iii), a semi-cured coating film of the composition (x) is laminated on the member (J), and the semi-cured coating film is formed as a resin layer (X).
This step is referred to as “step (iv)”. The lamination of the semi-cured coating film of the composition (x) and the member (J) may be in a form according to the use and purpose, and does not necessarily have to be the entire surface.

The shape of the member (J) does not need to be particularly limited, but may be any shape according to the purpose of use. For example, sheet (including film and ribbon), plate, coating, rod,
The surface to be bonded can be a flat surface or a quadratic surface, because it can be formed into a tube or other complicated shape, but it is easy to mold and easy to laminate and bond the composition (x) semi-cured coating film. It is preferably in the form of a sheet, and particularly preferably in the form of a sheet or a plate. In addition, a member (J ′) described later is a member (J).
Which have a specific shape.

The material of the member (J) is not particularly limited as long as the composition (x) can be adhered by the production method of the present invention. As a material that can be used as a material of the member (J), for example,
Examples thereof include polymers, crystals such as glass and quartz, semiconductors such as ceramic and silicon, and metals. Of these, polymers (polymers) are particularly preferable in terms of easy moldability, high productivity, low cost, and the like. .

The member (J) may be formed on a support. In this case, the material of the support is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like. The shape of the support is also arbitrary, and may be, for example, a plate-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. The support may be integrated with the present microdevice or may be removed after formation. A plurality of microdevices can be formed on one member (J), or after manufacturing, these can be cut into a plurality of microdevices.

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

Examples of the polymer usable for the member (J) include styrene-based polymers such as polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer and polystyrene / acrylonitrile copolymer; Polysulfone-based polymers such as ethersulfone; (meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; Polymaleimide-based polymers; Coalescence;

Polyethylene, polypropylene, poly-4
A polyolefin polymer such as -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; poly-2,6-dimethylphenylene oxide, polyphenylene sulfide Polyether or polythioether polymers such as polyether ketone; Polyether ketone polymers such as polyether ether ketone; Polyester polymers such as polyethylene terephthalate and polyarylate; Epoxy resins; Urea resins; Fluorine polymers such as ethylene and PFA (copolymer of tetrafluoroethylene and perfluoroalkoxyethylene), silicone polymers such as polydimethylsiloxane; active energy ray-curable composition (X) used in the present invention Hard Thing, and the like.

Of these, styrene-based polymers, (meth) acrylic-based polymers, polycarbonate-based polymers, polysulfone-based polymers, and polyester-based polymers are preferred from the viewpoint of good adhesiveness. The member (J) is also preferably a cured product of an active energy ray-curable resin.
The member (J) may be composed of a polymer blend or a polymer alloy, or may be a laminate or other composite. Further, the member (J) may contain additives such as a modifier, a colorant, a filler, and a reinforcing material.

Examples of the modifying agent that can be contained in the member (J) include hydrophobizing agents (water repellents) such as silicone oil and fluorine-substituted hydrocarbons; water-soluble polymers, surfactants, silica gels and the like. And a hydrophilizing agent such as an inorganic powder. Examples of the coloring agent that can be contained in the member (J) include an arbitrary dye or pigment, a fluorescent dye or pigment, and an ultraviolet absorber. Examples of the reinforcing material that can be contained in the member (J) include inorganic powders such as clay and organic and inorganic fibers.

When the member (J) 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 (J) and the use of a primer By
It is preferable to impart or improve the adhesiveness. Also,
Apply the active energy ray-curable composition to the surface of the member (J), form a layer that has been semi-cured by irradiating with active energy ray, and use this as the member (J). From the viewpoint of adhesiveness, it is more preferable to use the same active energy ray curable composition as the resin layer (X) to be adhered.

Further, in using the microdevice of the present invention, in addition to the purpose of improving the adhesiveness, the purpose of suppressing adsorption of solutes such as proteins to the device surface is as follows.
It is also preferable to make the surface of the member (J) hydrophilic.

The member (J) is a member having a concave portion such as a groove on the surface, a member having no concave portion on the surface, a composition (x) (half) cured resin layer having no defective portion in the layer, or a separation membrane. Or a composite of these. The member (J) may be removable after forming the resin layer (X) by laminating it thereon. Further, the member (J) is a single resin layer.
(X), a plurality of laminated resin layers (X), or a member in which the resin layer (X) is laminated on another member. Single resin layer (X)
Can be formed by the same method as the removal of the coated support in the step (v) of the present invention.

The resin layer (X) is transferred to the member (J) by removing the coating support from the resin layer (X) adhered to the member (J). This step is referred to as “step (v)”. The removal method is optional, and may be peeling, dissolving, decomposing, melting, or volatilizing.However, peeling is preferred in terms of high productivity, and the flexible thin resin layer (X) can be formed without damaging it. Is preferably dissolved.

In the case where the removal of the coated support is peeling, it is preferable to perform the below-mentioned step (vi) before this step (v).
Alternatively, it is also preferable to carry out before and after this step. The removal by peeling is optional such as peeling by pulling, peeling by a blade, peeling by a liquid flow such as a water flow, peeling by a gas flow by compressed air, or natural peeling by immersion in water. It is also preferable to change the conditions or to carry out in water.

Further, a combination of the material of the coating support and the composition (x) is selected, and a combination which is adhesive in the state of the uncured coating film and the semi-cured coating film and has a low adhesion after curing is selected. It becomes easy by choosing. The removal by peeling is a preferable method when the resin layer (X) has relatively high rigidity such that the tensile elastic modulus is 0.1 to 10 GPa.

In the case where the removal of the coated support is dissolution, the step (vi) described later may be before or after the step (v). Of course, it may be performed before or after this step. The removal by dissolution can be carried out by selecting a combination of the material of the coated support and the composition (x), and using a solvent that selectively dissolves the coated support. Examples of such solvents include water, acids, alkalis, lower alcohols, ketone solvents, ester solvents, ether solvents, and hydrocarbons. The dissolution method is also arbitrary, and for example, a method such as immersion in a liquid, a shower, or steam cleaning can be employed.

These do not require that the coated support be completely dissolved. That is, if a part of the coated support swells and dissolves and is separated from the resin layer (X), the object of the present invention is sufficiently achieved. Therefore, a method is also included in which a solvent such as water, which dissolves the coated support, is strongly sprayed to partially swell and dissolve the coated support, and the coated support is separated from the resin layer (X).

Among them, those based on water, acid and alkali are preferred. Removal by dissolution is performed when the step (vi) described below is before this step (v), and the defective portion of the resin layer (X) has a long linear shape, a curved shape, and a large number of linear shapes. It is suitable when it is difficult to remove by peeling. In addition, the removal by dissolution is performed when the cured resin layer (X) has a tensile elastic modulus of 1 to 7;
This is a preferable method when the rigidity is relatively low such as 00 MPa. Removal by decomposition is optional such as oxidative decomposition and hydrolysis, and can be handled in the same manner as the above-described removal by dissolution.

Before and / or after step (v), that is, with the coated support laminated and / or removed, the semi-cured resin layer (X) is re-irradiated with active energy rays. Then, the composition (x) is further cured and adhered to the member (J). This step is referred to as step (vi). Irradiation with active energy rays in this step cures the composition (x) layer to such an extent that the microdevice to be manufactured has sufficient strength, and simultaneously cures the composition (x) cured material layer and the member (J). It means bonding with sufficient strength.

When the removal of the coated support in the step (v) is due to peeling, it means that the support is cured to the extent that it can be peeled. Therefore, it is not always necessary to cure until the polymerizable group has completely disappeared. In particular, the resin layer (X)
When further laminating and bonding other members, the degree of curing is, while the coating support is cured to the extent that it can be peeled off,
It is preferable that the polymerizable group remains to such an extent that it can be adhered to another member by the third irradiation with the active energy ray.

As the active energy rays that can be used for curing in step (vi), those exemplified as the active energy rays that can be used for semi-curing the composition (x) can be used. The active energy rays used in this step may be the same as or different from those used in step (ii). Further, irradiation conditions such as intensity, irradiation temperature, and atmospheric oxygen concentration may be different.

The resin layer (X) has a defective portion of the resin formed by patterning exposure and development in the layer, and the defective portion is formed by laminating the layer with the member (J). Accordingly, by further laminating another member (K) on the resin layer (X) and sandwiching the resin layer (X) between the member (J) and the other member (K), as a flow path or the like. The cavities used can be configured. The cavity may or may not communicate with the outside of the microdevice. The resin layer (X ′) described later has a specific shape in the resin layer (X).

After laminating the resin layer (X) on the member (J), the member (J) on which the resin layer (X) is laminated is used instead of the member (J) in the step (iv), Step of forming (X), that is,
A series of steps (i), (ii), (iii), (iv), and (v), or steps (i), (ii), (iii), (iv), (v), and ( vi)
A series of steps, or steps (i), (ii), (iii), (iv), (v
By repeating a series of steps i) and (v),
A plurality of resin layers (X) can be laminated.

At this time, the step (vi) is not always required to be performed, but may be required depending on the method of peeling the support. The shape of the resin layer (X) of two consecutive resin layers (X) may be the same or different, and the thickness and the type of the composition (x) constituting the resin layer (X) It may be different. In the case where the process is repeated twice or more, a series of steps selected from any of the above processes can be selected and performed each time.

The preferred procedure of the production method of the present invention differs depending on the method of removing the coated support in step (v).
For example, if the removal of the coated support is due to dissolution, another member (K) is laminated on the semi-cured resin layer (X), and the member is removed.
It is preferable that the resin layer (X) is sandwiched between (J) and another member (K), and in this state, the active energy ray irradiation in the step (vi) is performed, and these are bonded.

If the removal of the coating support is due to dissolution, the semi-cured resin layer (X) formed on the member (J) and having the coating support removed is replaced with the member (J). ), And by repeating any one of the above-described steps, a plurality of resin layers (X) are laminated, and in this state, the active energy ray irradiation of the step (vi) is performed, and these are irradiated. Can be glued.

When the removal of the coated support is due to peeling, the step (vi) is performed before the step (v), and the hardening formed on the member (J) after the removal of the coated support is performed. Using the resin layer (X) in place of the member (J), the steps (i), (ii), (iii),
By repeating steps (iv), (vi), and (v),
A micro device in which a plurality of layers are laminated on the resin layer (X) can be manufactured.

In the same manner as described above, another resin layer (X) may be laminated on the resin layer (X) via another member, or the resin layer (X) may be formed on the member (J). ) To form a formed member,
By laminating a plurality of them, multiple resin layers
It is also possible to provide a micro device having (X).

By connecting the defective portions of three or more layers of continuous members, three-dimensional crossing of the hollow channel becomes possible, and the microdevice can have a complicated function. Such a form is a member having a defect portion penetrating the member, a member having a concave defect portion on the surface, or a member selected from a member having a defect portion penetrating the member and a member having a concave defect portion on the surface (J ), And a member (K) having the same structure as the member (J), a member (J) -resin layer (X) -member
(K) It may be a laminate. At this time, the member (K) may have the same material and structure as the resin layer (X), the resin layer (X) may have a plurality of layers, and the member (J) may have the same material as the resin layer (X). Materials and structures may be used.

It is also preferable that another member (K) is brought into close contact with the formed resin layer (X). The adhesion may be adhesion, adhesion, non-adhesion adhesion, or the like, but is preferably adhesion. The bonding method is optional, but using an active energy ray-curable composition for the material of the member (K), contacting the resin layer (X) in a semi-cured state, re-irradiating the active energy ray, and bonding The method is preferred. For example, it is also preferable to form the resin layer (X) by the same method except that no defective portion is formed. Note that a member (K ′) described later has a specific shape of the member (K).

The shape and dimensions of the member (K) are the same as those of the member (J). The member has a defective portion penetrating the member, the member has a concave defect portion such as a groove on the surface, and the member penetrates the member. A member having no defective portion or concave concave portion on the surface, a resin layer formed by the same method as the resin layer (X) of the present invention and having the same material and structure, a composition having no defective portion in the layer It may be a (semi) cured resin layer of the product (x), a separation membrane, and the like, and a composite thereof. Resin layer on any member instead of member (K)
A member in which (X) is laminated can also be used.

The resin layer (X) can be formed to a desired hardness by selecting the active energy ray-polymerizable compound (a) and blending each component of the composition (x). The tensile modulus of the resin layer (X) can be, for example, 0.01 GPa to 10 GPa, preferably 0.05 GPa to 3 GPa.

The micro device of the present invention comprises a resin layer (X)
By providing a structure that functions as a valve, a microdevice having a valve can be obtained. The valve structure is
It is preferable that it is in the form of a sheet in which a part of the sheet is fixed because manufacturing is easy. The partially fixed sheet shape may be, for example, a tongue shape, a circle or a rectangle fixed by one or more portions.

In the production method of the present invention, in the step (ii) of the present invention, a portion of the sheet is fixed by exposing a portion having a valve to the periphery and exposing the portion to a defect. Can be formed. For example, to form a tongue-shaped valve structure, exposure may be performed to form a horseshoe-shaped defect.

A member having a hole-shaped defective portion having an area smaller than that of the valve on one side of the resin layer (X) on which the valve is formed.
(J), the member (K) or the resin layer (X), the hole-shaped defective portion is laminated according to the valve, and the other side of the resin layer (X) is larger than the valve so that the valve can move. The valve can be formed by laminating the member (J), the member (K), or the resin layer (X) having a cavity that becomes a cavity.

The resin layer (X) is made of another member or a resin layer, for example, a member having a hole-shaped defect having an area smaller than that of the valve.
(J), the member (K) or the resin layer (X), in order to avoid that the valve part is also bonded, before the step (iv), the resin layer (X) of the valve It is preferable to irradiate the active portion with an active energy ray to advance the curing to such an extent that the portion does not adhere. The active energy ray irradiation is preferably carried out simultaneously with step (ii) and / or between step (iii) and step (iv).

The resin layer (X) on which the valve is formed is preferably formed of a flexible material, and is preferably formed of a material having a lower tensile modulus than the layers and members sandwiching the layer. The preferred tensile modulus of the material used for the resin layer (X) on which the valve is formed is 1 MPa to 1 GPa, and more preferably 10 to 5 GPa.
00 MPa, more preferably 50 to 300 MPa. If it is lower than this range, the strength and the repetition durability tend to be inferior, and if it is higher than this range, leakage tends to occur at the time of closing.

According to the manufacturing method of the present invention, similarly to the case of manufacturing a micro device having a valve, in the case of manufacturing a micro device having a movable diaphragm, the member adjacent to the diaphragm, that is, the resin layer
(X), in order to avoid being bonded to the member (J) or the member (K), when the resin layer (X) is adjacent to the diaphragm, between the step (i) and the step (iv). It is preferable to provide a step of irradiating an active energy ray to a portion of the resin layer (X) to be non-adhered and proceeding the curing to such an extent that the portion does not adhere.

Examples of microdevices that can be manufactured by such a method include microdevices having a diaphragm valve mechanism, a check valve mechanism, a diaphragm opening / closing valve mechanism, a diaphragm type flow control valve mechanism, and the like. it can.

The formed micro device can be subjected to post-processing such as punching and cutting. Further, since the microdevice of the present invention has a very small size as a whole, it is possible to simultaneously produce a large number of members on one resin layer, thereby improving the production efficiency.
It is also useful for precise positioning of details of each member. That is, by forming a plurality of minute microdevices on one exposure development plate, a large number of microdevices can be produced at once with good reproducibility and high dimensional stability with high accuracy.

The microdevice of the present invention can be obtained from a member having a defective portion penetrating the member, a member having a concave defect portion on the surface, or a member having a defective portion penetrating the member and a concave portion on the surface. The member (J ′)｝ to be selected, and a part of the layer has a defect, and the minimum width of the defect is 1 to 1000.
μm, one or more layers of the active energy ray-curable resin layer (X ′), a member having a defective portion penetrating the member, or a member having a concave defect portion on the surface, or penetrating the member. A laminated structure in which a defective portion and a member (K ′)｝ selected from a member having a concave defective portion on the surface are laminated, and at least two or more defective portions in the member are connected to form a cavity. It is a micro device having.

The member (J ') is a member having a defective portion penetrating the member, a member having a concave defect portion on the surface, or a member having a defective portion penetrating the member and a concave defect portion on the surface. Other than that, the member (J) used in the production method of the present invention is the same as the member (J) and has a specific shape. The member (K ′) is also a {member having a defective portion penetrating the member, or a member having a concave defect portion on the surface, or a member having a defective portion penetrating the member and a concave defect portion on the surface}. Except for this, it is the same as the member (K) used in the production method of the present invention, and has a specific shape of the member (K).

The position, shape, and size of the defect penetrating the member are arbitrary, except that the defect is open on a surface that can be connected to the resin layer (X ′). The shape of the defective portion penetrating the member is, for example, a round hole, a square hole, a slit shape, a conical shape, a pyramid shape,
It may be a barrel, screw hole, or other complicated shaped defect.
The defective portion of the member (J ') may be a large hole compared to the defective portion of the resin layer (X'). The dimensions and shape of the concave defective portion formed on the surface of the member (J ') are as described below. This is the same as the shape and size of the cavity formed in the micro device of the present invention.

The method for producing the member (j ′) and the member (K ′) having a deficient portion is arbitrary. For example, injection molding, a melt replica method, a solution casting method, and a photopolymer using an active energy ray-curable composition. It can be produced by a lithographic method or a cast molding method using an active energy ray-curable composition. The member (J ′) may be a resin layer having the same material and shape as the resin layer (X ′) according to the present invention, or may be a resin layer according to the present invention.
(X ′) may be a structure in which a plurality of layers are laminated, or the resin layer (X ′) referred to in the present invention may be a laminate in which another member is laminated.

The micro device of the present invention comprises a member (J ′),
It is a laminate of one or more resin layers (X ′) and members (K ′), and the total number of layers is 3 or more.
It is preferably 10 and more preferably 3 to 6.

In the micro device of the present invention, unlike the resin layer (X) in the manufacturing method of the present invention, the defective portion formed in the resin layer (X ′) penetrates the front and back of the resin layer. The resin layer is laminated with another resin layer (X ′) or a member having a through hole or a concave portion to form a cavity connecting these layers and members. The resin layer (X ′) is the same as the resin layer (X) in the production method of the present invention, except that the defective portion formed in the resin layer penetrates the front and back of the resin layer.

In the microdevice of the present invention, each of the defects formed in the member (J ′), the one or more resin layers (X ′), and the member (K ′) has at least two adjacent layers. The missing portions communicate with each other to form a cavity. Preferably, three or more continuous defective portions are connected to each other to form a cavity.

It is also possible to laminate another member, for example, a member having a defective portion, on the microdevice of the present invention. In addition, two or more microdevices of the present invention
It is possible to make a new micro device by bonding so that the cavities opened on the surface are connected to each other, or by laminating and bonding members that do not have through holes or recesses, and the cavities are connected to each other It is also possible to provide a microdevice composed of a plurality of parts not shown.

An example of such a device is a device having a diaphragm structure in which the microdevice has a diaphragm pump mechanism or a diaphragm valve mechanism, and a member having no through-hole or concave portion forms a diaphragm. A micro device can be exemplified. A member having no through-hole or concave portion is preferably formed of an active energy ray-curable resin because of high interlayer adhesion and high productivity. Further, such a member may be a porous membrane, a dialysis membrane, a gas separation membrane, or the like.

The shape of the cavity in the micro device of the present invention can be arbitrarily set according to the purpose of use. For example,
Connection channels, inflow / outflow ports, storage tanks, reaction tanks, liquid-liquid contact sections, development paths for chromatography and electrophoresis, detection sections, flow paths for fluids such as valves; pressurized tanks, depressurized tanks, pressure detection sections This space can be the whole or a part of a cavity-shaped defective portion used as a space used as a sensor embedded portion or the like.

The fact that a plurality of flow paths or branched flow paths formed in different resin layers (x ′) intersect three-dimensionally with the resin layer (X ′) interposed therebetween indicates that the flow paths are formed in a plane. This is preferable because it is free from restrictions to be performed and a complicated device can be configured.

In the present invention, the cavity may be a part of the valve. The type of valve is arbitrary, for example, a check valve (a valve that is normally closed and opens when a certain pressure is applied), a check valve (a normally open valve in one direction, and a normally closed valve in the opposite direction). A certain valve), an on-off valve, a flow control valve, and the like.

When the valve has a valve, the shape of the valve is arbitrary. For example, a sheet (film, film, ribbon, plate, etc.) having a part fixed, such as a tongue shape, may be used. Included), and may be an independent mass such as a sphere, a cone, or a plate trapped in a cavity. It is preferable that the structure serving as the valve is in the form of a sheet in which a part thereof is fixed, because manufacture is easy.

The sheet shape partially fixed may be, for example, a tongue shape, a circle or a rectangle fixed by two or more portions. In the micro device of the present invention, the resin layer
A part of (X ′) can be formed as a sheet-shaped valve in which a part around the part serving as a valve is a defect and a part thereof is fixed.

[0158] For example, when the defective portion is horseshoe-shaped, a structure serving as a tongue-shaped valve is obtained. Then, on one side of the resin layer (X ') on which the valve is formed, a hole-shaped defective portion having an area smaller than that of the valve is laminated according to the valve, and on the other side, the valve is movable. Can function as a valve by forming a cavity larger than the valve.

The resin layer (X ′) having a valve is preferably formed of a flexible material, and is preferably formed of a material having a lower tensile modulus than the layers or members sandwiching the resin layer. . The preferred tensile modulus of the material used as the resin layer (X ') having a valve is 1 MPa to 1 GPa, more preferably 10 to 500 MPa, and still more preferably 50 to 30 MPa.
0 MPa. If it is lower than this range, the strength and the repetition durability tend to be inferior, and if it is higher than this range, leakage tends to occur at the time of closing.

The present invention also provides a micro device having a diaphragm type valve mechanism. A first preferred example of the diaphragm type valve mechanism is such that a resin layer (X ′) is directly laminated on one side with a resin layer serving as a diaphragm and on the other side with another member having a defective portion. ') Becomes a cavity by laminating the defective part, and another member laminated on the back surface of the resin layer (X') has a hole-shaped defect that serves as an inlet or an outlet to the cavity, or both. Having a portion, at least one of the inflow port and the outflow port is formed on the facing surface of the diaphragm across the resin layer (X '), the periphery of which is not in contact with the diaphragm, deforming the diaphragm,
It has a structure capable of closing the flow channel by contacting at least one of the inflow port and the outflow port.

When the hole-shaped defective portion formed at a predetermined position of another member is either the inlet or the outlet, the other is formed by the linear member formed on the resin layer (X ′). The capillary channel formed by the defective portion and the resin layer serving as the diaphragm, or the capillary-shaped channel formed by the groove-shaped defective portion formed in the other member) and the resin layer (X ′) It may be a channel or the like.

As a valve having such a structure, a normally open diaphragm type valve can be mentioned. The structure in which the resin layer serving as the diaphragm, the resin layer (X ′), and other members are bonded and laminated can be manufactured by the manufacturing method of the present invention.

The present invention also relates to a member having a defective portion penetrating the member, a member having a concave defective portion on the surface,
Or a member (J ′)｝ selected from a member having a concave portion and a concave portion on the surface penetrating the member, and having a defective portion in a part of the layer, and the minimum width of the defective portion is 1 to 1000 μm. One or more layers of the active energy ray-curable resin layer (X ') and a member (K'') forming a diaphragm without a defect are laminated, and the member (K'') is laminated adjacently. Has a portion that is in contact with, but not adhered to, another member, and that portion is a diaphragm portion. At least two or more defective portions in the member (J ′) and the resin layer (X ′) Provided is a micro device having a laminated structure, which is connected to form a cavity.

That is, the member (J ′), one or more resin layers (X ′),
And a laminated body of a member (K '') having no deficient portion, wherein the member (K '') has a portion which is in contact with, but not adhered to, another member laminated adjacently, A microdevice is provided wherein the portion is a diaphragm portion.

The member (J ') and the resin layer (X') are the same as the member (J ') and the resin layer (X') described above. Instead of the member (K '), a diaphragm is used. , A member without a missing part
Except for using (K ''), the above-mentioned member (J '), resin layer
This is the same as the micro device composed of (X ′) and the member (K ′).

The member (K ″) has a portion that is in contact with, but not bonded to, another member laminated on the member, and that portion becomes a diaphragm portion. That is, when the diaphragm is deformed, the non-adhered portion may become a cavity.

A second preferred example of the diaphragm type valve mechanism of the present invention has the above structure and a resin layer.
(X ′) has an inflow port or an outflow port to the portion that can be the cavity, or a hole-shaped defective portion that becomes both, and at least one of the inflow port and the outflow port is formed on the facing surface of the diaphragm. The periphery is in contact with the diaphragm but is not adhered, and the flow path is opened by deformation of the diaphragm.

When the hole-shaped defective portion formed at a predetermined position of the resin layer (X ′) is either the inlet or the outlet, the other is a linear portion of the resin layer (X ′). Of the flow path formed by the deficient portion and the diaphragm, and a connection port to the hollow portion.

In the member (J '), a cut-off portion serving as a flow path connected to the inflow port, the outflow port, or both can be formed. The structure in which the felony (J ′), the resin layer (X ′) and the member (K ″) are bonded and laminated can be manufactured by the manufacturing method of the present invention. Examples of the valve having such a structure include a normally-closed diaphragm valve and a check valve.

In each of the first and second examples, the thickness of the diaphragm is preferably 1 to 500 μm.
m, more preferably 5 to 200 μm. The optimum value of the thickness of the diaphragm varies depending on the size of the cavity, and it is preferable that the diaphragm be thinner as the area of the cavity is smaller. However, if it is less than this range, it becomes difficult to manufacture, and if it exceeds this range, the merit as a micro device decreases.

The diaphragm preferably has a tensile modulus of 1 to 700 MPa, more preferably 10 MPa to 10 MPa.
It is formed of a material in the range of 300 MPa. Although it depends on the diameter of the diaphragm and the hardness of the material, if it is smaller than this, it becomes difficult to manufacture or maintain an open state, and if it exceeds this range, opening and closing becomes difficult.

The material forming the diaphragm is JIS
The elongation at break measured by K-7127 is preferably 2% or more, more preferably 5% or more. The upper limit of the elongation at break may naturally be limited, but since it is high, there is no inconvenience due to itself, so it is not necessary to set an upper limit, and it may be, for example, 400%. In the present invention,
Even a material showing a low elongation at break of 2 to 5% in a tensile test according to JIS K-7127 is hardly broken in the method of use of the present invention, and breaks even when a strain higher than the elongation at break in the above test is given. It can be used without doing.

The method of deforming the diaphragm is arbitrary, and for example, the method of deforming the diaphragm into a cavity formed on the opposite side of the diaphragm may be used.
The change may be pressure change such as press-in or depressurization of a fluid, mechanical compression or suction, or the like.

The present invention can provide a micro device having a multilayer structure in which a cavity partly used as a flow path is formed in a plurality of layers, particularly three or more layers. Further, it is easy to form a fine valve, a thin and flexible diaphragm, and to adhere to these target positions, thereby providing a microdevice having a valve mechanism. Further, a device is obtained in which the flow path is not blocked by the adhesive and the liquid does not leak between the layers or between the layers and other members. Further, by using an amphiphilic polymerizable compound, a chemical device having excellent reproducibility without adsorption or loss of biological components can be obtained.
Thus, a micro device capable of performing a reaction and analysis of a complicated process can be provided.

[0175]

EXAMPLES Hereinafter, 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.

[Activation Energy Beam Irradiation] Using a light source unit for a multi-light 200 type exposure apparatus manufactured by Ushio Inc. using a 200 W metal halide lamp as a light source, 36
Ultraviolet light having an intensity of 100 mW / cm ² at 5 nm was irradiated at room temperature in a nitrogen atmosphere.

[Preparation of composition (x)] [Preparation of composition (x-1)] Active energy ray-polymerizable compound
As (a), 30 parts of a trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidick V-4263” manufactured by Dainippon Ink and Chemicals, Inc.), 1,6-
45 parts of hexanediol diacrylate (“Kayarad HDDA” manufactured by Nippon Kayaku Co., Ltd.),

As the amphiphilic compound (b), nonylphenoxypolyethylene glycol (n = 17) acrylate (“N-177E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25
Part, 1 part of 1-hydroxycyclohexylphenyl ketone ("Irgacure 184" manufactured by Ciba Geigy) as a photopolymerization initiator, and 2,4-diphenyl-4-methyl-1-pentene (Kanto Chemical Co., Ltd.) as a polymerization retarder (1) was mixed to prepare an active energy ray-curable composition (x-1). The ultraviolet-cured product of the active energy ray-curable composition (x-1) has a tensile modulus of 560 MPa.
a, The contact angle with water was 12 degrees.

[Preparation of composition (x-1 ')] The composition was the same as that of composition (x-1) except that the amount of the photopolymerization initiator was 2 parts and that no polymerization retarder was contained. Composition (x-1 ′) was prepared. The ultraviolet-cured product of the active energy ray-curable composition (x-1 ′) had a tensile modulus of 580 MPa and a contact angle with water of 12 degrees.

[Preparation of Composition (x-2)] As an active energy ray-curable compound (a), polytetramethylene glycol (average molecular weight: 250) maleimide capriate (see Synthesis Example 13 of JP-A-11-124403) 75 parts of nonylphenoxy polyethylene glycol (n = 1) were synthesized as the amphiphilic compound (b).
7) Acrylate (“N-1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
77E ") 25 parts, 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) as a polymerization retarder
Active energy ray-curable composition by mixing 0.01 part
(x-2) was prepared. The ultraviolet-cured product of the active energy ray-curable composition (x-2) has a tensile modulus of 610 MPa.
a, The contact angle with water was 19 degrees.

[Preparation of composition (x-2 ')] A composition (x-') having the same composition as the composition (x-2) except that it did not contain a polymerization retarder.
2 ′) was prepared. The active energy ray-curable composition
(x-2 ') UV cured product has a tensile modulus of 630 MPa,
The contact angle with water was 19 degrees.

[Preparation of Composition (x-3)] As an active energy ray polymerizable compound (a), a trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidick V- 4263 ") 30
Parts, 45 parts of an alkyl diacrylate (“Sartomer C2000” manufactured by Somar Corporation) containing ω-tetradecanediol diacrylate and ω-pentadecanediol diacrylate as main components,

And 25 parts of nonylphenoxypolyethylene glycol (n = 17) acrylate (“N-177E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1 as a photopolymerization initiator
5 parts of hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy) and 0.1 part of 2,4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) as a polymerization retarder were mixed. Thus, an active energy ray-curable composition (x-3) was prepared. In addition,
The ultraviolet cured product of the active energy ray-curable composition (x-3) had a tensile modulus of 160 MPa and a contact angle with water of 14 degrees.

[Example 1] In this example, a method for producing a microdevice of the present invention using an acrylic resin for the composition (x) by a method of removing by peeling off a coated support will be described.

[Step (i)] As a coating support (1), a 30 μm thick biaxially oriented polypropylene film (OPP film, manufactured by Nimura Chemical Co., Ltd.) having a corona discharge treatment on one side was cut into 5 cm × 5 cm. On the corona-treated side using a 127 μm bar coater
(x-1) was applied to form a coating film (2).

[Step (ii)] Next, in a nitrogen atmosphere, ultraviolet light was applied to portions other than the non-exposed portion (3) shown in FIG. 1 for 1 second through a photomask having a non-exposed portion width of 100 μm and a non-exposed portion length of 30 mm. Exposure to irradiation was performed and semi-cured.

[Step (iii)] The semi-cured coating film is exposed to running water from a tap to expose the uncured composition (x
By removing the -1) by washing, a semi-cured coating film (2) having a defective portion (3) was formed on the coating support (1).

[Preparation of member (J-1)] 5c made of polystyrene ("Dick Styrene x C-520" manufactured by Dainippon Ink and Chemicals, Inc.) instead of coating support (1)
The use of a plate-shaped substrate (4) having a size of mx 5 cm x a thickness of 3 mm, the use of the composition (x-1 ') instead of the composition (x-1), and the photo exposure Except that no mask was used, a semi-cured coating film (5) of the composition (x-1 ′) was formed on the surface of the substrate (4) in the same manner as in the preparation of the semi-cured coating film (2) described above. A member (J-1) on which was formed was produced.

[Step (iv)] The semi-cured coating film (2) formed on the coating support (1) is brought into close contact with the surface of the member (J-1) on which the semi-cured coating film (5) is formed. Laminated, semi-cured resin layer
(X-1) Precursor (2 ′).

[Step (vi)] The laminated body was irradiated with the same ultraviolet ray used for exposure for 5 seconds without a photomask, to further cure the resin layer (X-1) precursor (2 ′). Layer (X-
1) At the same time as (2 '), resin layer (5) of member (J-1)
And glued.

[Step (v)] Next, the coating support (1) was peeled off from the four-layer laminate, and the resin layer (5) of the member (J-1) was removed.
To form a microdevice (D-1) having a resin layer (X-1) (2 '), that is, a layer of a cured product of the composition (x-1), having a defect (3) thereon did.

[Adhesion of member (K-1)] Polystyrene (Dick Styrene XC manufactured by Dainippon Ink and Chemicals, Inc.)
-520 ") in the same manner as the member (J-1) except that a plate having a size of 5 cm x 5 cm x 3 mm thick was used instead of the substrate as the member (K-1) (6). -1) Form a semi-cured coating film (7) of the composition (x-1 ') as an adhesive resin layer on (6), and adhere it to the surface of the resin layer (X-1) (2'). I let it.

[Step (vi)] In this state, the same ultraviolet ray as used for the exposure was irradiated for 30 seconds without a photomask to form the semi-cured coating film (7) into the cured resin layer (7).
The member (K-1) (6) and the resin layer (7) are converted into a resin layer (X-1) (2)
The resin layer (X-1) was adhered to the surface to form a void (3 ′) in the defective portion (3) of the resin layer (X-1) (2), and all the active energy ray-curable compositions (x) were sufficiently cured.

[Formation of Other Structure] Thereafter, at both ends of the capillary cavity (3 '), the member (K-1) (6) and the adhesive resin layer (7) were drilled to a diameter of 1.6 mm. And a stainless steel pipe having a diameter of 1.6 mm is bonded with an epoxy resin to form an inflow port (8) and an outflow port (9). Microdevices with capillary cavities (3 ') (D-
1) was prepared.

[Leak Test] Water was injected from the inlet (8) of the microdevice (D-1), the outlet (9) was closed, and a pressure of 0.1 MPa was applied to the cavity for one hour. Upon leaving, no water leakage was observed.

[Observation of Cavity] Micro Device (D-1)
Was cut and observed with a scanning electron microscope (SEM). As a result, the cross section of the capillary cavity (3 ′) was rectangular, having a width of 95 μm and a height of 60 μm.

[Embodiment 2] In this embodiment, a manufacturing method of the present invention using a member (J) having a concave defect on the surface will be described.

[Preparation of member (J)] A plate made of polystyrene ("Dick Styrene x C-520" manufactured by Dainippon Ink and Chemicals, Inc.) and a mold made of silicon wafer having a size of 5 cm × 5 cm × thickness were 3 mm And heated in a hot air oven at 120 ° C. for about 2 hours, cooled at room temperature, and peeled off to obtain a groove with a width of 50 μm.
A member (J-2) was formed by forming a groove-shaped concave portion having the same shape and length as in Example 1 on the surface of the polystyrene plate except that the m and the depth were 25 μm.

[Formation of semi-cured coating film]
On the coated support, in the same manner as in Example 1, except that holes each having a diameter of 300 μm are formed at positions corresponding to both ends of the groove formed in the member (J-2). , 2
A semi-cured coating film having two hole-shaped defects was formed [Process
(i), (ii), (iii)].

[Preparation of Resin Layer (X-2)] The semi-cured coating film formed on the coating support was brought into close contact with the groove forming surface of the member (J'-2) by aligning each other with each other. Step (iv)], in that state, the same ultraviolet light used for exposure is irradiated for 30 seconds without a photomask, and the semi-cured coating film is cured to form a resin layer (X-2) [Step (vi)]. . Next, the coating support was peeled off from the three-layer laminate [Step (v)], and a resin layer (X-
2) That is, a micro-cavity having a cavity having the same shape as the cavity in FIGS. 2 and 3 to which a layer of a cured product of the composition (x-1) having a defect portion serving as an inlet and an outlet is bonded. Device (D-
2) was prepared.

[Example 3] In this example, a method for producing a microdevice of the present invention using a maleimide resin for the composition (x) by a method of removing by removing a coated support will be described. The composition (x-2) was used instead of the composition (x-1) as the composition (x), and the composition (x-2 ') was used instead of the composition (x-1') A microdevice (D-3) having the same structure as in Example 1 was produced in the same manner as in Example 1 except that the exposure time was 2 seconds.

[Embodiment 4] In this embodiment, a microdevice in which a resin layer (X ') is laminated in three phases and which has a three-dimensionally intersecting flow path therein and a method of manufacturing the same will be described.

[Formation of Member (J-4-1)] A composition having no defect on the surface of the base material (35) in the same manner as in Example 1.
(x-1 ') Member on which semi-cured resin layer (36) is formed (J-4-1)
Was prepared.

[Formation of Resin Layer (X'-4-1)] As shown in FIG. 4, a non-exposed part (33) having a width of 100 μm and a length of 30 mm and a non-exposed part (33) having a width of 100 μm and a length of Same as Example 1 except that two straight lines each having a length of 14 mm are separated from each other by 2 mm and are non-exposed portions (34) linearly arranged in a direction perpendicular to the non-exposed portions (33). And the coating support (3
1) A semi-cured coating film (32) having defective portions (33) and (34) of the coating film is formed thereon, and is laminated on the surface of the member (J-4-1) (35), and is formed for 10 seconds. Irradiation with ultraviolet light, the defect (3
3 ′), resin layer having (34 ′) (X′-4-1) (32 ′)
Was formed as a member (J'-4-2).

[Formation of Resin Layer (X'-4-2)] The member (J'-4-2) was used instead of the member (J-4-1), and the non-exposed portion (38) was 8 is the same as the formation of the resin layer (X'-4-1) except that it is a two-circle portion having a diameter of 300 μm and a gap of 2 mm serving as a defective portion (38 ') functioning as an interlayer communication path shown in FIG. Then, the semi-cured coating film (37) having the defective portion (38) of the coating film was transferred onto the resin layer (X'-4-1), and the defective portion (3
A resin layer (X′-4-2) (37 ′) having 8 ′) was formed to obtain a member (J′-4-3).

[Formation of Resin Layer (X'-4-3)] The member (J'-4-3) was used instead of the member (J-4-1).
The shape (0) connects the two defective portions (34 ') in FIG. 8 via the interlayer communication path (38').
In the same manner as the formation of the resin layer (X′-4-1) except that it is a linear shape having a width of 100 μm and a length of 2 mm, a semi-cured coating film (39) having a defective portion (40) of the coating film is obtained. ) For the resin layer (X'-4-2)
Resin layer (X′-4-
3) was formed.

[Adhesion of member (K-4)] The member (K-1) of Example 1 was used, except that it was adhered to the resin layer (X'-4-3) instead of the resin layer (X-1). The same members (K-4) and (41) as in Example 1 were adhered by an adhesive resin layer (42) in the same manner as in Example 1.

[Formation of Inflow / Outflow Portion] At both ends of the defective portion (33 ') of the resin layer (X'-4-1), the base material (35) and the resin layer (36) were drilled with a diameter of 1. Drill a 6mm hole and attach a 1.6mm diameter stainless steel pipe to the resin layer.
Inflow part (43) communicating with the defect part (33 ') of (X'-4-1)
And an outflow portion (44). In addition, resin layer (X'-4-1)
At both ends of the defective portion (34 '), a hole having a diameter of 1.6 mm was drilled in the base material (35) and the resin layer (36), and a stainless steel pipe having a diameter of 1.6 mm was bonded.
The inflow portion (45) and the outflow portion (46) communicating with the deficient portion (34 ') of the resin layer (X'-4-1) were formed to produce a micro device (D-4).

[Water flow test] The dye-colored water introduced from the inflow section (45) was found to be defective (34 '), (38'), (4
0 '), (38'), and (34 '), the distilled water flowing out of the liquid outlet (46) and separately introduced from the inlet (43) passes through the defective portion (33'). Then, it flowed out of the outlet (44) without being mixed with the dye-colored water. That is, it was confirmed that two independent flow paths crossed three-dimensionally.

[Embodiment 5] In this embodiment, a method for manufacturing a micro device having a diaphragm valve function will be described.

[Formation of Member (J-5-1)] A resin layer having no defect on a polystyrene base material (54) in exactly the same manner as the member (J-1) prepared in Example 1. A member (J-5-1) on which (55) was formed was produced.

[Formation of Resin Layer (X-5-1)] A member (J-5-) was formed in the same manner as the formation of the resin layer (X-1) in Example 1 except that the width of the non-exposed portion was different. On the surface of 1), the missing part (5
3 ′) having a width of about 200 μm (X-5-1) (5
2) was formed to obtain a member (J-5-2).

[Formation of Intermediate Layer] The member (J-5-2) was used instead of the member (J-1), and the composition (x-3) was used instead of the composition (x-1). In the same manner as in the formation of the resin layer (X-1) in Example 1 except that the irradiation was performed on the entire surface without using a photomask, Formed on (X-5-1).

[Formation of Resin Layer (X-5-2)] FIG. 9 shows that the member (J-5-3) was used instead of the member (J-1), and the shape of the non-exposed portion was shown in FIG. A circular portion having a diameter of 1 mm at the center and a length 1 connected to the circular portion forming a defect (58 ').
A resin layer (X-5-) was formed on the intermediate layer (56) in the same manner as in the formation of the resin layer (X-1) in Example 1 except that the pattern was a linear portion having a width of 5 mm and a width of 200 μm. 2)
(57) was formed to obtain a member (J-5-4).

[Adhesion of member (K-5)] Except for bonding to the resin layer (X-5-2) instead of the resin layer (X-1), the member (K-1) in Example 1 was adhered. In the same manner as the bonding, the same member (K-5) (59) as the member (K-1) is bonded via the bonding resin layer (60).
(J-5-4).

[Formation of Inflow / Outlet] At both ends of the defective portion (53 ') of the resin layer (X-5-1), holes of 5.1 mm in diameter were drilled in the member (J-5-1). Pierce and adhere a 5mm outer diameter vinyl chloride tube with an epoxy adhesive to form a resin layer (X-5-
A liquid inflow portion (61) and a liquid outflow portion (62) connected to the defective portion (53 ') of 1) were formed.

At the outer end of the defective portion (58 ′) of the resin layer (X-5-2) (57), the base material (5
9) and 1.6 mm in diameter by drilling on the resin layer (60)
And a stainless steel tube having an outer diameter of 1.6 mm is bonded with an epoxy-based adhesive, and a gas introduction portion (58 ′) communicating with the defective portion (58 ′) of the resin layer (X-5-2) (57) is formed. 63) to form a microdevice (D-5). FIG. 9 is a schematic view of a plan view of the manufactured microdevice, and FIG.
FIG. 10 is a cross-sectional view of the portion.

[Flow control test] Water was introduced from the liquid inflow section (61) at a pressure of about 10 kPa, and was discharged from the liquid outflow section (62) released to the atmosphere.
When nitrogen at a pressure of 0.5 MPa was introduced from 3),
The water flow was almost zero. Further, the flow rate of water could be adjusted by changing the nitrogen pressure. That is, it was confirmed that the valve operated as an opening / closing valve and a flow control valve.

[Embodiment 6] In this embodiment, the micro device of the present invention in which the resin layer (X ') is sandwiched between the member (J') and the member (K ') each having a groove on the surface, The method for producing by the production method of the present invention in which the removal of the coated support is removal by dissolution is described.

[Preparation of Coated Support] Polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) was placed on the corona-treated side of a 30 μm-thick biaxially stretched polypropylene film (OPP film, manufactured by Nimura Chemical Co., Ltd.) having one surface subjected to corona discharge treatment. Apply a 20% aqueous solution (made by Kobekisha Co., Ltd., polymerization degree 2000),
After performing hot air drying and vacuum drying at 40 ° C., the film was peeled from the OPP film to form a polyvinyl alcohol film, which was used as a coating support.

[Preparation of Member (J'-6)] The polystyrene plate (4) in Example 1, the resin layer (5) having no defect, and FIG. A member having a concave portion having a shape similar to the shape in which the resin layer (X-1) having the three linear defects shown was laminated was prepared, and a member (J'-6) was prepared. .

[Preparation of Resin Layer (X ') Precursor] The coating support is a polyvinyl alcohol film, and the shape of the defect portion is the two hole-like defect portions shown in FIG. 38) The process of Example 2 except that the shape is the same as
A semi-cured coating film was formed in the same manner as in (i), (ii) and (iii).

After laminating the semi-cured coating film produced on the coated support on the member (J'-6), the coated support was dissolved and removed by washing with running water at 40 ° C. The precursor of the resin layer (X′-6) in the semi-cured state laminated on -6) was formed (steps (iv) and (v)).

[Preparation of member (K ')] Except that the shape of the concave portion on the surface is the same as that of the defective portion shown in FIG. A member (K'-6) was produced.

[Lamination and Adhesion of Member (K ')] The member (K'-6) is laminated on the precursor of the resin layer (X'-6), and irradiated with ultraviolet rays for 40 seconds (step (vi) )), The precursor of the resin layer (X'-6) was cured, and at the same time, the member (J'-6) and the member (K'-6) were bonded to the resin layer (X'-6).

[Formation of Other Structures] Then, the embodiment 1
In the same manner as described above, a stainless steel pipe is bonded to the end of each flow passage to form an inflow portion and an outflow portion, thereby forming a flow channel structure similar to that of the microdevice (D-4) shown in FIGS. 7 and 8. (D-6).

[Embodiment 7] In this embodiment, a micro device of the present invention in which two layers of a resin layer (X ') are laminated on a member (J') having a groove on the surface is coated on a coating support. Described below is an example of production by the production method of the present invention, in which removal is removal by dissolution.

[Coating support, member (J'-7)] In the same manner as in Example 6, a coating support of a polyvinyl alcohol film was prepared. Further, as the member (J '), the member of Example 6
The same material as (J'-6) was used, and a member (J'-7-1) was used.

[Production of member (J'-7-1) -resin layer (X'-7-1) laminate] The member (J'-6) of Example 6 A member exactly the same as the resin layer (X'-6) laminate was prepared, and a laminate of the member (J'-7-1) and the resin layer (X'-7-1) precursor was obtained.

[Formation of Resin Layer (X'-7-2)] A laminate of the member (J'-7-1) and the resin layer (X'-7-1) precursor was newly added to the member (J'-7-1). 7-2), and the resin layer was formed by the same operation except that the shape of the defective portion was the same as that of the concave defective portion of the member (K'-6) of Example 6.
(X'-7-1) resin layer on the precursor (X'-7-2) laminated precursor,
The member (J'-7-2) was used.

[Lamination and Adhesion of Member (K'-7)] The polystyrene plate used in Example 6 was directly used as the member (K'-7).
This is laminated on the precursor of the resin layer (X'-7-2), and irradiated with ultraviolet rays for 40 seconds in this state, and the precursor of the resin layer (X'-7-1) and the resin layer (X'-7- 2) At the same time as curing the precursor, the member (J'-7),
The resin layer (X'-7-1), the resin layer (X'-7-2), and the member (K'-7) were bonded.

[Formation of Other Structures] Then, Embodiment 1
In the same manner as described above, a stainless steel pipe is bonded to the end of each flow passage to form an inflow portion and an outflow portion, thereby forming a flow channel structure similar to that of the microdevice (D-4) shown in FIGS. 7 and 8. (D-7).

[Embodiment 8] In this embodiment, an example of manufacturing a microdevice of the present invention having a valve and functioning as a pump by the manufacturing method of the present invention will be described.

[Preparation of member (J'-8-1)] Polystyrene (Dick Styrene X manufactured by Dainippon Ink and Chemicals, Inc.)
C-520 ") and a composition (x-1 ') was applied thereto using a 5 cm x 5 cm x 3 mm thick plate as a substrate (71),
Ultraviolet rays were irradiated for 1 second without a photomask to form a semi-cured coating film (72) having no defect.

Further, the composition (x-1) was applied thereon, and a portion other than the portion formed as the defective portion (74) shown in FIG. 11 was irradiated with ultraviolet rays for 3 seconds using a photomask. The uncured composition (x-1) in the irradiated area was removed with methanol to form a coating having a width of 100 μm and a gap of 0.6 m on the surface as a defective part of the coating film.
a resin layer (73) in which two concave cutouts (74) and (74 ') having a length of 10 mm and arranged in series with an interval of m
Was formed. The concave defects (74), (7)
4 ′) 3 mm diameter through holes (75) at both ends,
(75 ') was punched to form a member (J'-8-1).

[Formation of Resin Layer (X'-8-1)] As shown in FIG. 12, two holes 100 mm and 600 μm in diameter with a center-to-center distance of 1 mm were formed. Except for the shape (77) and (77 ′), a defect of the above shape is formed on the member (J′-8-1) by the coating support peeling method in the same manner as in Example 1. Resin layer (X'-8-1) (76)
To form a member (J'-8-2).

[Formation of Resin Layer (X'-8-2)] The use of the composition (x-3) as the composition (x) and the shape formed with the deficient portion were as shown in FIG. And a tongue-shaped valve (80), (80 ') having a diameter of 400 μm and provided with a center distance of 1 mm.
A horseshoe (79) with a width of 100 μm around the part
(79 ') except that (79')
A semi-cured coating was formed on a coating support (not shown).

Next, using a photomask, the tongue-shaped valve (8) surrounded by the horseshoe-shaped defects (79) and (79 ') is used.
0) and (80 ') were further irradiated with ultraviolet rays for 20 minutes.
Irradiation was performed for 2 seconds to cure the irradiated portion of the composition (x-3), and the other portions were kept in a semi-cured state [step (iii ′)]. In the same manner as in Example 6, a structure in which the resin layer (X'-8-2) (78) was laminated on the member (J'-8-2) by the dissolution and removal method of the coated support was used. This was used as a member (J'-8-3).

[Formation of Resin Layer (X'-8-3)] Two large and small holes (82) were formed on the resin layer (X'-8-2) of the member (J'-8-3). (8
2 ′) is positioned at the hole (77) of the resin layer (X′-8-1) (76),
(77 '), except that the resin layer (X'-
8-1) In the same manner as in (76), the resin layer shown in FIG.
(X'-8-3) (81) was prepared and laminated, and this was used as a member (J'-8-).
4).

[Formation of Resin Layer (X'-8-4)] Deletion (84)
Is a resin layer (X'-8-1) except that it is a linear shape having a length of 1.5 mm and a width of 700 μm as shown in FIG.
In the same manner as (76), the resin layer (X'-8-4) (83)
This was laminated on the resin layer (X'-8-3) (81) of (J'-8-4) to obtain a member (J'-8-5).

[Formation of Intermediate Layer] Except that the member (J'-8-5) was used instead of the member (J'-5-2), the same procedure as in the formation of the intermediate layer (56) in Example 5 was carried out. Then, on the resin layer (X'-8-4), an intermediate layer (85) (diaphragm layer) formed of a flexible material and having no defect was laminated and bonded.

[Preparation and Adhesion of Member (K'-8)] The shape of the concave defect portion (88) was 1.5 m long as shown in FIG.
m, a straight line with a width of 700 μm, a length of 10 mm, and a width of 300 μm
The member (J ′) except that it has a T-shape consisting of a straight line of m and a hole-shaped defect (89) penetrating the member is provided at one end of the concave defect having a width of 300 μm. -8-1)
A member (K'-8) similar to that of was prepared in the same manner as the member (J'-8-1). That is, the member (K'-8) is made of a polystyrene base material (8
6) and a resin layer (87) having a defective portion (88).

Next, the member (K'-8) was replaced with a defective portion (8
8) is layered on the intermediate layer (85) by aligning the intermediate layer (85) with the position facing the defect (84) of the resin layer (X'-8-4) with the intermediate layer (85) therebetween, and irradiating ultraviolet rays for 30 seconds. By irradiation, it adhered to the intermediate layer (85) to form the intermediate layer (85) as a diaphragm. In addition, the other resin layers were sufficiently cured by the ultraviolet irradiation.

[Formation of Inflow / Outflow Portion] Member (J'-8) and Member
Holes (75), (75 '), (89) provided in (K'-8)
, A vinyl chloride tube having an outer diameter of 3 mm is bonded with an epoxy-based adhesive to form a liquid inflow portion (90), a liquid outflow portion (91),
And a gas introduction part (92) to form a microdevice
(D-8) was prepared. FIG. 17 is a schematic diagram of a plan view of the manufactured microdevice, and FIG. 18 is a schematic diagram of an elevation view.

[Liquid feeding test] When water was introduced from the liquid inflow section (90), the water was released to the atmosphere.
Spilled from 1). Conversely, even if water was introduced into the liquid outlet (91), it did not flow out of the liquid inlet (90). Next, when nitrogen at a pressure of 0.5 MPa was intermittently introduced into the gas introduction section (92), water was sucked in from the liquid inflow section (90) and flowed out from the liquid outflow section (91). That is, the microdevice operated as a pump.

[Embodiment 9] In this embodiment, an example of a microdevice having a diaphragm valve function and having a structure in which a diaphragm is in contact with an adjacent member but not bonded thereto, and a method of manufacturing the same will be described.

[Preparation of Micro Device] Resin layer (X-5-
The shape of the non-irradiated portion of 1) is two holes corresponding to the liquid inflow portion (61) and the liquid outflow portion (62), and the resin layer (X
After removing the uncured resin in the non-irradiated portion of -5-1) and before laminating the intermediate layer (56), the resin layer (X-5
-1) irradiate ultraviolet rays to the part corresponding to the non-irradiated part,
The portion was cured, and the portion serving as the diaphragm of the intermediate layer (56), that is, the shape of the cavity (53) of Example 5 was irradiated with ultraviolet rays to cure the irradiated portion. ) Is a member in the micro device of the present invention.
(K ''), except that it corresponds to (K '').
A micro device similar to that produced in Example 5 was produced except that the thickness of the cavity (53) in Example 5 was zero.

[Water flow test] Water was introduced from the liquid inflow section (61) at a pressure of about 5 kPa, but water did not flow out of the liquid outflow section (62) released to the atmosphere. 15 kPa pressure
When it was raised, the water flowed out of the liquid outlet (62). In this state, 0.5M from the gas introduction part (63)
When nitrogen at a pressure of Pa was introduced, the flow rate of water became zero. Also, the flow rate of water could be adjusted by changing the nitrogen pressure. That is, it was confirmed that the valve operated as a check valve, an opening / closing valve, and a flow control valve.

[0249]

The present invention relates to a method for manufacturing a micro device having a fine capillary cavity formed as a defect in a very thin layer that is easily broken, and particularly to a method for manufacturing a three-dimensionally formed complicated flow path. Providing a highly productive manufacturing method of a micro device, and a plurality of resin layers are laminated, fine capillary cavities penetrate through each layer and communicate with each other, and three-dimensionally intersect fine capillary tubes A multifunctional microdevice having a flow path, a space to be a reaction tank, a diaphragm valve, a valve structure, and the like can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of a coating support and a resin layer (X-1) used in Examples 1 and 3 as viewed from a direction perpendicular to the surface.

FIG. 2 is a schematic plan view of the microdevice of the present invention manufactured in Example 1 and Example 3. FIG.

FIG. 3 is a schematic diagram of a partially enlarged elevation view of the microdevice manufactured in Example 1 and Example 3.

FIG. 4 shows a coating support and a resin layer (X′-4-
It is a schematic diagram of the top view of 1).

FIG. 5 shows a coating support and a resin layer (X'-4-) used in Example 4.
It is a schematic diagram of the plan view of 2).

FIG. 6 shows a coating support and a resin layer (X'-4-) used in Example 4.
It is a schematic diagram of the plan view of 3).

FIG. 7 is a schematic plan view of a micro device manufactured in Example 4.

FIG. 8 shows the micro device produced in Example 4;
It is a schematic diagram of the cross section in A part of.

FIG. 9 is a schematic diagram of a plan view of a micro device manufactured in Example 5.

FIG. 10 is a schematic diagram of a cross-sectional view of the micro device manufactured in Example 5 taken along a section A in FIG. 9;

FIG. 11 is a schematic plan view of the member (J′-8-1) manufactured in Example 8 as viewed from a direction perpendicular to the surface on which the defect is formed.

FIG. 12 is a schematic plan view of a resin layer (X'-8-1) and a resin layer (X'-8-3) manufactured in Example 8.

FIG. 13 is a schematic plan view of a resin layer (X′-8-2) manufactured in Example 8.

FIG. 14 is a schematic plan view of a resin layer (X′-8-4) manufactured in Example 8.

FIG. 15 is a plan view of an intermediate layer (diaphragm layer) manufactured in Example 8.

FIG. 16 is a schematic plan view of a member (K′-8) manufactured in Example 8 as viewed from a direction perpendicular to a surface on which a defect is formed.

FIG. 17 is a schematic plan view of the microdevice manufactured in Example 8.

FIG. 18 is a schematic view of a cross-sectional view of the micro device manufactured in Example 8 taken along a section A in FIG. 17;

[Explanation of symbols]

1: coated support 2: coated film, semi-cured coating film 2: resin layer (X-1) precursor, resin layer (X-1) 3: non-exposed area, semi-cured coating film defective area 3 ': Cavity 4: Base material of member (J-1) 5: Resin layer of member (J-1) 6: Base material of member (K-1) 7: Coating film of member (K-1), resin layer 8: Inflow portion 9: Outflow portion 31: Coating support 32: Resin layer (X'-4-1) 33: Non-exposed portion, defective portion of semi-cured coating film 33 ′: Defected portion 34: Non-exposed portion, semi-cured portion Defective portion of coating film 34 ': Defective portion 35: Base material of member (J-4) 36: Coating film of member (J-4), resin layer 37: Resin layer (X'-4-2) 38: Non Exposed portion, defective portion of coating 38 ': defective portion, interlayer connection 39: resin layer (X'-4-3) 40: non-exposed portion, defective portion of coating 40': defective portion 41: member (K -4) Base material 42: Resin layer of member (K-4) 43: Inflow portion 44: Outflow portion 45: Inflow portion 46: Outflow portion 52: Resin layer (X′-5-1) 53 Defective part 54: Base material of member (J-5) 55: Resin layer of member (J-5) 56: Intermediate layer 57: Resin layer (X'-5-2) 58: Defective part 59: Member (K- 5) Base material 60: Resin layer of member (K-5) 61: Liquid inflow portion 62: Liquid outflow portion 63: Gas introduction portion 71: Base material of member (J'-7-1) 72: Member (J) Resin layer without defect in '-7-1) 73: Resin layer with defect in member (J'-7-1) 74: Depressed defect in member (J'-7-1) 75 , 75 ': Through hole of member (J'-7-1) 76: Resin layer (X'-8-1) 77, 77': Hole-shaped defect 78: Resin layer (X'-8-2) 79, 79 ': Horseshoe-shaped defect 80, 80': Valve 81: Resin layer (X'-8-3) 82, 82 ': Porous defect 83: Resin layer (X'-8-4) 84 : Defective portion 85: Intermediate layer 86: Base material of member (K'-7) 87: Resin layer of member (K'-7) 88: Depressed defective portion of member (K'-7) 89: Member (K) '-7) Porous defect 90: liquid Inlet 91: Liquid outflow section 92: gas introduction portion

Front page of the continued F-term (reference) 4F100 AK01B AK01C AK01D AK02B AK02C AK02D AK12A AK12E AK25A AK25B AK25C AK25D AK25E AK41A AK41E AK45A AK45E AK54B AK54C AK54D AK55A AK55E AL01B AL01C AL01D AL05B AL05C AL05D AT00A AT00E BA05 BA07 BA10A BA10E BA32A BA32B BA32C BA32D BA44B BA44C BA44D DC12B DC12C DC12D DD01A DD01E DD21 DD27 DD28 EC042 EG001 EH032 EH461 EJ081 EJ082 EJ301 EJ303 EJ33A EJ33E EJ333 EJ541 EJ542 EJ581 GB51 GB90 JB06B JB06C JB06D JB14JB02JB02JB02JB02

Claims (34)

[Claims] The method includes the following steps, comprising one or more resin layers (X) having a defective portion, wherein the resin layer is laminated with another member or another resin layer (X), Forming a cavity,
A method for manufacturing a micro device having a laminated structure. (I) An active energy ray polymerizable compound (a)
Applying an active energy ray-curable composition (x) containing: (i) forming an uncured coating film (i), (ii) applying an active energy ray to the uncured coating film other than the portion to be formed as a defective portion Irradiate and make the uncured coating of the irradiated part non-flowable or hard-flowing,
And semi-cured to the extent that unreacted active energy ray polymerizable functional groups remain, a step (ii) of forming a semi-cured coating film,
(Iii) the uncured composition of the non-irradiated portion from the semi-cured coating film (x)
To obtain a semi-cured coating film having a defective portion of the coating film
(iii), (iv) the semi-cured coating film having the defective portion is replaced with another member (J)
(Iv), (v) forming the resin layer (X) and transferring the resin layer (X) to the member (J) by removing the coated support from the resin layer (X). ), And (vi) after the step (iv) and before the step (v), or after the step (v), or before and after the step (v), the semi-cured resin layer (X) The resin layer (X) is further cured by irradiation with active energy rays, and the resin layer (X) is
Step (vi) of bonding to (J). 2. The method according to claim 1, wherein the removal of the coating support in the step (v) comprises:
The method for producing a microdevice according to claim 1, wherein the removal is performed by dissolving the coated support. 3. Step (vi) is before step (v), and step (v)
The method for producing a microdevice according to claim 1, wherein the removal of the coating support in step (c) is peeling. 4. Steps (i), (ii), (iii), (iv) and (v)
Or after performing steps (i), (ii), (iii), (iv), (v),
And (vi) or after performing steps (i), (ii), (iii), (i
v), (vi), and (v), after performing in this order, the resin layer (x)
By using the laminated member (J) instead of the member (J) in the step (iv), by repeating the steps (i) to (v) or the steps (i) to (vi), the resin layer (X The method for manufacturing a micro device according to claim 1, wherein a plurality of are stacked. 5. A plurality of resin layers (X) are laminated so that at least a part of their defective portions are overlapped to form a cavity in which the defective portions of the plurality of resin layers (X) are connected in a laminate. The method for manufacturing a micro device according to claim 1. 6. The member (J) has a defective portion penetrating the member, or a member having a concave defect portion on the surface, or has a defective portion penetrating the member and a concave defect portion on the surface. The member (J) and the resin layer (X) so that at least a part of the defect portion of the member (J) and the defect portion of the resin layer (X) overlap with each other.
The method for manufacturing a microdevice according to claim 1, wherein a void is formed in the laminate by connecting the defective portion of the member (J) and the defective portion of the resin layer (X) by laminating the components. 7. The method according to claim 7, wherein the step (vi) is after the step (v) and the step (v)
In (i), another member (K) is brought into contact with the resin layer (X) in a semi-cured state, and in that state, an active energy ray is irradiated to bond the resin layer (X) to the member (J) and at the same time, 2. The method for manufacturing a micro device according to claim 1, wherein the micro device is adhered to the member (K). 8. The member (K) has a defective portion penetrating the member and / or a concave defective portion on the surface, and at least the defective portion of the member (K) and the defective portion of the resin layer (X) By laminating the member (K) and the resin layer (X) so as to partially overlap each other, a cavity is formed in the laminate in which the defective portion of the member (K) and the defective portion of the resin layer (X) are connected. The method for manufacturing a micro device according to claim 7. 9. One or more selected from {between step (i) and step (ii), between step (ii) and step (iii), and between step (iii) and step (iv)}. During the process, by irradiating a part of the resin layer (X) with an active energy ray and performing a partial curing in which the irradiated portion is cured to the extent that it does not adhere to other members in the step (iv), The method for manufacturing a microdevice according to claim 1, wherein a portion which is in contact with another member or a resin layer but is not adhered is formed in the layer (X). 10. Irradiation of active energy rays in the step (ii) into a shape for forming a valve, a structure serving as a valve is provided in a part of the resin layer (X), and a part to be partially cured is a resin layer. The method for manufacturing a microdevice according to claim 9, which is a portion serving as a valve of (X). 11. The resin layer (X) has a thickness of 1 to 1000 μm.
The method for manufacturing a micro device according to claim 1, wherein 12. The minimum width of the defective portion of the resin layer (X) is from 1 to 1.
The method for manufacturing a micro device according to claim 1, wherein the thickness is in a range of 000 µm. 13. An active energy ray polymerizable compound (a)
Is a compound having two or more active energy ray-polymerizable functional groups in one molecule. 14. An active energy ray polymerizable compound (a)
Is a compound having an acryloyl group or a maleimide group. 15. An active energy ray-curable composition (x)
However, the homopolymer contains a hydrophobic active energy ray polymerizable compound (a) showing a contact angle with water of 60 degrees or more, and an amphiphilic polymerizable compound (b) copolymerizable therewith. 2. The method for manufacturing a micro device according to claim 1, wherein: 16. The method according to claim 15, wherein the amphiphilic polymerizable compound (b) is a compound containing a polyethylene glycol chain having 6 to 20 repetitions and an alkyl group having 6 to 20 carbon atoms in the molecule. A manufacturing method of the microdevice according to the above. 17. The member (J) is formed of a polymer selected from the group consisting of a styrene polymer, a (meth) acrylic polymer, a polycarbonate polymer, a polysulfone polymer, and a polyester polymer. The method for manufacturing a microdevice according to claim 1, wherein 18. A member selected from a member having a defect portion penetrating the member, a member having a concave defect portion on the surface, or a member having a defect portion penetrating the member and a member having a concave defect portion on the surface. ')｝, One or more layers of the active energy ray-curable resin layer (X') having a defect in a part of the layer, and the minimum width of the defect is 1 to 1000 µm; A member having a defect portion penetrating the member, a member having a concave defect portion on the surface, or a member selected from a member having a concave defect portion on the surface and a member having a concave defect on the surface (K ′)｝ is laminated. A micro device having a laminated structure, wherein at least two or more defective portions in a member are connected to form a cavity. 19. A member (J ′), a resin layer (X ′), and a member (K ′)
20. The microdevice according to claim 18, wherein one or more members selected from the group consisting of one or more linear cavities provided in a direction parallel to a stacking surface of the members. 20. The thickness of the resin layer (X ′) having a deficient portion,
The micro device according to claim 18, which has a thickness of 5 to 1000 m. 21. A part of the cavity is a fluid flow path, and a plurality of flow paths formed in different resin layers (X ′) or branched flow paths are three-dimensionally separated by the resin layer (X ′). 19. The micro device according to claim 18, which intersects. 22. A member (J ′), a resin layer (X ′), and a member (K ′)
The microdevice according to claim 18, further comprising a portion that is in contact with, but not adhered to, another member stacked adjacent to a part of one or more members selected from the group consisting of: 23. A structure that serves as a valve by providing at least a part of one layer of the resin layer (X ′) with a part of a peripheral part being a defective part, 23. The microdevice according to claim 22, wherein a portion that is in contact with but not adhered to the member is a valve. 24. The micro device according to claim 23, wherein two or more structures serving as valves are provided in one resin layer (X ′). 25. A resin layer (X ′) provided with a valve structure
23. The micro device according to claim 22, wherein the micro device is made of a material having a lower tensile modulus than a member or a resin layer sandwiching the material. 26. An active energy ray-curable resin layer (X ′)
Is a cured product of an active energy ray-curable composition containing a (meth) acryloyl group-containing compound. 27. A member (J ′), a resin layer (X ′), and a member (K ′)
One or more members selected from the above are members in which one side is a diaphragm, the other side is directly laminated with another member having a defective portion, and the defective portion is laminated to form a cavity, and the diaphragm and The other member laminated on the back surface of the member has an inlet or an outlet to the cavity, or has a hole-shaped defective portion serving as both, and at least one of the inlet and the outlet is provided with the member. The diaphragm is formed on the opposing surface of the diaphragm, and its periphery is not in contact with the diaphragm. ,
The micro device according to claim 18. 28. The microdevice according to claim 18, wherein the active energy ray-curable composition contains an amphiphilic active energy ray-polymerizable compound copolymerizable with the active energy ray-polymerizable compound. 29. The compound according to claim 28, wherein the amphiphilic active energy ray-polymerizable compound is a compound containing a polyethylene glycol chain having 6 to 20 repetitions and an alkyl group having 6 to 20 carbon atoms in the molecule. A microdevice as described. 30. The micro device according to claim 18, wherein a part or all of the cavity is a fluid flow path. 31. A member selected from a member having a defect portion penetrating the member, a member having a concave defect portion on the surface, or a member having a defect portion penetrating the member and a member having a concave defect portion on the surface. ')｝, One or more layers of the active energy ray-curable resin layer (X') having a defect in a part of the layer, and the minimum width of the defect is 1 to 1000 µm; The member (K '') that forms the diaphragm without the
At least two of the member (J ′) and the resin layer (X ′) having a portion that is in contact with, but not adhered to, another member laminated adjacent thereto, and that portion is a diaphragm portion. A micro device having a laminated structure, in which the above-mentioned defective portions are connected to form a cavity. 32. The defective portion of one or more members of the member (J ′) and the resin layer (X ′) is a hole-shaped defective portion serving as an inlet or an outlet or both of them, 32. The flow channel according to claim 31, wherein at least one of the inlet and the outlet is formed on the opposite surface of the diaphragm, and its periphery is in contact with the diaphragm but is not adhered, and the flow path is opened by deformation of the diaphragm. Micro device. 33. The diaphragm according to claim 1, wherein the thickness of the diaphragm is 1-50.
33. The microdevice according to claim 27, 31 or 32, wherein the microdevice is formed of a material having a tensile elasticity of 1 μm and a tensile modulus of 1 to 700 MPa. 34. A micro device manufactured by the manufacturing method according to claim 1.