JP2002122488A - Micro chemical device with temperature display mechanism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a micro chemical device with a temperature display mechanism dispensing with connection with the exterior and capable of accurately displaying the temperature of a micro region and adjusting the temperature with high accuracy. SOLUTION: This micro chemical device with the temperature display mechanism has micro capillary passages 4 inside and a substance whose optical characteristic is changed by the change of temperature, fixed therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the chemical industry, biochemical industry, agriculture, forestry, fisheries, medical care (including inspection and diagnosis), food industry, pharmaceutical industry, environmental protection, criminal investigation, sports, and others. Microchemical devices used in a wide range of fields, that is, microdevices (microreactors) for chemical and biochemical reactions, membrane filtration devices, and dialysis devices in which members have structures such as microchannels and reaction vessels , Chemical and physico-chemical processing devices such as degassing / aspirating devices, extraction devices, etc., and microanalytical devices such as DNA analysis devices, electrophoresis devices, and chromatography devices. More specifically, optical characteristics change due to temperature changes. The present invention relates to a microchemical device having a temperature display mechanism on which a substance is fixed.

[0002]

2. Description of the Related Art As a microchemical device, a thin groove-like channel having a width of several μm to several hundred μm is formed on a base material such as silicon, quartz, glass, or polymer by an etching method, and a cover is formed thereon. It is known that a groove is formed into a capillary channel by bonding to form a liquid channel, a reaction tube, or a gel channel for separation. As a mechanism for heating a specific region of such a microchemical device, Methods for incorporating electric heaters have been reported (eg, Science, 199).
8 years, volume 282, page 484).

[0003] However, it has been extremely difficult to detect the temperature of a specific portion of such a minute flow path with a normal temperature detecting element. For example, alcohol thermometers, mercury thermometers, and resistance thermometers are difficult to miniaturize, and thermocouples and resistance thermometers have the ability to input and output heat through conductors connected to the outside. An error occurs in the measurement temperature of a microchemical device having a small heat capacity.

[0004] In addition, the infrared detection type non-contact thermometer tends to have a large measurement error with respect to a microchemical device made of a transparent material in which the internal structure such as a flow path and a reaction tank can be confirmed. With a microchemical device, it has been extremely difficult to control the temperature of a microregion with high accuracy.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a temperature control device which does not need to be connected to the outside, can accurately display the temperature of a minute area, and can perform temperature control with high accuracy. It is to provide a microchemical device having a display mechanism.

[0006]

Means for Solving the Problems As a result of intensive studies on means for solving the above problems, the present inventors have found that the problems can be solved by incorporating a substance whose optical characteristics change with temperature into a microchemical device. And completed the present invention.

That is, the present invention provides: (1) a microchemical device having a temperature display mechanism, which has a microcapillary flow path therein and in which a substance whose optical characteristics change due to a temperature change is fixed;

(2) The fixing of a substance whose optical properties change due to a temperature change is fixing by enclosing a substance whose optical properties change with a temperature change into a member constituting a microchemical device. Micro chemical devices,

(3) The microchemical device according to (1) or (2), wherein the substance whose optical characteristics change due to a temperature change is a liquid crystal;

(4) The microchemical device is composed of a member (A) and a member (B), and the capillary channel has a groove formed on the surface of the member (A), and a groove formed on the surface of the member (A). A substance formed by the member (B) adhered to the groove forming surface of A), and a substance whose optical characteristics change due to a temperature change is formed by the concave portion formed on the groove forming surface of the member (A) and the member (B). A) a microchemical device according to any one of (1) to (3), which is enclosed in the space formed by

(5) The microchemical device is composed of a member (A), a member (B), and a member (C) filled between these members, and the flow path is defective in the member (C). The member is formed between the member (A) and the member (B) as a part, and a substance whose optical property changes due to a temperature change is formed as a defective part of the member (C) by the member (A) and the member (B). (1)-enclosed in the space formed between
(3) the microchemical device according to any one of (1);

(6) The microchemical device includes the microchemical device according to any one of (1) to (5), wherein the microchemical device is made of an organic polymer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A microchemical device according to the present invention has a capillary channel (hereinafter sometimes simply referred to as a "channel") inside a member, and performs some kind of chemical operation (biochemical (Including manual operations).
The flow channel referred to in the present invention refers to a portion through which a fluid flows, other than a simple transfer channel, a reaction channel, a reaction section such as a reaction tank; an analysis section such as chromatography or electrophoresis; dialysis, membrane filtration, Separation unit for extraction, etc .; detection unit for flow rate detection, optical detection, etc .;

The shape of the cross section of the flow path is arbitrary, and may be rectangular (including a rectangle with rounded corners), trapezoid, triangle, slit,
A circle, a semicircle, an ellipse, and the like can be exemplified, but a rectangle is preferable. The vertical and horizontal dimensions of the channel cross section are arbitrary,
Preferably 1 μm to 3 mm, more preferably 3 μm to 1
mm, most preferably from 5 μm to 0.5 mm. If the size is less than this, the manufacturing difficulty tends to increase, which is not preferable. If the size exceeds this, the characteristics of the microchemical device tend to decrease, which is not preferable.

The external shape of the microchemical device of the present invention is not particularly limited, and can take a shape according to the purpose of use. For example, it may be in the form of a sheet (including a film, a ribbon, etc .; the same applies hereinafter), a plate, a coating, a rod, a tube, a cylinder, and a molded article having a complicated shape, but other microchemical devices. It is preferably in the form of a sheet or a plate from the viewpoint of ease of integration with the substrate and ease of molding.

It is preferable that the microchemical device of the present invention is laminated, adhered, or connected to another member or another mechanism. Further, a plurality of microchemical devices can be formed in one member.

The microchemical device of the present invention is preferably a device in which a capillary channel is formed between two members directly or indirectly bonded, that is, a member (A) and a member (B). It is.

The channel may be formed, for example, by (a) bonding another member (B) to the grooved surface of the member (A) having a groove on the surface. (B) A portion other than the flow path between the member (A) and the member (B) may be formed by filling the member (C). The above (a)
The bottom surface and the side surface of the flow path are made of the member (A), and the top surface is made of the member (B) or an adhesive applied to the member (B).

However, the member (A) may be made of a plurality of materials, for example, the bottom and side surfaces of the groove may be made of different materials. In addition, the flow path in (b) above has a member (A) on the bottom surface when the member (B) is turned up, a member (C) filled on the side surface, and a member (B) on the top surface.

When the flow path is formed by bonding another member (B) to the grooved surface of the member (A) having a groove on the surface, the groove is lower than its peripheral portion, that is, as a so-called groove. It may be formed, or may be formed between walls standing on the surface of the member (A). The depth of the groove may vary from location to location.

The method of forming grooves on the surface of the member (A) is arbitrary. For example, injection molding, solvent casting, melt replica method, cutting, patterning exposure of energy ray-curable resin coating film and removal of uncured portions , Photolithography (including energy beam lithography), wet etching, dry etching, laser etching, vapor deposition, vapor phase polymerization, bonding between sheet-like and plate-like members with cut-out portions to be grooves, etc. Method is available.

In the case where the flow path has a structure in which the member (C) is filled between the member (A) and the member (B), the thickness of the member (C) is not necessarily required to be uniform. , And is preferably uniform. When a substance whose optical characteristics change due to a temperature change described later is a liquid crystal, the member (A)
It is also preferable that at the stage when the groove is formed, the inside of the groove is rubbed with a cloth or the like to form an oriented surface.

The shape of the member (A) is arbitrary, but is preferably a sheet, a plate, a coating, or a rod. When the member (A) has a groove on the surface, the surface on which the groove is formed preferably has a planar shape. Further, the member (A) may be formed on a support.

The member (B) is bonded to the grooved surface of the member (A) having a groove on the surface, and a capillary channel is formed by the groove of the member (A) and the member (B). Or between the member (A) and the member (B),
If the member (A), the member (B), and the solid substance can form a capillary channel by filling the solid substance except for a part to be a flow path, the shape, The structure, surface condition, and the like are arbitrary.

These are the same as in the case of the member (A). The member (B) does not need to have a groove formed on its surface, but may have a groove or a structure other than the groove. For example, the member (B) may be a mirror image of the member (A) having a groove formed on the surface.

Member (A) and member (B) having grooves on the surface
Any method can be used as long as the groove on the surface of the member (A) is formed as a capillary channel, and a solvent type adhesive, a solventless type adhesive, a melting type adhesive, and a member (A) as well as/
Alternatively, solvent application to the surface of the member (B), fusion by heat or ultrasonic waves, or the like can be used, but use of a solventless adhesive is preferred.

The method of using an energy ray-curable resin as a solventless adhesive and curing it by irradiation with energy rays and bonding the same enables precise bonding of minute devices.
It is preferable because productivity is high. Further, it is also possible to adopt a method of removing the protective material after bonding the groove with the protective material filled therein. The member (B) may be a cured product of the adhesive itself.

A method of forming a flow path having a structure formed by filling the part other than the flow path between the member (A) and the member (B) with the member (C) includes, for example, the method of forming the member (A) The energy ray-curable composition is sandwiched between the member and the member (B), and the outside of the member (A) and / or the member (B) is irradiated with an energy beam except for a part serving as a flow path to form an irradiation part. A method for curing the composition to form a member (C), removing the uncured composition in the non-irradiated portion, and a method of removing an adhesive sheet-like member (C) from which a portion to be a flow path is cut out. A method of sandwiching between the member (A) and the member (B) and bonding them to each other;

A protective material such as a rod made of tetrafluoroethylene is placed in a portion to be a flow channel, and after filling and solidifying an adhesive or a molten resin to form a member (C), the protective material is removed. And the like. This method has a small number of steps, but when the channel diameter is small, it is difficult to remove the uncured energy ray-curable composition and the protective substance. Therefore, this method is suitable as a method for forming a channel having a relatively large dimension. .

The material constituting the present microchemical device,
For example, the material of the member (A) or the member (B) may be a substance fixed in the microchemical device and having a change in optical characteristics due to a temperature change (hereinafter, a “substance in which the optical properties change due to a temperature change” may be simply referred to as a “substance”). The optical temperature-sensitive substance may be observable from the outside of the member. When the optical temperature-sensitive substance is sealed in the microchemical device, it comes into contact with the optical temperature-sensitive substance. It is sufficient if a window made of a transparent material is provided in the portion.

However, it is preferable that one side or all of the microchemical device is transparent. To be transparent here means that the optical temperature-sensitive substance enclosed in the microchemical device can be observed from the outside,
It is not always necessary to be colorless and transparent, but it may be translucent or colored and transparent, depending on the type of optical thermosensitive substance. Examples of the transparent material include glass, crystals such as quartz, ceramics, and organic polymer (which may contain an inorganic component; hereinafter, simply referred to as “polymer”).

When the portion other than the observation window or the optical temperature-sensitive substance is fixed on the surface of the microchemical device, the material does not need to be transparent, and any material can be used.
Such a material may be, for example, glass, crystal such as quartz, metal such as stainless steel, semiconductor such as silicon, ceramic, carbon, polymer, or the like.

The material of the microchemical device of the present invention is:
Polymers are preferred in many applications. The polymer may be a homopolymer or a copolymer, and may be a thermoplastic polymer or a thermosetting polymer. From the viewpoint of productivity, a cured product of a thermoplastic polymer or an energy ray-curable composition is preferable.

Examples of the polymer usable for the member include styrene polymers such as polystyrene, poly-α-methylstyrene, polystyrene / maleic acid copolymer and polystyrene / acrylonitrile copolymer; porsulfone and polyethersulfone. (Meth) acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; polymaleimide polymers;

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; cellulosic polymers such as cellulose acetate and methylcellulose; polyurethane polymers; polyamide polymers; polyimide polymers;

Polyether or polythioether polymers such as poly-2,6-dimethylphenylene oxide and polyphenylene sulfide; polyether ketone polymers such as polyether ether ketone; polyester polymers such as polyethylene terephthalate and polyarylate Coalescing; epoxy resin; urea resin; phenolic resin and the like. Among 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 energy ray-curable compound constituting the energy ray-curable composition may be any one such as a radical polymerizable compound, an anionic polymerizable compound and a cationic polymerizable compound. The energy ray-curable compound is not limited to one that polymerizes in the absence of a polymerization initiator, and one that is polymerized by an energy beam only in the presence of a polymerization initiator can also be used. As such an energy ray-curable compound, those having a polymerizable carbon-carbon double bond are preferable, and among them, a highly reactive (meth) acrylic compound, vinyl ethers, and the absence of a photopolymerization initiator are preferable. A maleimide-based compound that cures even below is preferred.

Examples of the crosslinkable polymerizable (meth) acrylic monomer which can be preferably used as an energy ray-curable compound include diethylene glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate.
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,

Bifunctional monomers such as neopentyl glycol hydroxy (dipivalate) di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate and N-methylenebisacrylamide; trimethylolpropane Trifunctional monomers such as tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, and caprolactone-modified tris (acryloxyethyl) isocyanurate;

Examples include a tetrafunctional monomer such as pentaerythritol tetra (meth) acrylate; and a hexafunctional monomer such as dipentaerythritol hexa (meth) acrylate.

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

Examples of the maleimide-based crosslinked polymerizable oligomer include polytetramethylene glycol maleimide alkylate such as polytetramethylene glycol maleimide capriate and polytetramethylene glycol maleimide acetate. The maleimide-based monomer or oligomer can be copolymerized with each other and / or with a compound having a polymerizable carbon-carbon double bond such as a vinyl monomer, vinyl ether, or an acrylic monomer. Further, the above-mentioned energy ray-curable compounds may be used alone or as a mixture of two or more.

A photopolymerization initiator can be added to the energy ray-curable 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 maleimide compound.

Examples of monofunctional maleimide monomers that can be used in combination include N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-dodecylmaleimide; and N-cyclohexylmaleimide. N-alicyclic maleimide; N-benzylmaleimide; N-phenylmaleimide, N- (alkylphenyl) maleimide, N-dialkoxyphenylmaleimide,

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

Maleimide having an alkoxy group such as N-methoxyphenylmaleimide; maleimide having an amino group such as N- [3- (diethylamino) propyl] maleimide; and 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;

Examples of the energy ray 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.

The material may be a polymer blend or a polymer alloy, or may be a foam, a laminate, or another composite. Further, the material may contain other components such as a modifying agent and a coloring agent.

Examples of the modifying agent that can be contained in the material include a hydrophobizing agent (water repellent) such as silicone oil and a fluorine-substituted hydrocarbon; a surfactant such as an anionic, cationic or nonionic surfactant; Hydrophilizing agents such as inorganic powders such as silica gel and hydrophilic polymers such as polyvinylpyrrolidone; and plasticizers for adjusting the tensile modulus. As a coloring agent that can be contained in the material, for example, any dye or pigment, fluorescent dye or pigment,
UV absorbers.

In the microchemical device of the present invention, a substance whose optical characteristics change due to a change in temperature, that is, an optical temperature-sensitive substance is fixed. The term "optical temperature-sensitive substance" as used in the present invention refers to a substance whose optical properties such as absorbance, absorption spectrum (visible, ultraviolet, infrared), reflectance, reflection spectrum, fluorescence intensity, fluorescence spectrum, etc., change with temperature. is there. The form of the optical temperature-sensitive substance is arbitrary, such as liquid, solid,
It may be in the form of a gel, a dispersed state, or other forms.

Examples of the optical temperature-sensitive substance include liquid crystals such as cholesteric liquid crystals and twisted nematic liquid crystals; thermochromic dyes such as spiropyrans, bianthrones and dixanthylenes; phenylmethane compounds such as fluorans and phenylphthalides; Dorirufutarido acids, spiropyrans, leuco auramine compounds, electron donative coloration dyes and phenols such as auramine, triazoles, the combination of the electron accepting substance such as carboxylic _{acids; CoC 12 · 2 (CH 2} ) 6 Metal complex salt crystals such as 10H ₂ O, metal salt crystals such as Ag ₂ HgI ₄ and Cu ₂ HgI ₄ ;
A temperature-sensitive gel having a gel transition temperature of 0 ° C to 100 ° C can be exemplified.

The optical temperature-sensitive substance may be one in which optical properties such as color tone and absorbance change continuously with temperature, and those in which optical properties such as transparency / coloring change at a specific temperature. Can be selected according to purpose. Although it depends on the purpose of use, those in which a change is observed in a temperature range of 0 ° C to 100 ° C are preferable for a wide range of uses. Further, it is preferable that the color tone changes continuously with temperature. Among them, a liquid crystal is particularly preferable because a change in color tone can be clearly observed even when the thickness of the enclosing portion is small, and the temperature at which the optical characteristics change by blending various liquid crystal components is easily adjusted.

In the present invention, the optical thermosensitive substance is fixed at an arbitrary position on the microchemical device. The fixation may be fixation to the surface of the microchemical device, but is preferably sealed inside, and for the purpose of measuring the temperature of the flow channel, it is sealed at the same depth as the flow channel. Is preferred.

The encapsulation is not necessarily required to be hermetically sealed. For example, the optically sensitive substance may remain in a depression provided in the microchemical device or in a cavity connected to the outside. . The position where the optical thermosensitive substance is filled in the microchemical device is arbitrary as long as it can be optically observed from the outside. In the case of fixing to a surface, it is preferable to be adhesive or sticky.

The microchemical device of the present invention can not only display the temperature but also adjust the temperature of the microchemical device based on the displayed or detected temperature. The temperature control portion may be the entire microchemical device or a specific region in the microchemical device. It is useful and preferable that the region to be temperature-controlled is a region including a flow path. The microchemical device of the present invention is suitable for a microreactor, and particularly suitable for a PCR device.

The method of controlling the temperature of the microchemical device is arbitrary, and a heating element and a heat absorber are incorporated into the microchemical device; a heat medium such as a liquid or a gas is introduced into the microchemical device; Contact with heated or cooled solids, liquids, gases, etc .; Irradiation of electromagnetic waves such as infrared rays, microwaves, etc., but the incorporation of heating elements into microchemical devices or solids from outside microchemical devices Preferably, the contact is

When a heating element is incorporated in the microchemical device, the heating element is preferably an electric heater, and the electric heater may be, for example, a nichrome wire or other metal, metal oxide, carbon, semiconductor, conductive plastic, or the like. And bonding, embedding, and vapor deposition. The position where the electric heater is mounted may be the periphery in the same plane as the flow channel, or the upper surface and / or lower surface of the flow channel.

When the microchemical device is in the form of a sheet or a plate, and the method of controlling the temperature of the microchemical device is contact with a solid from outside the microchemical device, the microchemical device may be formed on both sides of the microchemical device. Is preferable.

[0061]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the examples, "parts" means "parts by weight" unless otherwise specified.

[Embodiment 1] In this embodiment, a flow path and an optically thermosensitive substance enclosing portion are provided between a member (A) having grooves and recesses formed on the surface and another member (B). An example of manufacturing a microchemical device was shown.

[Preparation of a microchemical device] A trifunctional urethane acrylate oligomer having an average molecular weight of about 2000 (“Unidick V” manufactured by Dainippon Ink and Chemicals, Inc.)
-4263 "), 35 parts of 1,6-hexanediol diacrylate (" New Frontier HDDA "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and nonylphenoxy polyethylene glycol (n = 17) acrylate (Daiichi Kogyo Seiyaku) 30 copies of "N-177E" manufactured by Co., Ltd.
5 parts of hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy), and 2,
0.1 part of 4-diphenyl-4-methyl-1-pentene (manufactured by Kanto Chemical Co., Ltd.) is mixed and a homogeneous composition [x-
1] was prepared.

A composition [x-1] was applied to a substrate (1) made of an acrylic resin plate ("Acrylite L" manufactured by Mitsubishi Rayon Co., Ltd.) of 5 cm × 5 cm × 1 mm using a bar coater.
Is applied, and the coating is semi-cured by irradiating 50 mw / cm ² of ultraviolet light for 3 seconds to obtain a 85 μm thick semi-cured resin.
The layer (2) was formed.

The composition [x-1] is applied on the first resin layer (2) using a bar coater, and the flow path (4) shown in FIG. And the part other than the part that becomes the optically thermosensitive substance enclosing part (5),
After irradiating the same ultraviolet ray as above for 3 seconds to semi-curing the irradiated portion of the coating film, the uncured portion of the uncured composition [x
-1] is removed, and a groove having a width of 92 μm, a depth of 88 μm, a length of 15 mm × 10 turns to become a flow path (4), and a width of 290 μm and a depth to become an optically thermosensitive substance enclosure (5) A resin second layer (3) in which a U-shaped groove-shaped concave portion was formed as a resin defective portion when viewed from above 88 μm was formed, and a member (A) having a groove was obtained.

Using a bar coater, the composition [x-1] is applied to the same acrylic resin plate base (7) as above with a size of 5 cm × 5 cm × 1 mm, and the same ultraviolet rays as used above are applied to the photomask. Irradiate for 3 seconds without any, to make the coating semi-cured,
98 μm thick semi-cured resin layer (6) on substrate (7)
Was formed as the member (B).

The surface of the semi-cured resin layer (6) of the member (B) is brought into close contact with the resin second layer (3) of the member (A), and the same ultraviolet ray is further irradiated for 30 seconds in this state, to thereby remove all the resin. The layer was cured and adhered, and the groove and the recess formed in the member (A) were formed as a capillary channel (4) and an optically thermosensitive material enclosure (5), respectively.

Next, 1.6 mm each was placed on both ends of the flow path (4) of the base material (7) of the member (B) and the resin layer (6).
And a stainless pipe having a diameter of 1.6 mm was adhered to the hole to form an inlet (8) and an outlet (9), thereby obtaining a microchemical device [D-1] precursor.

[Immobilization of an optically thermosensitive substance] 5 parts of cholesteryl nonanoate (manufactured by Kanto Chemical Co., Ltd.), 5 parts of 3-chlorocholest-5-ene (manufactured by Kanto Chemical Co., Ltd.), and cholesteryl oleyl carbonate (Macros Olga) The liquid crystal [LC-1], which is an optically thermosensitive substance, was prepared by mixing 50 parts of Nix. This liquid crystal [LC-1] is filled in the optically thermosensitive substance enclosing part (5) of the precursor of the microchemical device [D-1], and both ends are sealed with epoxy resin.
A microchemical device [D-1] in which a liquid crystal which is an optically thermosensitive substance is encapsulated and has a reaction channel (4) and a thermosensitive substance enclosing section (5) having a shape shown in FIGS. ] Was produced.

[Temperature Control Test] A brass temperature control block (not shown) having an area of 20 mm × 20 mm was connected to a temperature control region α indicated by a virtual line in FIG. 1 of the microchemical device [D-1].
With a thin film of silicone oil. In addition, the microchemical device [D-1] was placed under a stereoscopic microscope of 30 times, and the optically thermosensitive substance sealed portion (5) was observed with reflected light.

At room temperature 25 ° C., distilled water was continuously flowed from the inlet (8) of the microchemical device [D-1] using a micropump at a flow rate of a residence time of 10 minutes. ). On the other hand, in this state, when the temperature of the brass temperature control block was raised from room temperature at 1 ° C. per minute, the hue of the optically thermosensitive material enclosure (5) was from room temperature to 40 ° C.
The color changed to blue at 42 ° C, yellow at 42 ° C, and transparent at 45 ° C. The cycle of temperature decrease and temperature increase was repeated 10 times, but reproducibility was observed even when the temperature was decreased and when the temperature was increased again. Similar results were obtained even when the temperature increase rate was set to 10 ° C. per minute.

[Comparative Example] [Preparation of microchemical device] A thermocouple prepared by electric welding of a chromel wire and an alumel wire having a diameter of 100 µm instead of filling a liquid crystal in the optically thermosensitive substance filling portion (5). A microchemical device (CD-1) similar to that of Example 1 was prepared, except that sealing (not shown) was sealed (simultaneously during the formation of the optically thermosensitive substance sealing portion (5)).

[Temperature Control Test] The same test as in Example 1 was performed except that the temperature was measured while displaying the temperature measured by a thermocouple. As a result, when the temperature of the brass block is 40 ° C,
The display temperature of the thermocouple was 37.6 ° C. under the heating condition of 1 ° C./min, and 35.4 ° C. under the heating condition of 20 ° C./min.
It can be seen that the error changes depending on the heating condition. When the temperature was lowered at the same rate as the temperature rise, when the temperature of the brass block was 40 ° C., 37.8 ° C. at 1 ° C./min and 10 ° C./min.
In this case, about 41.1 ° C. was displayed. It can be seen that the error due to the history is large.

[Embodiment 2] In this embodiment, a member (C) is filled between the member (A) and the member (B). A production example of a microchemical device provided with a thermosensitive substance enclosing portion was shown.

[Fabrication of microchemical device]
A 5 cm × 5 cm × 1 mm acrylic resin plate (“Acrylite L” manufactured by Mitsubishi Rayon Co., Ltd.) was used as the member (A) and the member (B), respectively. On the member (A),
The same composition [x-1] as that used in Example 1 was applied using a bar coater, and about 20 glass rods (self-made) having a diameter of 60 μm and a length of 1 mm were used as spacers, a portion serving as a channel (4) and Sprinkle at a position where it does not cover the portion that will become the optically thermosensitive material enclosure (5), and place the member (B) on it.
Was adhered.

Using a photomask, a portion other than the portion serving as the flow path (4) and the portion serving as the optical temperature-sensitive material enclosing portion (5) shown in FIG. 50mw
/ Cm ² for 3 seconds to cure the irradiated portion of the composition [x-1] layer to obtain a member (C). Then
Holes were drilled in the member (B) at both ends of the portion to be the flow path (4), and the uncured portion of the uncured composition [x -1], and a flow path (4) having a width of 92 μm, a depth of 60 μm, a length of 15 mm × 10 turns, and a width of 290 μm
A member (C) layer was formed in which a U-shaped optical temperature-sensitive substance enclosing portion (5) having a depth of m and a depth of 60 μm was formed as a resin defective portion. After that, the whole is irradiated with the same ultraviolet ray for 30 seconds,
The member (C) layer was completely cured.

Next, in the same manner as in Example 1, stainless steel pipes were bonded to the holes at both ends of the flow path to form an inlet (7) and an outlet (8). As the liquid crystal, 5 parts of cholesteryl nonanoate (manufactured by Kanto Chemical Co., Ltd.), 7 parts of 3-chlorocholest-5-ene (manufactured by Kanto Chemical Co., Ltd.), and 20 parts of cholesteryl oleyl carbonate (manufactured by Macross Organics) are mixed. Liquid crystal was sealed in the optically thermosensitive substance sealing portion (5) in the same manner as in Example 1 except that the liquid crystal [LC-2] thus obtained was used.

Thus, in FIGS. 1 and 2,
The first resin layer (2) of the member (A) and the resin layer (6) of the member (B) do not exist, and the second resin layer (3) is the member (C). A microchemical device [D-2] similar to the microchemical device [D-1] prepared in Example 1 was prepared except that the composition was different.

[Temperature Control Test] A thermo-cooler (SAMOLSL-1 manufactured by Nippon Blower Co., Ltd.) was used as a temperature control block.
0F type), the whole of the microchemical device was brought into close contact with it, and the temperature of the temperature control block was set to 25 ° C.
The same test as in Example 1 was performed except that the temperature was lowered at a rate of 6 ° C./min. As a result, when the temperature was lowered to 18 ° C., the color tone of the optically thermosensitive substance sealed portion (5) changed from red to orange, and further changed to yellow-green at 15 ° C. Thereafter, a cycle of heating and cooling was repeated 10 times, and reproducibility was observed even when the temperature was increased or when the temperature was decreased again.

[Example 3] [Preparation of microchemical device] One part of 3-chlorocholest-5-ene (manufactured by Kanto Chemical Co., Ltd.) and cholesteryl oleyl carbonate (macros organics) were used as liquid crystals as optical temperature-sensitive substances. Except for using 8 parts of the mixture, a microchemical device [D-3] was produced in the same manner as in Example 1.

[Temperature Control Test] The same test as in Example 2 was performed except that the temperature was raised from 25 ° C. at a rate of 6 ° C./min. As a result, at 30 ° C., the color of the optically thermosensitive substance sealed portion (5) changed from blue to colorless and transparent. After that, cool down,
The heating cycle was repeated 10 times, but reproducibility was observed even when the temperature was lowered or when the temperature was raised again.

[0082]

According to the present invention, there is no need to connect to the outside,
Moreover, it is possible to provide a microchemical device having a temperature display mechanism capable of accurately displaying the temperature of a micro area and controlling the temperature with high accuracy, and generally, it is difficult to accurately measure the temperature. It is possible to control the temperature of a specific region with high precision, and it is particularly suitably used for microreactors and microPCR devices.

[Brief description of the drawings]

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

FIG. 2 is a schematic view of an elevation view of the microchemical device manufactured in the example.

[Explanation of symbols]

 1: base material of member (A) 2: resin first layer of member (A) 3: resin second layer of member (A) 4: flow path 5: optically thermosensitive substance enclosing portion 6: member (B) Resin layer 7: base material of member (B) 8: inlet 9: outlet α: temperature control region

Claims (6)

[Claims] 1. A substance having a micro-capillary flow path therein, and a substance whose optical characteristics are changed by a temperature change is fixed.
A microchemical device with a temperature display mechanism. 2. The microscopic device according to claim 1, wherein the fixing of the substance whose optical properties change due to the temperature change is fixing by enclosing the substance whose optical properties change due to the temperature change into a member constituting a microchemical device. Chemical device. 3. The microchemical device according to claim 1, wherein the substance whose optical characteristics change with a temperature change is a liquid crystal. 4. The microchemical device is composed of a member (A) and a member (B), and the capillary channel has a groove formed on the surface of the member (A) and a groove formed on the surface of the member (A). And (B) formed by a member (B) bonded to the groove forming surface of the member (A), wherein a substance whose optical characteristics change due to a temperature change is formed on the groove forming surface of the member (A). Claim 1 which is enclosed in the space formed by
3. The microchemical device according to any one of 3. 5. The microchemical device, comprising: a member (A);
It is composed of the member (B) and the member (C) filled between these members, and a flow path is formed between the member (A) and the member (B) as a defective portion of the member (C). Wherein a substance whose optical properties change due to a temperature change is sealed as a defective portion of the member (C) in a space formed between the member (A) and the member (B). Items 1-3
A microchemical device according to any one of the above. 6. The microchemical device according to claim 1, wherein the microchemical device is made of an organic polymer.