JP2002370200A - Method of manufacturing miniature valve mechanism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a diaphragm type miniature valve mechanism for efficiently forming a diaphragm by being adhered to the other member by incorporating a very thin, flexible, and handling difficult thin film into the miniature valve mechanism as a diaphragm film. SOLUTION: This manufacturing method of the diaphragm type miniature valve mechanism is characterized in that a diaphragm forming material composed of a liquid resin composition is developed on a liquid surface, a thin film-like member formed by solidifying this material is sandwiched and adhered between two members having a defective part in a part of a surface or having the defective part by penetrating through the member, the thin film-like member is formed as the diaphragm, and the respective defective parts are formed as a cavity partitioned by the diaphragm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a micro-diaphragm type valve, that is, a diaphragm which is deformed by changing the pressure on one side of a cavity partitioned by the diaphragm, and which changes the fluid flow passing through the other side of the cavity. A method of manufacturing a micro valve mechanism for adjusting.

More specifically, a thin film-like member formed by spreading a diaphragm-forming material made of a liquid resin composition on a liquid surface and solidifying the same is provided with a defective portion on a part of its surface, or The present invention relates to a method for manufacturing a micro valve mechanism, wherein a diaphragm is formed by laminating and adhering in a shape sandwiched between two plate-shaped members having a defect portion penetrating through the diaphragm.

[0003] The microvalve mechanism produced by the manufacturing method of the present invention is used in combination with a microchemical device in which a structure such as a microchannel, a reaction tank, an electrophoresis column, and a membrane separation mechanism is formed in a member. Or formed as part of the chemical device.

More specifically, microreaction devices (microreactors) for chemistry, biochemistry, etc .; microanalysis devices such as integrated DNA analysis devices, microelectrophoresis devices, microchromatography devices, mass spectra, liquid chromatography, etc. It is used as a part of, or in combination with, a microvalve mechanism useful as a microdevice for preparing an analytical sample, a physicochemical processing device such as extraction, membrane separation, and dialysis.

[0005]

2. Description of the Related Art The journal "Science" (Vol. 288, p. 113, 2000) discloses that a liquid channel is formed entirely of silicon rubber and is formed with a diaphragm separated from the channel. A microvalve mechanism having a pressurized cavity is described. Then, a method is described in which compressed air is introduced into a pressurizing cavity, a silicon rubber diaphragm is deformed and extruded toward a flow path side to change a flow path cross-sectional area, thereby adjusting a flow rate of a liquid.

However, since this minute valve mechanism is made of a flexible material having low rigidity, the pressure resistance is low. In addition, this microvalve mechanism is made of a hydrophobic material, easily adsorbs biochemical substances such as proteins and enzymes, and its use in the biochemical field is limited. Furthermore, this micro valve mechanism requires time for manufacture and has low productivity.

[0007]

The problem to be solved by the present invention is that a very thin, flexible and difficult to handle thin film is incorporated into a minute valve mechanism as a diaphragm film.
Glue with other members to form a diaphragm efficiently,
An object of the present invention is to provide a method of manufacturing a diaphragm type micro valve mechanism.

[0008]

Means for Solving the Problems As a result of intensive studies on a method for solving the above-mentioned problems, the present inventors have found that a deformable diaphragm, which is a component of a minute valve mechanism, is formed by a thin film formed by a liquid surface spreading method. It is possible to easily form a diaphragm-type minute valve mechanism by sandwiching and laminating between two other members as a thin film without processing into a shape of a minute diaphragm portion. The present inventors have found that the problem can be solved more advantageously by using a solution of a chain polymer or an energy ray-curable resin composition as a material to be spread over the surface, and have completed the present invention.

That is, according to the present invention, a thin film-like member formed by spreading a diaphragm-forming material comprising a liquid resin composition on a liquid surface and solidifying the same is provided with a defective portion on a part of the surface. Alternatively, the thin film-shaped member is formed into a diaphragm by sandwiching and bonding between two members having a defective portion penetrating the member, and each defective portion is formed as a cavity partitioned by the diaphragm. Characterized by
Provided is a method for manufacturing a diaphragm type micro valve mechanism.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a method for manufacturing a diaphragm type micro valve mechanism. The diaphragm type micro valve mechanism referred to in the present invention is a micro valve mechanism that deforms the diaphragm by changing the pressure on one side of the cavity partitioned by the diaphragm and adjusts the flow rate of the fluid flowing on the other side of the cavity. Means

The outer shape of the microvalve mechanism of the present invention, that is, the outer shape of the member to which the diaphragm is fixed is not particularly limited, and can take a shape according to the purpose of use. The outer shape of the member may be, for example, a sheet shape (including a film shape, a ribbon shape, and the like; the same applies hereinafter), a plate shape, a coating film shape, a rod shape, a tube shape, and a molded product having a complicated shape. It is particularly preferable that the shape is plate-like or rod-like.

The component may be configured as a composite of a plurality of the same or different materials. Hereinafter, for the sake of simplicity of description, “sheet shape” includes “sheet shape”. When the microvalve mechanism of the present invention is in the form of a plate, its thickness is arbitrary, but is preferably 20 μm to 20 mm.
And more preferably 100 μm to 2000 μm. If the thickness is too small, manufacturing becomes difficult, and if the thickness is too large, the merit as a minute valve mechanism decreases.

The microvalve mechanism manufactured by the manufacturing method of the present invention includes: a surface on which a defective portion A is formed on a member (member A) having a concave portion on the surface or a defective portion (defective portion A) penetrating the member; In addition to this, the surface of the member (member B) having a concave portion or a defective portion (defective portion B) penetrating through the member is formed on the surface of the thin film-like member (member C) constituting the diaphragm. ) Are bonded to each other to form a cavity (cavity A) between the defective portion A and the member C, and a cavity (cavity B) between the defective portion B and the member C. B and B are formed at positions opposite to each other across a diaphragm made of member C, and cavity A is provided with an inlet (inlet A) and an outlet (outlet A).
Has a connection port (connection port B).

Alternatively, the cavity (A) may be directly open to the outside of the microvalve mechanism without being connected to the flow path. In this case, the flow path A and the flow path B are connected to the main valve. Since it can be considered that the micro valve mechanism is provided outside the mechanism, a case where the present micro valve mechanism has the flow path A and the flow path B in the present micro valve mechanism will be described below.

The relative position and shape of the valve structure of the microvalve mechanism of the present invention, that is, the relative positions and shapes of the cavity A, the cavity B, the diaphragm, the inlet A, the outlet A, and the inlet B are controlled through the channel B. Any structure can be used as long as the diaphragm can be deformed by the pressure change and the volume change of the cavity B to change the gap size of the cavity A and adjust the flow rate of the fluid flowing through the flow path A.

The outer shape of the member A does not need to be particularly limited.
It can take a shape according to the purpose of use. The shape of the member A is the same as the description regarding the shape of the member to which the diaphragm is fixed. The member A may be composed of a composite of a plurality of the same or different materials, for example, a laminate.

The thickness of the member A is arbitrary, but is preferably 10 μm to 10 mm, and more preferably 50 μm to 10 μm.
1 mm. If the thickness is too small, manufacturing becomes difficult,
If it is excessively large, the withstand pressure decreases, and the merit as a minute valve mechanism decreases. The shape and dimensions of the member B are the same as those of the member A.

The shapes and dimensions of the deficient portions A and B can be designed so that the cavities A and B have the desired dimensions. Normally, the shapes and dimensions of the defective portions A and B are substantially the same as those of the cavities A and B, respectively.

The shape of the cavities A and B can be arbitrary as viewed from the direction perpendicular to the bonding surface between the members A and B, but the aspect ratio is preferably close to 1, and the circle, ellipse and rectangle are preferable. (Including a rectangle with rounded corners; the same applies hereinafter). The diameter of each of the cavities A and B is preferably 1 μm to 1 μm when viewed from a direction perpendicular to the bonding surface between the members A and B.
000 μm, more preferably 5 μm to 500 μm. Here, the diameter refers to a diameter converted into a circle having the same area when the shape of the cavity is other than a circle. The diameters of the cavities A and B need not be the same, but are preferably close to each other or the same.

The depths (dimensions from the surface) of the cavities A and B viewed from a direction perpendicular to the bonding surface between the members A and B are preferably 0 (however, not bonded) to 1000 μm, more preferably 5-500 μm
It is. If the cavity is larger than these dimensions, it is not preferable because the merit as the micro valve mechanism is reduced. The cavity A preferably has a maximum height / maximum width ratio of 1 or less. When this ratio exceeds 1, it is difficult to completely close the valve, that is, to make the gap of the cavity A zero.

If the valve is of the normally-closed type and this gap is pushed open by the fluid entering through the inlet, this ratio is zero (but not glued).
May be. Otherwise, this ratio is 0.05
To 1, more preferably 0.1 to 0.5. The ratio of the cavities B is arbitrary. For example, 1
It may be 000 or conversely zero (but not bonded).

The height of the cavities A and B need not be constant, but may be different depending on the location within the cavities.
It is preferable that the cavity A has a portion with a low height, that is, a portion with a narrow gap, because it can be completely closed.

The cavities A and B viewed from the direction perpendicular to the bonding surface between the members A and B need not have the same shape, but preferably have substantially the same shape. The cavity A and the cavity B are provided at positions facing each other with the diaphragm interposed therebetween, but the relative positions may be shifted, and it is only necessary that the cavities overlap. However, it is preferable that the relative positions completely match.

The flow path A is a flow path through which a fluid to be flow-adjusted flows. If the cavity A is on the way, its dimension and shape are arbitrary. However, the connection between the channel A and the cavity A, ie the inlet A and / or the outlet A, may be the same as the diameter of the cavity, but at least one of them is preferably smaller than the diameter of the cavity. . The flow path A may communicate with the outside of the microvalve mechanism of the present invention, or may not communicate with the outside, but may communicate with another structure in the device.

The connection port B controls the pressure and volume of the cavity B therethrough to deform the diaphragm to open and close the valve. The fluid passed through the flow path B is arbitrary, and may be a liquid or a gas. The change in pressure may be pressurized or depressurized. The channel B may be open to the outside of the micro valve mechanism, or may not open to the outside, and may communicate with another mechanism in the device, such as a gas generating unit or a gas absorbing unit. good. Channel B and connection B
May have any diameter.

In a preferred shape of the microvalve mechanism manufactured by the manufacturing method of the present invention, at least one of the inlet A and the outlet A is formed on the opposite surface of the diaphragm in the cavity A, and the cavity B is added. The diaphragm deformed by being pressed has a structure capable of closing the inflow port A and / or the outflow port A over the entire circumference. The diaphragm may block one or both of the inlet A and the outlet A.

Therefore, the diameter of the inlet A and / or the outlet A to be closed by the deformed diaphragm needs to be smaller than the diameter of the cavity A. Such an inlet A and / or
Alternatively, the outlet A can be obtained by forming the flow path A as a hole formed in the member A from within the defect A. In such a structure, the height of the cavity A is uniform,
Alternatively, a structure in which the peripheral portion to be closed by the diaphragm is high is preferable.

In the above description, the inflow port A or the outflow port A which is not blocked by the diaphragm is formed by a groove (in which the flow path A communicates with the defective portion A formed on the surface of the member A where the defective portion A is formed). It is preferably formed with the groove A) and the member C. That is, a part of the circumference of the inflow port A or the outflow port A is constituted by the member C.

In the micro valve mechanism manufactured by the manufacturing method of the present invention, members other than the diaphragm, for example, member A,
The members B may be formed of arbitrary materials, respectively, and may be formed of the same material or different materials. For example, glass, crystals such as quartz, metals such as stainless steel, semiconductors such as silicon, ceramics, carbon, and organic polymers (those containing an inorganic element such as polydimethylsiloxane. Polymer ").

Of these, polymers are preferred in many applications in terms of moldability, adhesion, price, productivity, and the like. The polymer may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. In terms of productivity, the polymer is preferably a thermoplastic polymer or a solidified energy ray-curable composition.

By using a material having high hardness and strength for the member, the pressure resistance and strength can be increased. However, when a material having low hardness is used or when the thickness is reduced, the support member may be provided on a support. It is also preferable to form them. In particular, as the member B, it is preferable to use a material having a high pressure resistance or a structure having a high pressure resistance in terms of a mechanism for opening and closing the valve by pressurizing the flow path B and the cavity B provided in the member B. The material forming the members A and B preferably has a tensile modulus of 10
It is 0 MPa or more, more preferably 500 MPa or more, and most preferably 1 GPa. The upper limit of the tensile modulus is
Although there is a limit naturally, there is no inconvenience due to its highness, so there is no need to set an upper limit. For example, 100G
Pa or 500 GPa.

As the polymer that can be used for the member A or the member B, a polymer that can be used for the member C described below can be selected and used. The polymer that can be used for the member A or the member B is also preferably a solidified product of the energy ray-curable composition. The energy ray-curable composition is preferably a crosslinked polymer in order to increase strength and hardness. The energy ray-curable composition is also the same as that of the member C described below, except that the preferred tensile modulus is different. The energy ray-curable compound contained in the energy ray-curable composition can also be selected from those exemplified as the energy ray-curable compound that can be used for the member C and used.

In the member A or the member B, a defective portion, a groove, an inflow port,
The method of providing a structure such as an outlet is arbitrary, for example,
Photolithography; Injection molding; Hot pressing; Solvent casting; Drilling; Etching; Methods of forming by laser perforation, sand blasting, etc., and thin-film members or coatings formed by these methods and having a cutout penetrating the front and back. A method of laminating and bonding the film layer to another member can be employed.

Of these, a method in which a layer having a defective portion formed by a photolithographic method is formed and laminated with another layer to form a concave defective portion formed on the surface is preferable. That is, the energy ray-curable composition is applied on a substrate to form a coating-like shaped product, and the portions other than the portion formed as the defective portion are irradiated with energy rays to be solidified, and the non-irradiated portion is not solidified. The energy ray-curable composition is removed by an arbitrary method such as washing to form a coating film having a defective portion of the material (that is, a layered member formed on the substrate),
This is a method of laminating and bonding this to another layer.

After completely forming the member A and / or the member B, the member A and / or the member B may be laminated and adhered. Then, the member A and / or the member B may be completely formed. For example, when the member A is a laminate of a plurality of layers, one of the layers constituting the member A may be laminated and adhered to the member C, and then the other layers of the member A may be laminated and adhered. The order of laminating and bonding the member C between the members A and B is also arbitrary. The members A, B, and C may be bonded at a time in any order. You may adhere.

The member C has a thickness of the diaphragm, that is, 0.1 to 500 μm, preferably 1 to 200 μm.
m, more preferably in the range of 5 to 100 μm. Of course, when increasing the thickness of the diaphragm, it is necessary to use a material having a low elastic modulus, and the value of “tensile elastic modulus × thickness of the diaphragm” is 10 to 5000.
It is preferably in the range of 0 Pa · m,
More preferably, it is in the range of 00 Pa · m.

The thickness of the member C need not be uniform, but may be uneven or inclined. Although it depends on the diameter of the diaphragm and the hardness of the material, if it is smaller than this, it tends to be difficult to manufacture or maintain the open state, and if it exceeds this range, it will be difficult to open and close. Become.

The material of the member C is a material having flexibility enough to function as a diaphragm and can be formed into a thin film by a liquid surface spreading method by any method. It is preferred that The material forming the member C has a tensile modulus of 0.1 MPa to 1
It is in the range of 0 GPa, preferably 10 MPa to 7 GPa.

The material constituting the member C is JIS K-7
Elongation at break measured according to 127 is preferably 5%
Above, more preferably 10% or more. Although the upper limit of the elongation at break may naturally be limited, it is not necessary to provide an upper limit because it is high and there is no inconvenience due to itself, and may be, for example, 800%. In the present invention, JIS
Even a material showing a low elongation at break of 5 to 10% in a tensile test according to K-7127 is difficult to break in the method of use of the present invention, and even if a material having a deformation equal to or more than the elongation at break according to the above test is given. It can be used without breaking.

The polymer forming the member C may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. It may be a crosslinkable polymer. In terms of productivity, the polymer is preferably a thermoplastic polymer or a solidified energy ray-curable composition. Suppresses plastic deformation of the diaphragm,
In order to increase the durability of the valve, when the material forming the member C is a solidified product of the energy ray-curable composition,
The solidified product is preferably a crosslinked polymer.

Examples of the thermoplastic polymer usable for the member C include styrene polymers such as polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer, and polystyrene / acrylonitrile copolymer;
Polysulfone polymers such as porsulfone and polyether sulfone; (meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide polymers; cellulose polymers such as cellulose acetate and methyl cellulose;

Bisphenol A-based polycarbonate, bisphenol F-based polycarbonate, bisphenol Z
Polycarbonate-based polymers such as polycarbonate-based;
Polyolefin-based polymers such as polyethylene, polypropylene and poly-4-methylpentene-1; vinyl chloride;
Chlorine-containing polymers such as vinylidene chloride; polyurethane polymers; polyamide polymers; fluoropolymers;
Polyether-based or polythioether-based polymers such as 2,6-dimethylphenylene oxide; and polyester-based polymers such as polyethylene terephthalate and polyarylate.

Among these, styrene polymers, (meth) acrylic polymers, polycarbonate polymers, polysulfone polymers, and polyester polymers are preferred from the viewpoint of good adhesiveness.

Examples of the thermosetting polymer that can be used for the member C include a polyurethane polymer; a polyamide polymer; a polyimide polymer; an epoxy resin; a (meth) acrylic polymer; a polymaleimide polymer; And the like. In the polymer exemplified above alone, even if it is out of the preferable range of the tensile modulus as the member C,
It can be used by using a plasticizer or copolymerizing.

The polymer that can be used for the member C is also preferably a solidified product of the energy ray-curable resin composition. The energy ray-curable resin composition contains an energy ray-curable compound as an essential component, and may be an energy ray-curable compound alone or a mixture of a plurality of types of energy ray-curable compounds. The energy ray-curable resin composition is preferably a crosslinked polymer in order to increase strength and hardness. As the energy ray-curable compound, those which can be solidified in the absence of an energy ray polymerization initiator and those which are polymerized by energy rays only in the presence of an energy ray polymerization initiator can be used.

As the energy ray-curable compound, a compound having a polymerizable carbon-carbon double bond is preferable. Among them, a highly reactive (meth) acrylic compound, vinyl ethers, and the absence of a photopolymerization initiator are preferable. A maleimide-based compound that solidifies even below is preferred. The energy ray-curable compound that can be used for the member A or the member B can be selected from the compounds exemplified below that can be used for the member C and used.

The diaphragm may be a composite such as a laminate composed of different materials. In this case, the tensile modulus and the thickness of the composite are in the above ranges. As such a composite, for example, a laminate of a solidified product of an energy ray-curable composition and a thermoplastic polymer is also preferable, and a diaphragm formed of a thermoplastic polymer or a thermosetting polymer is preferably used. It is further preferable that a solidified layer of a low-adsorption energy-ray-curable composition is adhered (coated) to the member A side.

The material which can be formed into the composite is preferably a polymer having a low tensile modulus, such as silicone rubber; neoprene-based, chloroprene-based, niloryl-based, butadiene-based rubber; polyurethane, polyester elastomer, and polyamide elastomer. It is preferable that the elastomer is a flexible thermoplastic resin such as an ethylene-vinyl acetate copolymer.

The energy ray-curable composition used as the material of the diaphragm contains an energy ray-curable compound as an essential component, and may be used alone or as a mixture of a plurality of types of energy ray-curable compounds. It may be a mixture. Using such a solidified product of the energy ray-curable resin composition as the material of the diaphragm makes it easy to form a thin diaphragm, and it is easy to bond the thin diaphragm to other members. In a preferred embodiment of the present invention, it becomes easy to adhere the diaphragm to the members A and B without closing the defective portions and grooves formed in the members A and B, and the flexibility of the diaphragm Are easy to control, and they can be implemented with high productivity.

The solidified product of the energy ray-curable resin composition may be a chain polymer or a crosslinked polymer. However, if repeated durability or long-term durability is required, plastic deformation is suppressed. Since it is possible, it is preferable that the polymer is a crosslinked polymer. In order to make the solidified product of the energy ray-curable resin composition into a crosslinked polymer, in the energy ray-curable composition, in the case of an addition polymerizable compound, the polymerizable functional group is 2 or more, or In the case of a polycondensable compound, the method is carried out by including a monomer and / or oligomer having three or more polymerizable functional groups (hereinafter, having such a functional group is referred to as “polyfunctional”). it can.

The energy ray-curable composition is preferably a mixture of monofunctional monomers and / or oligomers for the purpose of adjusting the tensile modulus and improving the adhesiveness. The energy ray-curable compound constituting the energy ray-curable resin composition used as the material of the diaphragm may be any one such as radical polymerizable, anionic polymerizable, and cationic polymerizable. The energy ray-curable compound is not limited to one that polymerizes in the absence of a polymerization initiator, and one that is polymerized by an energy beam only in the presence of a polymerization initiator can be used.

As such an energy ray-curable compound, those having a polymerizable carbon-carbon double bond are preferable. Among them, highly reactive (meth) acrylic compounds and vinyl ethers, and photopolymerization initiators are preferable. A maleimide compound which solidifies even in the absence of is preferred.

Examples of the crosslinkable polymerizable (meth) acrylic monomer which can be preferably used as an energy ray-curable compound include, for example, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxy polyethyleneoxyphenyl) propane,

2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, neopentyl glycol dihydroxy dipivalate di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxy 2 such as ethyl isocyanurate and N-methylenebisacrylamide
Functional monomer;

Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate,
Trifunctional monomers such as caprolactone-modified tris (acryloxyethyl) isocyanurate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate;
Hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate are exemplified.

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

Examples of the maleimide-based crosslinkable polymerizable energy ray-curable compound include 4,4′-methylenebis (N-phenylmaleimide) and 2,3-bis (2,
4,5-trimethyl-3-thienyl) maleimide, 1,
2-bismaleimide ethane, 1,6-bismaleimide hexane, triethylene glycol bismaleimide, N,
N′-m-phenylenedimaleimide, m-tolylenedimaleimide, N, N′-1,4-phenylenedimaleimide,

N, N'-diphenylmethane dimaleimide, N, N'-diphenylether dimaleimide,
N'-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo-
Bifunctional maleimides such as [2,2,2] octane dichloride, 4,4'-isopropylidenediphenyl dicyanate.N, N '-(methylenedi-p-phenylene) dimaleimide; N- (9-acridinyl) maleimide A maleimide having a maleimide group and a polymerizable functional group other than the maleimide group is exemplified.

Examples of the maleimide-based cross-linkable polymerizable oligomer include polytetramethylene glycol maleimide alkylate such as polytetramethylene glycol maleimide capriate and polytetramethylene glycol maleimide acetate.

The maleimide-based monomer or oligomer is
These may be copolymerized with each other and / or with a compound having a polymerizable carbon-carbon double bond such as a vinyl monomer, a vinyl ether, or an acrylic monomer.

These compounds can be used alone or in combination of two or more. Some of the compounds exemplified above alone may have a solidified product outside the specified tensile modulus range. However, other copolymerizable compounds such as monofunctional (meth) acrylic monomers and other monofunctional compounds may be used. By mixing and using a monomer or a non-reactive compound such as a plasticizer, a tensile elastic modulus in a specified range can be obtained and used.

A photopolymerization initiator can be added to the energy ray-curable resin composition, if necessary. The photopolymerization initiator is not particularly limited as long as it is active with respect to the energy rays used and can polymerize the energy ray-curable compound. For example, a radical polymerization initiator, an anionic polymerization initiator And a cationic polymerization initiator. The photopolymerization initiator may be a polyfunctional or monofunctional maleimide compound.

Examples of the energy rays include light rays such as ultraviolet rays, visible light rays, and infrared rays; ionizing radiation rays such as X-rays and gamma rays; and particle rays such as electron rays, ion beams, beta rays, and heavy particle rays.

Further, the energy ray-curable resin composition comprises:
It may contain other components such as a solvent, a modifier, and a coloring agent. Examples of the modifying agent that can be contained in the energy ray-curable resin composition include anionic, cationic, and nonionic surfactants; hydrophilic agents such as hydrophilic polymers such as polyvinylpyrrolidone; And a plasticizer for adjusting the elastic modulus. Examples of the colorant that can be contained in the energy ray-curable resin composition include an arbitrary dye or pigment, a fluorescent dye or pigment, and an ultraviolet absorber.

The subject of the present invention resides in that as a method of forming the member C, the member C is formed by spreading a material for forming the member C made of a liquid resin composition on a liquid surface and solidifying the material. The material for forming the member C is a material that becomes a material of the member C by being solidified, and is arbitrary as long as the material can be spread on the liquid surface. The liquid surface development method and the solidification method can employ a method according to each material.

For example, a method in which a liquid energy ray-curable resin composition is used as a material for forming the member C, and the composition spread on the liquid surface is irradiated with energy rays to be solidified. Using a combined solution, a method of volatilizing the solvent from the solution developed on the liquid surface, using a solution of an unsolidified thermosetting polymer as a material for forming the member C,
A method in which the solvent is volatilized from the solution developed on the liquid surface, and then the mixture is heated and polymerized may be used. The solidification of the material for forming the member C may be complete solidification, or may be incomplete solidification in which fluidity has been lost to such an extent that a defective portion or groove of another member is not closed.

By forming the member C by such a liquid surface spreading method, it is easy to form a very thin and flexible thin film member C, and to form a very thin and flexible thin film member C. The operation of stacking on the member A or the member B becomes easy.

The liquid for developing the liquid member C forming material is arbitrary, for example, water (including an aqueous solution; the same applies hereinafter),
Examples thereof include silicon oil, mercury, and halogenated naphthalene, but water is preferred. When the specific gravity of the liquid member C forming material is greater than 1, or when the member C forming material contains a hydrophilic compound, the developing liquid is an aqueous solution of a salt such as salt or potassium bromide. Is preferred.

The method of spreading the liquid material for forming the member C on the liquid surface is arbitrary, and a known method for producing a Langmuir film or a polymer thin film can be used. For example, a method of dropping or flowing down from a nozzle placed in contact with the liquid surface or at an appropriate height above the liquid surface, a method of discharging from a nozzle placed below the liquid surface, changing the area of the liquid surface And the like.

The thickness of the material for forming the member C spread on the liquid surface is determined by the relationship between the area of the liquid surface to be spread and the supply amount of the material for forming the member C, and also when the solvent is used, its volatility. However, in many cases, the viscosity largely depends on the viscosity of the material for forming the member C, and the higher the viscosity, the thicker the material. The viscosity of the material for forming the member C used in the present invention is preferably 0.5 to 10000 mPa · s, and more preferably 2 to 5000 mPa · s.

When the material for forming the member C is a liquid such as an energy ray-curable composition, it can be used without adding a solvent, and when the viscosity is higher than the target viscosity, Can also adjust the viscosity by adding a solvent. When the member C forming material is fixed like a thermoplastic polymer, the viscosity can be adjusted by adjusting the solution concentration.

For the operation of bringing the member C formed in a liquid surface state into close contact with the member A or the member B, a known method for producing a Langmuir film can be used. For example, a method of scooping from the bottom, a method of assembling other members to be laminated from the submerged liquid onto the liquid surface at an angle substantially perpendicular to the liquid surface and attaching it to the liquid surface member C, a method of adhering from above, A method of pushing another member to be laminated from above the liquid into the liquid at an angle substantially perpendicular to the liquid surface and attaching it to the surface of the liquid member C can be adopted.

One preferred embodiment of the present invention is a method in which an energy ray-curable resin composition is used as a material for forming the member C, and the composition spread on the liquid surface is irradiated with energy rays. The use of the energy-ray-curable resin composition as the material for forming the member C means that adhesion to the member A or the member B is easy, control of the flexibility of the member C is easy, and It has the advantage that it can be implemented with productivity.

The viscosity of the energy ray-curable resin composition is adjusted by adding a solvent as needed, and the energy ray-curable resin composition is spread on the liquid surface. The method of removing the solvent is arbitrary, and may be volatilization, absorption into a developing solution, or the like. The step of removing the solvent may be a step of an arbitrary step such as after liquid surface development, after irradiation with energy rays, after bonding with another member, or may be performed over these steps, or these steps may be performed. Although it may be performed inside, it is preferable after the liquid surface development and before the energy beam irradiation.

The energy ray-curable resin composition spread on the liquid surface is irradiated with energy rays and solidified to form a member C. Irradiation may be performed by irradiating a dose sufficient to cure the energy ray-curable resin composition to almost completely solidify, or by irradiating an insufficient dose to form an incompletely solidified member C. In the case where the member C is almost completely solidified, the formed member C can be bonded to another member using an adhesive, or another member in a semi-cured state or a semi-dried state without using an adhesive. Can be glued.

The member C in a semi-cured state irradiated with an insufficient dose can be laminated on another member, and then irradiated again with an energy beam in that state, and bonded to the other member without an adhesive. . At this time, when the other member is formed of a cured product of the energy ray-curable resin composition, it is preferable that the cured product is also a semi-cured product because the adhesion becomes strong. In order to form the member C in a semi-cured state, it is preferable to irradiate an energy ray with a dose that is insufficient for complete curing. The use of an energy ray-curable resin composition that does not solidify even when irradiated with a sufficient dose is not preferred because subsequent adhesion and complete curing are difficult.

Among these, the method of forming the member C in a semi-cured state, re-irradiating with an energy beam in a state sandwiched between the member A and the member B formed of an arbitrary material, and bonding them is preferable. . Further, the member C is formed in a completely cured state or a semi-cured state, and the energy beam is re-irradiated in a state where the member C is sandwiched between the member A and the member B formed of the semi-cured product of the energy ray-curable resin composition. Is preferred. In any of the above cases, the energy beam to be re-irradiated may be different from that used for the first irradiation.

Another preferred embodiment of the present invention is a method in which a solution of a thermoplastic polymer is used as a material for forming the member C, and a solvent is removed from the solution spread on the liquid surface and solidified. The thermoplastic polymer mentioned here refers to a polymer that is not a crosslinked polymer, and includes a linear polymer, a branched polymer, and a planar polymer. Therefore, those having a softening temperature higher than the decomposition temperature and exhibiting no thermoplasticity are also included. Of course, the thermoplastic polymer that can be used in the present method is soluble in a solvent. The method of removing the solvent is arbitrary, and may be volatilization, absorption into a developing solution, or the like.

The solvent used is removed by some method,
It is optional as long as it can solidify the polymer,
Preferably, it is a volatile solvent. The volatile solvent preferably has a boiling point of 150 ° C. or lower, more preferably 100 ° C. or lower.

When water is used as the developing solution, preferred solvents are, for example, ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran; hydrocarbon solvents such as hexane, heptane, octane, toluene and cyclohexane; acetone, Ketone solvents such as 2-butanone; ester solvents such as ethyl acetate and butyl acetate; and fluorine solvents.

The thermoplastic polymer solution spread on the liquid surface is solidified by removing the solvent to form a member C. The method of removing (drying) the solvent is arbitrary, such as volatilization and absorption into a developing solution. In the step of removing the solvent, at least the fluidity is lost at the time of lamination on another member (that is, the member A and / or the member B), and the solvent is dried to such an extent that the defective portion formed on the other member is not closed. However, the complete drying may be performed in a subsequent step, may be performed over these steps, or may be performed simultaneously with these steps.

In the case where drying is performed almost completely by the time of lamination with another member, the formed member C can be bonded to another member using an adhesive, or an adhesive can be used. Instead, it can be bonded to another member in a semi-dry state formed of a thermoplastic polymer. Alternatively, it can be bonded to another member formed of a semi-cured product of the energy ray-curable resin composition and irradiated with energy rays.

The member C in a semi-dry state can be laminated on another member, dried in that state, and bonded to the other member without an adhesive. In this case, it is preferable that the other members are formed of a thermoplastic polymer because the adhesion becomes strong. At this time, it is preferable that the other members are also in a semi-dry state in which the solvent is absorbed, because the adhesion becomes strong. The drying method in this case may be standing, heating drying, hot air drying, vacuum drying, or the like. Vacuum drying is preferred because of high productivity.

The thermoplastic polymer used in this embodiment preferably has a crosslinkable residue which is crosslinked by energy rays or moisture. Among these, a method in which the member C is formed by semi-drying, and is completely dried and bonded while sandwiched between the member A and the member B formed of an arbitrary material is preferable. In addition, the member C is formed in a completely dried or semi-dried state, and the member A is formed of a semi-cured product of the energy ray-curable resin composition.
It is also preferable to perform the method of re-irradiating the energy beam while being sandwiched between the member and the member B to bond the members.

Further, the member C is formed in a completely dried or semi-dried state, and a semi-dried thermoplastic polymer (or a solvent-impregnated material) is formed.
It is preferable to completely dry and adhere in a state sandwiched between the member A and the member B formed by the above.

In the same manner as in the present embodiment, a method in which a thermosetting polymer material is developed on a liquid surface and then heat-solidified is also possible. This embodiment using a plastic polymer is preferable because of high productivity.

[0087]

EXAMPLES The present invention will be specifically described below 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" means "parts by weight" unless otherwise specified.

<Measurement of Viscosity> VM manufactured by Yamaichi Electric Co., Ltd.
Room temperature (24 ± 1 ° C) using a -100A type viscometer
Was measured.

<Measurement of Tensile Elastic Modulus and Elongation at Break> [Preparation of Measurement Sample] A tensile test sample was 10 mm in width.
Cut into strips of 100mm length and made 24 ± 1
The sample was left standing in a room at a temperature of 55 ° C. and a humidity of 55 ± 5% for 16 hours or more.

[Measurement] Using a "Strograph V1-C" manufactured by Toyo Seiki Seisakusho as a tensile tester, in an atmosphere of 24 ± 1 ° C. and 55 ± 5% humidity, a distance between grippers of 80 mm and a tensile speed of 20 mm / min. Was measured.

<Preparation of Energy Radiation-Curable Composition> The method of preparing the energy radiation-curable composition used in the examples is shown below. [Preparation of energy ray-curable composition [e1]] 10 parts of "Unidick V4263" (trifunctional urethane acrylate oligomer manufactured by Dainippon Ink and Chemicals, Inc.)
70 parts of "R-684" (dicyclopentanyl diacrylate manufactured by Nippon Kayaku Co., Ltd.) and "N-177E" [nonylphenoxy polyethylene glycol (n = 17) acrylate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 20 parts, 5 parts of "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Geigy) as an ultraviolet polymerization initiator, and 2,4-diphenyl-4-methyl-1-pentene (Kanto Chemical Co., Ltd.) as a polymerization retarder 0.1 part of an energy ray-curable composition [e
1] was prepared.

[Preparation of energy ray-curable composition [e2]] 20 parts of "Unidick V4263", "Sartomer C2000" (containing mainly ω-tetradecanediol diacrylate and ω-pentadecanediol diacrylate manufactured by Somar) Diacrylate mixture) 60
Department, "New Frontier HDDA" (1,6-hexanediol diacrylate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
20 parts, 5 parts of Irgacure 184, and 2,4-
0.1 part of diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) was mixed to prepare an energy ray-curable composition [e2].

[Energy ray-curable resin composition [e3]
Preparation] 40 parts of "Unidick V4263" and 40 parts of "Sartomer C2000" as a crosslinkable polymerizable energy ray-curable compound, 20 parts of "N-177E" as an amphiphilic polymerizable compound, and a polymerization retarder 2, 4
0.5 parts of -diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) and 5 parts of "Irgacure 184" as a photopolymerization initiator are uniformly mixed to form an energy ray-curable composition [ e3] was prepared.

<Irradiation of energy rays> Ultraviolet rays were used as energy rays. Using a Multilight 200 type light source unit manufactured by USHIO INC. In a nitrogen atmosphere,
Ultraviolet light having an intensity of 365 mW / cm ² at 365 nm was applied.

<Example 1> [Production of member A] 10 cm x 10 cm x made of polystyrene ("Dick Styrene XC-520" manufactured by Dainippon Ink and Chemicals, Incorporated, hereinafter referred to as [p1]).
127 μm on the support A (1) using a 3 mm flat plate
Energy curable composition [e using a bar coater
1], and irradiate with ultraviolet rays for 1 second to obtain a thickness of about 97 μm.
m of the semi-cured resin layer A1 (2) having lost the fluidity.

[0096] On this resin layer A1 (2), 50 µm
The energy ray-curable composition [e1] is applied using a bar coater of a m.m. to form a coating film to be a resin layer A2 (3). A portion other than the portion formed by the concave defect portion A (4) and the groove A (5) is irradiated with the same ultraviolet ray as above for 1 second to form a resin layer A2 (3) in which the irradiated portion is semi-cured. Then, the uncured energy ray-curable composition [e1] in the unirradiated portion is washed and removed with a stream of distilled water spouted from a washing bottle, and a concave defect A as a defect in the resin layer A2 (3). (4) and the groove A (5) were formed.

By the above operation, the cylindrical concave defect A (100 μm in diameter and 28 μm in depth) having the pattern shape shown in FIG. 1 and composed of the cured product of the energy ray-curable composition [e1] 4), a width of 50 μm, a depth of 28 μm, which is connected to the concave defect A (4) at the inlet A (6);
Resin layer A1 (2) and resin layer A having a groove A (5) having a rectangular cross-sectional shape with a rounded bottom corner having a length of 15 mm
A sheet-like member A having a thickness of about 127 μm, comprising the laminate of 2 (3), was prepared on a support A (1).

Then, a hole having a diameter of 0.3 mm penetrating the support A (1) and the resin layer A1 (2) is formed at the center of the concave defect A (4), thereby forming the outlet A.
(7) The flow path A2 (5'-2) and the connection port 2 (9) are formed, and the support A is formed at the other end of the groove A (5).
A hole having a diameter of 0.3 mm penetrating (1) and the member A was formed to form a channel A3 (5'-3) and a connection port 1 (8).

[Production of member B] Separately, in the same manner as for member A, support A (1), resin layer A1 (2), resin layer A2
(3), concave defect A (4), cavity A (4 '), groove A
(5), channel A1 (5'-1), channel A3 (5'-
3), portions corresponding to the inflow port A (6) and the connection port 1 (8) are respectively a support B (11), a resin layer B1 (12),
Resin layer B2 (13), concave defect B (14), cavity B
(14 '), groove B (15), channel B1 (15'-1),
Flow path B2 (15'-2), inflow / outflow port B (16), connection port 3 (17), and flow path A2 (15'-
2), support A (1) -member A, except that a structure corresponding to outlet A (7) and connection port 2 (9) is not provided
A support B (11) -member B composite having a structure similar to that of the composite and each part having the same dimensions is prepared, and the support B (11)- The periphery of the member B composite was cut off to have a size of 2.5 cm × 5 cm.

[Formation of Member C] An energy ray-curable composition [e2] (viscosity: 4900 mPa · s) was dropped on the surface of a saturated saline solution and irradiated with ultraviolet rays for 3 seconds to cure the composition. The member C (10) was in a cured state.

[Adhesion of members A, B and C] This member C
From above (10), the support A (1) -member A composite was pushed vertically below the liquid surface, and the member C was laminated on the surface of the member A where the defective portion A was formed, washed with water, and dried. The member C attached to the side surface of the member A and the support member A is cut off, and the defective portion A of the member A is removed.
One layer of the member C (10) is laminated on the formation surface, the remaining solvent contained in the member C is volatilized and removed by hot air from a hair dryer, and the support B (11) is placed on the member C. )-
The member B side of the member B composite is divided into a groove A (5) and a groove B (15).
Are laminated so that the concave portions A (4) and the concave portions B (14) are aligned with each other so that they do not overlap with each other. ,
All of the members C (10) are completely cured, and these members are bonded to each other to form a concave defect A (4) and a member C (10).
(10) and the cavity A (4 '), the groove A (5) and the member C
With (10), a capillary channel A1 (5'-1) is formed, and a concave B (14) and a member C (14) form a cavity B (1).
4 ′) is formed by the flow path (1) between the groove B (15) and the member C (10).
5′-1) were formed, and a microvalve mechanism [# 1] having the structure shown in FIGS. 2 and 3 was obtained.

[Tensile Properties of Materials of Members A, B and C] Separately, a biaxially stretched polypropylene sheet (“FOR” manufactured by Nimura Chemical Co., thickness 30 μm, single-sided corona treatment) as a coating support; An OPP sheet is abbreviated), an energy-ray-curable composition is applied thereon, and the applied support is peeled off after being completely cured by irradiating ultraviolet rays for 60 seconds. A cured product sheet of the energy ray-curable composition was produced. As a result of measuring the tensile properties of this sheet, the cured product of the energy ray-curable composition (e1) was found to have a tensile modulus of 1160 (MPa) and an elongation at break of 76.
(%), The cured product of the energy ray-curable composition (e2) has a tensile modulus of 265 (MPa) and an elongation at break of 8.0.
(%)Met.

On the other hand, the semi-cured material sheet prepared in the same manner as above except that the ultraviolet irradiation time was set to 3 seconds, the semi-cured material of the energy ray-curable composition (e1) had a tensile modulus of about 130 (MPa). ), The elongation at break was about 3 (%), and the semi-cured product of the energy ray-curable composition (e2) had a tensile modulus of about 30 (MPa) and an elongation at break of about 3 (%).

[Channel Opening / Closing Test] When distilled water was injected into the channel from the connection port 1 (8) using a microsyringe, the water was supplied to the channel A3 (5'-3) and the channel A1 (5 '). −
1), flowing out from the connection port 2 (9) through the inflow port (6), the cavity A (4 '), the outflow port (7), and the flow path A2 (5'-2). Next, when compressed air of 0.3 MPa (gauge pressure) was introduced from the connection port 3 (17), the flow of water was interrupted, and when the pressure was returned to normal pressure, the water flowed again. This test is
Repeated times, all gave similar results.

In addition, when ten microvalves of the same kind were manufactured and subjected to a test, there was no one that caused leakage of the liquid from the flow path or damage of the diaphragm, and all the same results as above were obtained. As a result, the yield was 100%.

<Example 2> [Preparation of member A] 10c made of polystyrene [p1]
Support A using a flat plate of mx 10 cm x 3 mm (3
In 1), the energy ray-curable composition [e1] is applied using a 127 μm bar coater, and irradiated with ultraviolet rays for 1 second in a nitrogen atmosphere, to thereby obtain a semi-cured resin layer A1 (32) having lost fluidity. ) Formed.

On the resin layer A1 (32), 50
The energy ray-curable composition [e1] is applied using a bar coater of μm, and the flow path A2 (35′-2) shown in FIGS. 4 and 5 is applied in a nitrogen atmosphere using a photomask.
A portion other than the portion to be formed is irradiated with the same ultraviolet ray for 1 second as described above, and the resin layer A2 (3
3) The unirradiated portion of the uncured energy ray-curable composition [e1] was washed away with a stream of distilled water spouted from a washing bottle to remove the unirradiated portion as a defective portion of the resin layer A2 (33). A groove A (35'-2) serving as a path A2 (35'-2) was formed. Then, at one end of the groove A, the support A (3
1) A hole having a diameter of 0.3 mm was formed in the resin layer A1 (32) and the resin layer A2 (33) to form a flow path A3 (35'-3) and a connection port 1 (38).

Next, O was used as a coating support (not shown).
Use by cutting the PP film into 10cm x 10cm
The energy ray-curable composition [e2] is applied to the corona-treated surface using a 50 μm bar coater, and the flow-in port A (37) and the flow path shown in FIGS. A portion other than the portion that becomes A4 (35′-4) is irradiated with the same ultraviolet ray for 3 seconds as described above to form a semi-cured resin layer A3 (39) on the irradiated portion of the coating, and the uncured portion of the uncured portion is uncured The energy ray-curable composition [e1] is washed and removed with an ethanol stream spouted from the washing, and the resin layer becomes a cylindrical inflow port A (37) having a diameter of 70 μm and a flow path A4 (35′-4). A3 (39) hole-shaped defect was formed.

This resin layer A3 (39) is connected to the inlet A (3
7) should be a groove (35'-) to be a flow path A2 (35'-2).
2) The resin layer A is laminated on the member A in accordance with the position where the resin layer A
3 (39) was solidified, the coated support (not shown) was peeled off, and the resin layer A3 (39) was bonded to the resin layer A2 (33).

Subsequently, the inflow port A (37) and the flow path A (3
Instead of 5′-4), the cavity A (34 ′) and the channel A1
A resin layer A4 (40) was formed on a coating support (not shown) in the same manner as the resin layer A3 except that a resin defect portion to be (35'-1) was formed. A (37)
Were positioned and centered on a defect A (34 ') to be a cavity A (34'), and were laminated and bonded.
Then, the groove (35 ') to be the channel A1 (35'-1) is formed.
-1) at the other end, a support A (31), a resin layer A1
(32), a hole having a diameter of 0.3 mm penetrating the resin layer A2 (33), the resin layer A3 (39) and the resin layer A4 (40) is formed, and the flow path A5 (35'-5) and the connection port 2 ( 41) was formed.

By the above operation, the member A having a thickness of about 180 μm and consisting of four resin layers composed of the cured product of the energy ray-curable composition [e1] was converted to the support A (3
Formed on 1).

[Production and Adhesion of Member B] In the same manner as in Example 1, the defective portion B (54 ') serving as the cavity B (54') and the groove B (55 'serving as the flow path B1 (55'-1)) are formed. '-1), an inflow / outflow port B (56), a flow path B2 (55'-2), and a connection port 3 (57), and a resin layer B1 having a thickness of 95 μm each.
A member B composed of (52) and a resin layer B2 (53) having a thickness of about 28 μm was formed on a support B (51).

[Preparation and Adhesion of Member C] Instead of the energy ray-curable composition [e2], a 10% by weight solution of the energy ray-curable composition [e3] in 2-butanone (viscosity 1050 mPa · s), instead of dripping from the top of the developing solution, using a stainless steel pipe with an inner diameter of 1 mm, and discharging directly below the liquid surface. Prior to UV irradiation, the solvent was removed at room temperature under a slight airflow for 10 minutes. A member C (42) having a thickness of about 7 μm was prepared in the same manner as in Example 1 except that the material was evaporated,
After vacuum drying at 0 ° C. for 10 minutes, the laminate was sandwiched and laminated between the members A and B and irradiated with ultraviolet rays to be bonded.
The cavity B (54 '), the flow path B1 (55'-
1) forming the inflow / outlet B (56) and supporting the support A
(31) -Member A-Member C (42) -Member B-Support B
(51) was laminated and bonded to produce a microvalve mechanism [# 2].

[Tensile Properties of Material of Member C] The tensile properties of the cured product of the energy ray-curable composition [e3] measured in the same manner as in Example 1 were such that the tensile modulus was 220 (MPa) and the elongation at break was 7 0.5 (%). On the other hand, the semi-cured sheet produced in the same manner as above except that the ultraviolet irradiation time was 3 seconds had a tensile modulus of about 25 (MPa) and an elongation at break of about 3 (%).

[Flow Channel Opening / Closing Test] When distilled water was injected into the flow channel from the connection port 1 (38) using a microsyringe, water was supplied to the flow channel A3 (35'-3) and the flow channel A2 (35 '). −
2), channel A4 (35'-4), inlet A (37), cavity A (34 '), outlet A (36), channel A5 (35')
-5) and the connection port 1 through the channel A1 (35'-1).
It leaked from (41). Next, 0.
When compressed air of 3 MPa (gauge pressure) was introduced, the flow of water was shut off, and when the pressure was returned to normal pressure, the water flowed again. This test was repeated ten times, all with similar results.

Further, when ten identical microvalves were prepared and subjected to a test, there was no one that leaked liquid from the flow path or one that caused damage to the diaphragm, and all the same results as above were obtained. As a result, the yield was 100%.

Example 3 A member C was treated with a 10% tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) solution (viscosity of 1420 mpa · s) of thermoplastic polyurethane (manufactured by Dainippon Ink and Chemicals, Inc., Pandex T-5205). Discharge just below the surface of the water.
Example 1 except that it was prepared by drying at 30 ° C. for 30 minutes.
A micro valve mechanism (# 3) similar to the micro valve mechanism (# 1) was manufactured in the same manner as described above except that the material of the member C constituting the diaphragm was a thermoplastic polyurethane having a thickness of about 10 μm.

[Tensile Properties of Material of Member C] Separately, a solvent casting method and vacuum drying at 45 ° C. for 2 hours were performed to obtain a material having a thickness of about 100 μm.
m of a thermoplastic polyurethane (manufactured by Dainippon Ink and Chemicals, Inc., Pandex T-5205) sheet, and its tensile properties were measured. As a result, the tensile modulus was about 12 (MP).
a), the elongation at break was about 800 (%).

[Flow Channel Opening / Closing Test] Micro Valve Mechanism (#
The same test as in Example 1 was performed using 3), and the same result as in Example 1 was obtained. In addition, when ten identical microvalves were manufactured and subjected to the test, there was no one that caused leakage of the liquid from the flow channel or one that caused the damage of the diaphragm,
All gave the same results as above, and the yield was 100%.

<Example 4> [Preparation of member (A)] A flat substrate (1) of polystyrene [p1] having a size of 2.5 cm x 5 cm x 3 mm was heated with an electric hot air torch. After softening the surface, pressing it against a glass mold (not shown) heated to 180 ° C. and cooling it, it was peeled off, and the substrate (1) surface was 30 μm wide and 3 μm deep.
A groove having a diameter of 90 μm and a depth of 30 μm, which is a groove having a substantially rectangular cross section and having a diameter of 0 μm and a length of 30 mm;
An inlet (4) and an outlet (5) are formed by forming a cylindrical defect (3) having a diameter of μm and drilling holes having a diameter of 0.5 mm at both ends of the groove (2). A member [A-4] having the shape shown in FIG. 1 was prepared except that the member [A-4] was formed of a single material instead of a plurality of materials and layers.

[Preparation of Member (B)] A member "B-4" having the same structure as the member [A-4] was prepared in the same manner as described above.

[Preparation and Adhesion of Member (C)] A member [C-4] was prepared in the same manner as in Example 3 except that drying after liquid level development was half-drying at 25 ° C. for 5 minutes without wind. Then, the energy beam was not irradiated, and the member C
Was not dried, the laminated members A-4, B-
4, the member [A-4] -member was obtained in the same manner as in Example 3 except that the adhesion of C-4 was performed by vacuum drying at 45 ° C. for 5 hours in a state where the adhesion was performed using a spring clamp. [C
-4] -A minute valve mechanism [# 4] in which the member [B-4] is laminated and bonded.

[Channel Opening / Closing Test] A test was conducted in the same manner as in Example 3, and similar results were obtained. However, when ten identical microvalves were produced, there were five that produced leakage of liquid from the flow channel and five that produced breakage of the diaphragm, and the yield was 50%.

<Example 5> [Production of member (A)] A member [A-4] produced in exactly the same manner as in Example 4 was used. [Production of Member (B)] A member [B-4] produced in exactly the same manner as in Example 4 was used.

[Preparation and Adhesion of Member (C)] A member [C-2] made of a semi-cured product of the energy ray-curable composition (e3) was prepared in the same manner as in Example 2, and the member [A-2] ] Was used in place of the member [A-4], and the member [B-
In the same manner as in Example 2 except that the member [B-4] was used instead of the member [2], the member [A-4] -the member [C-2] -the member [B-4] was laminated and bonded. Micro valve mechanism [#
5].

[Channel Opening / Closing Test] A test was conducted in the same manner as in Example 4, and similar results were obtained. However, when ten identical microvalves were produced, there were two that produced leakage of the liquid from the flow channel and two that caused breakage of the diaphragm, and the yield was 80%.

[0127]

According to the present invention, a thin and flexible thin film to be formed as a diaphragm of a minute valve mechanism can be easily manufactured, and the thin film having poor handleability is directly processed without being processed into a finer diaphragm shape. Provided is a method for manufacturing a diaphragm-type micro valve mechanism which can be laminated and adhered to other members with good workability and has excellent productivity.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of a pattern formed on a member A and a member B of a micro valve mechanism manufactured in Example 1 and Example 3. FIG.

FIG. 2 is a schematic plan view of a micro valve mechanism manufactured in Example 1 and Example 3.

FIG. 3 is a schematic elevational view of a microvalve mechanism manufactured in Example 1 and Example 3;

FIG. 4 is a schematic diagram of a plan view of a micro valve mechanism manufactured in Example 2.

FIG. 5 is a schematic elevational view of a micro valve mechanism manufactured in Example 2.

[Explanation of symbols]

1: Support A2: Resin layer A13: Resin layer A24: Concave defect A4 ': Cavity A5: Groove A; Defect of resin layer A1 5'-1: Channel A1; Resin layer A2 5'-2: flow path A2; hole drilled through support A and resin layer A1 5'-3: flow path A3; support A, tree layer A1 and tree layer A2 Hole 6 drilled: Inlet A 7: Outlet A 8: Connecting port 19: Connecting port 2 10: Member C 11: Supporting body B 12: Resin layer B1 13: Resin layer B2 14: Residual defect B: defective portion of resin layer B1 14 ': cavity B15: groove B; defective portion of resin layer B1 15'-1: flow channel B1: defective portion of resin layer B1 15'-2: flow channel B2; support B, a hole penetrated through the dendritic layer B1 and the dendritic layer B2 16: inflow / outflow port B 17: connection port 3 31: support body A 32: resin layer A1 3: resin layer A2 34 ': cavity A, defective portion A 35'-1: channel A1; defective portion of resin layer A4; groove 35'-2: channel A2; defective portion of resin layer A2; groove 35' -3: channel A3; hole drilled through support A, resin layer A1 and resin layer A2 35'-4: channel A4; hole-shaped defective portion of resin layer A3 35'-5: flow Path A5: Hole formed through support A, resin layer A1, resin layer A2, resin layer A3, and resin layer A4 36: Outlet A37: Inlet A38: Connection port 39: Resin layer A3 40: Resin layer A4 41: Connection port 2 42: Member C51: Support B52: Resin layer B1 53: Resin layer B2 54 ': Cavity B; Defect B55'-1: Flow path B1; Resin layer B2 55'-2: channel B2; hole drilled through support B and resin layer B1 56: inflow / outlet B57: connection 3

Claims (9)

[Claims] 1. A thin film-like member formed by spreading a diaphragm-forming material made of a liquid resin composition on a liquid surface and solidifying the same, has a defective portion on a part of the surface, or has a member. The thin film-like member is formed into a diaphragm by being sandwiched and bonded between two members having a defective portion through which a defective portion is formed, and each defective portion is formed as a cavity partitioned by the diaphragm. Manufacturing method of diaphragm type micro valve mechanism. 2. The thickness of the diaphragm is 0.1 to 500 μm.
The method for manufacturing a micro valve mechanism according to claim 1, wherein m is m. 3. A diaphragm having a tensile modulus of elasticity of 0.1.
The method for manufacturing a microvalve mechanism according to claim 1, wherein the microvalve mechanism is formed of a material in a range of MPa to 10 GPa. 4. The method according to claim 1, wherein the diaphragm has a value of “tensile elastic modulus × diaphragm thickness” in a range of 10 to 50,000 Pa · m. 5. The microvalve according to claim 1, wherein the diaphragm forming material is an energy ray-curable resin composition, and the solidification of the forming material is due to energy beam irradiation. Mechanism manufacturing method. 6. The diaphragm-forming material is an energy-ray-curable resin composition, wherein the solidification of the forming material is semi-cured by irradiation of an insufficient dose of energy rays, and has a thin-film member and a defective portion. Adhesion with the member is performed by a method of irradiating energy rays in a state where a thin-film member in a semi-cured state and a member having a defective portion are laminated and completely solidifying and bonding the thin-film member. Item 6. A method for manufacturing a micro valve mechanism according to Item 5. 7. The manufacture of a microvalve mechanism according to claim 1, wherein the diaphragm forming material is a solution of a thermoplastic polymer, and the solidification of the forming material is performed by removing a solvent. Method. 8. The diaphragm forming material is a solution of a thermoplastic polymer, the solidification of the forming material of the thin film member is semi-dry due to insufficient solvent removal, and has a thin film member and a defective portion. The method for manufacturing a micro valve mechanism according to claim 7, wherein the bonding with the member is a method in which the solvent is completely removed in a state where the members are laminated, and the thin film member is completely dried and bonded. 9. The bonding between the thin film member and the member having the defective portion is performed by forming the member having the defective portion with a semi-cured material of the energy ray-curable resin composition, and laminating the member with the thin film member. The method for manufacturing a microvalve mechanism according to any one of claims 1 to 8, wherein the method is a method of irradiating the semi-cured product by completely irradiating the semi-cured product with the energy beam in a state and bonding the semi-cured product.