JP2006187730A - Method for manufacturing resin-made micro flow passage chemical device and structure of resin-made micro flow passage chemical device manufactured thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a micro flow passage chemical device having specific high quality in large quantities inexpensively in a short period of time in order to solve the preblem of the conventional micro flow passage chemical device that an inorganic material is used mainly from standpoints of the workability and accuracy however it is difficult to form a micro flow passage and obtain specific joining strength and it takes much times to manufacture the micro flow passage chemical device. <P>SOLUTION: The method for manufacturing the resin-made micro flow passage chemical device is provided by which a substrate which is made of resin and is formed with a groove for a micro flow passage and a cover substrate which is made of the resin and is used for forming the groove into the micro flow passage are joined to each other, the resin capable of being joined by being subjected to irradiation of ultraviolet rays in vacuum and pressurization. The method comprises the steps of: pretreating the substrate and the cover substrate by irradiating the surfaces to be joined of these substrates with ultraviolet rays (having 200-120 nm, preferably, 172 nm wavelength, for example) in vacuum; laminating these substrates thus irradiated on each other; and joining the laminated substrates to each other by heating them to the temperature lower than the plastic deformation temperature of the resin or pressurizing them without heating them. The micro flow passage chemical device manufactured by this method is excellent in stability of a cross-sectional structure of the micro flow passage and pressure-resistant performance. The micro flow passage chemical device can be easily manufactured inexpensively according to this simple method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method of manufacturing a resin microchannel chemical device used for chemical reactions utilizing microchannels, separation, analysis, detection, and the like, and a resin microchannel chemical device manufactured thereby. .

In recent years, attention has been focused on the specificity of chemical reactions in the microscopic area, and research is being actively conducted to apply them to biopolymer measurement, organic synthesis, and other fields. These have minute channels (microchannels) on the order of millimeters to micrometers, and are intended to perform chemical reactions, separation, analysis, detection, etc. in the space of these microchannels. A device / chip having a micro flow channel is generally called a micro total analysis system (μ-TAS), a microreactor, a micro flow channel chemical device, or the like.
Conventionally, materials such as glass, synthetic quartz glass, polydimethylsiloxane (PDMS) (silicon rubber-based) are used to manufacture this microchannel chemical device (commercial production and production at the laboratory level). If the resin is used as a material, the resin substrate on which the microchannel is formed is laminated by using an adhesive, or is laminated by heating and fusing. It is manufactured by.

  These are composed of at least two or more substrates having a flat surface on the front surface and back surface of the substrate, and a micro flow path is formed on a part of the flat surface of the substrate. The target gas or liquid, such as synthesis, is allowed to flow in for analysis and reaction.

  The dimensions of the microchannel itself in this microchannel chemical device are currently mainly in the order of millimeters to micrometers. Especially in micrometer-order capillaries, when different liquid phases merge, the reaction time is shortened due to the efficient diffusion of mutual molecules, and in the micro region, the reaction efficiency at the liquid-liquid interface is reduced. In addition, since the efficiency of heating and cooling is increased, there is an advantage that a short time reaction can be achieved with a small number of samples. For this reason, in the field of bioanalysis and clinical application chemistry, as well as in the development of nanometer-sized particles, reaction using a microchannel chemical device from a conventional test tube-sized reaction in a laboratory. The demand for is increasing.

  In general, a microfabrication technique typified by photolithography is often employed as a manufacturing technique of the microchannel, depending on a requirement of a channel dimension on the order of micrometers. In particular, due to dimensional accuracy and processing stability, there is a background in which micro processing technology favored processing technology based on semiconductor processes, and it is known that microlithography is also used for microchannel formation. Development of manufacturing technology by fusion with machining and electroforming technology is also actively studied.

  For example, based on photolithography, isotropic etching using a hydrofluoric acid-based etchant (etchant) of glass or a silicon substrate, anisotropic etching to a silicon substrate, Deep RIE (RIE: Aiming at high aspect ratio) Reactive ion etching) and thick film formation chemically amplified photoresists are photocast with synchrotron radiation and electrocasted using high-aspect-ratio shaped products as molds. The current situation is being done.

  For this reason, inorganic materials such as glass plates, quartz plates, silicon plates, metals and ceramics are mainly used from the viewpoint of processability and accuracy using the above-described micromachining technology. Manufacturing a flow channel substrate and a lid substrate by forming a micro flow channel in the material, and joining them firmly to form a micro flow channel chemical device with the required narrow tubes (micro flow channels) embedded, is expensive to manufacture. In addition, since manufacturing has to spend a long time, it was far from being applicable to low-cost, disposable (disposable) applications.

  On the other hand, looking at the technology for joining the flow channel substrate with the micro flow channel and the lid substrate, a method of making the micro-processed product male and then inverting it to a resin has recently been reported. At the room level, it is common to seal the male mold with silicon rubber-based polydimethylsiloxane (PDMS), peel off after curing, obtain a microchannel transfer, and bond it to a glass substrate. However, since the bonding to the glass serving as the support substrate is only due to the self-adhesive property of PDMS, it is limited to applications that do not require a large internal pressure, and cannot be applied to high-pressure liquid passage such as liquid chromatography. Therefore, in order to achieve high pressure resistance, a microchannel chemical device with high pressure resistance performance can be created by creating a microchannel structure material with silicon wafer, glass, some metals, etc., and performing solid phase bonding at high temperatures. Although it is possible, there is a problem that it is not practical because it is not suitable for manufacturing cost and mass production as described above.

For these reasons, devices using resin have been proposed in recent years.
For example, a microchip for performing electrical and / or optical measurement of a liquid sample, which has at least a lower substrate having a minute flow path through which the liquid sample flows and an upper substrate, and at least the lower substrate is specified After the oxygen plasma treatment is performed on at least the surface of the lower substrate having the flow path, the lower substrate and the upper substrate are less than the glass transition temperature (Tg) of the transparent hydrocarbon polymer. There has been proposed a microchip obtained by thermocompression bonding at a temperature of (see, for example, Patent Document 1).
However, there is a problem that it is difficult to uniformly treat the surface of the substrate with oxygen plasma or that oxygen plasma must be produced.
Also, it comprises a flow path having an inlet and an outlet for the sample to be analyzed and an inlet and an outlet for the medium for analysis, and consists of a laminate of two resin molded parts having transparency in the ultraviolet or visible light region. A method for manufacturing a micro-channel device, in which a resin-molded part in which a groove serving as the channel is formed on the surface of at least one resin-molded part is bonded to each other, and the bonded body having the channel formed therein There is also proposed a manufacturing method of a micro-channel device characterized by having a manufacturing process of a bonded body for manufacturing a film and a coating process for coating the bonded body with a silicon dioxide film (for example, Patent Document 2). reference).
However, it is difficult to say that it is practical because it is not covered with a silicon dioxide film, and there are problems such as production cost and production time.

  In this way, conventional microchannel chemical devices use materials such as glass, synthetic quartz glass, and polydimethylsiloxane (PDMS) (silicon rubber), so that microchannels are formed and laminates with bonding strength are formed. There are also problems such as difficulty in manufacturing and time-consuming manufacturing, and there are resin-made micro-channel chemical devices manufactured by adhesives and heat fusion, but the cross-sectional shape of the channel follows the entire channel In fact, there is no established technology that can produce a certain high-quality microchannel chemical device in a mass production, at a low cost, and in a short time. is there.

JP 2003-240755 A JP 2002-139419 A

From the above situation, there has been a demand for a resin-made microchannel chemical device in which a microchannel is formed with a resin and a lid substrate joined without using glass, ceramics, a silicon substrate, or the like. . However, when an adhesive is used for bonding, the adhesive oozes out into the micro flow path and the flow path is blocked, and the homogeneous characteristics of the flow path wall surface are disturbed. It is not preferable because a part of the micro flow path becomes narrow and the flow path becomes non-uniform, and if it is fused at a temperature higher than the heating melting temperature, the flow path may be collapsed in the heating stage, or the flow path may have a predetermined cross-sectional shape. Problems such as inability to hold.
Therefore, resin materials are used in order to obtain the same or better workability and accuracy achieved by using inorganic materials such as glass plates, quartz plates, silicon plates, metals, and ceramics. There is a need to establish a method for producing a high-quality micro-channel chemical device that can maintain the micro-channel cross-sectional shape by a simple method without using an adhesive and has high pressure resistance.

Therefore, the present inventors manufactured a resin-made micro-channel substrate and a lid substrate by a simple method, without using an adhesive, the type and surface state of the material resin, the cross-sectional structure stability of the channel, As a result of earnestly researching the development of a stable processing method that can maintain the micro-channel cross-sectional shape in consideration of pressure resistance performance, etc., a resin-based channel substrate that forms micro-channels by combining the modification of the bonding interface and crimping The present inventors have obtained the knowledge that a resin-made microchannel chemical device having excellent cross-sectional structure stability, pressure resistance performance, and the like can be manufactured by joining the lid substrate to the lid substrate.
That is, according to the present invention, the surface to be bonded with the resin flow path substrate or the cover substrate in which the groove of the micro flow path is formed is first subjected to pretreatment by irradiating with vacuum ultraviolet rays, and then both are pressure bonded. This is a method of manufacturing a resin microchannel chemical device. The microchannel chemical device manufactured by such a method is excellent in cross-sectional structure stability of the channel, pressure resistance, etc., and can be manufactured easily and inexpensively by a simple method.

  The present invention will be described in more detail.

The material resin for the resin substrate and the resin lid substrate for forming the groove of the micro flow path used in the present invention may be any resin as long as the resin surface adheres by the pressurizing means when the resin surface is treated with vacuum ultraviolet rays. Can be used. Representative resins include, for example, polymethyl methacrylate, cycloolefin polymer (COP), and polyether ether ketone (PEEK).
Among these resins, there is a resin that adheres very well under heating conditions up to a temperature lower than the plastic deformation temperature, although the adhesive strength is weak at room temperature when bonded by a pressure means.
In the present invention, in the case of pressure bonding, it means either pressure bonding at normal temperature or pressure bonding under heating conditions up to less than the plastic deformation temperature.

  The resin substrate and the resin lid substrate in which the grooves of the microchannels are formed may be the same type of resin or different types of resin, but the same type of resin is preferable from the viewpoint of adhesiveness.

  Moreover, what blended two or more types of resin can be used for these resin. However, if they are not mixed uniformly, bonding failure may occur when bonded, and pressure resistance decreases, which is not practical.

  The polymethyl methacrylate may be a homopolymer or a copolymer. Any comonomer that can be copolymerized with methyl methacrylate can be used as long as it does not impair the properties of polymethyl methacrylate.

  Polyetheretherketone resin is composed of a combination of phenylketone and phenylether, and is usually abbreviated as PEEK. It is well known that it has already been marketed under trade names such as Victrex, Kedell, PEKK, and Ultrapec. Resin.

  The cycloolefin polymer (COP) is a polymer having an alicyclic structure in the main chain synthesized using cycloolefins as monomers. Examples of the polymer include a ring-opening metathesis polymer hydrogenated polymer obtained by ring-opening metathesis polymerization of a norbornene-based monomer and then hydrogenating a double bond in the polymer. Examples of commercially available products include ZEONEX (manufactured by Nippon Zeon Co., Ltd.).

  The shape of the substrate may be a plate shape, a sheet shape, or a film shape. An assembly of resin substrates on which microchannel grooves are formed in advance may be manufactured first, and then cut into resin substrates with the required dimensions. You may form the groove | channel of a microchannel. From the standpoint of ease of manufacture, it is better to first manufacture an assembly of resin substrates in which the grooves of the microchannels are formed in advance, and then cut into individual resin substrates.

  In addition, when using a sheet-like or film-like one as it is, first, a microchannel is formed on the surface, vacuum ultraviolet treatment is performed and this treatment is performed, and a sheet-like or film-like one that becomes a lid substrate After joining, it is good also as a product cut | disconnected to a predetermined dimension.

Next, a method for forming a microchannel on the surface of the resin substrate will be described.
As a technique for forming the micro flow path, for example, there are a photolithography method and an injection molding method.
In photolithography, a photoresist film is coated on a resin substrate to be processed, and the coated film is exposed to a figure through a photomask having a predetermined graphic pattern, and then the photoresist is coated using a developer. The development is performed, the photoresist remaining on the substrate after development is used as a protective film, the substrate is etched, and finally the photoresist film is removed to form a microchannel having a required shape. The minute flow path may be formed by lithography using an electron beam (EB) as well as those using visible light, ultraviolet light, far ultraviolet light, and X-rays.

Although the reagent for etching varies depending on the resin, it may be etched using a known etching solution and is not limited to a specific one.
As an etching method, a dry etching method is also applied. As this dry etching method, an ordinary known dry etching method such as reactive ion etching (RIE) or plasma ashing can be applied.

  In the case of the injection molding method, for example, a negative photoresist is applied on a metal substrate as an auxiliary mold, exposed, developed, etched, and the resist is removed to form a convex portion of a required shape. The auxiliary mold is prepared, and the auxiliary mold is provided in the mold, and a microchannel having a required shape is formed on the resin surface by injection molding. It is also possible to manufacture by the compression molding method using this auxiliary mold.

  When manufacturing a resin substrate with a microchannel groove formed using a resin sheet that exhibits flexible physical properties, a long roll-shaped sheet is continuously micropatterned on the surface by photolithography. After forming the groove of the flow path and cutting it into the required shape and forming it as a resin substrate, it is treated with high-energy vacuum ultraviolet light with a single wavelength of 172 nm, or vice versa. It can also be cut into a required shape to form a resin substrate.

Next, processing using vacuum ultraviolet rays will be described.
Among the ultraviolet rays, those having a wavelength region of 200 nm or less require a vacuum atmosphere, and the region below this is called vacuum ultraviolet rays. In the present invention, the resin material to be bonded is pretreated using this vacuum ultraviolet ray. Any wavelength range of this vacuum ultraviolet ray can be used, but among these wavelength ranges, a wavelength range of 200 to 120 nm, and further a wavelength of 172 nm is preferable. In the case of 172 nm, it is a single wavelength.

In the present invention, when irradiated with vacuum ultraviolet rays, the surface is modified and can be joined by pressure bonding, but the cause is not clear.
As methods for increasing the wettability of the surface of the resin substrate, ultraviolet irradiation, oxygen plasma treatment, corona discharge treatment, and the like are generally known. These treatments are thought to improve wettability because oxidative degradation products of the resin are formed and deposited on the surface. Taking ultraviolet irradiation as an example, oxygen in the atmosphere generates ozone O ₃ by ultraviolet (UV) irradiation, and active oxygen Ox is generated from O ₃ that has absorbed UV. Due to the high oxidizing power of Ox, the resin on the front substrate is cut off by bonding between molecules, and a clean surface is obtained.
Vacuum ultraviolet rays make it possible to dramatically improve the effects of these oxidative decomposition processes and allow them to be processed in a short time. When a dielectric barrier discharge excimer lamp is used, active oxygen species are excited and generated directly from O _{2 as} well as O ₃ , so that the concentration of active oxygen species contributing to oxidative decomposition is high, and highly efficient oxidative decomposition is possible. . Further, it has been found that when at least an amorphous resin is irradiated with vacuum ultraviolet rays, the polymer itself is damaged by bonding. The reason for this is not clear, but it is not just a hydrophilization effect by oxidative decomposition, but the active species are expressed everywhere due to the generation of carbonyl groups, carboxyl groups, hydrosyl groups, other free radicals, and damage to the polymer. It is thought that this greatly contributes to the strong bonding by the pressure bonding process.

  The processing time in the case of irradiation with vacuum ultraviolet rays generally relates to the intensity of the light source, the distance (distance) between the material to be processed and the light source, and the wavelength. The stronger the light source, the shorter the irradiation time when the interval is narrowed, and the shorter the wavelength, the shorter the irradiation time. In general, the irradiation time is from several seconds to several tens of seconds to several minutes.

  Further, as a light source for obtaining vacuum ultraviolet light having a single wavelength of 172 nm, there is the above-described dielectric barrier discharge lamp. The treatment is performed by irradiating high-energy vacuum ultraviolet light having a single wavelength of 172 nm for several seconds to several minutes under atmospheric pressure. In view of the fact that vacuum ultraviolet rays are easily absorbed in the atmosphere, the gap between the light source and the material to be processed should be several mm, preferably 1.0 mm. In the pressure treatment for bonding, it is expected that atmospheric components may hinder the effect depending on the state of chemically active species at the bonding interface. In such a case, the pressure may be reduced, inert gas, However, it is important to be able to perform processing in the atmosphere in order to reduce the process cost.

  This treatment can be applied to one or both surfaces of the substrates to be joined.

  Prior to this treatment, it is desirable that the surface of the substrate to be treated is appropriately degreased and cleaned to remove oils and fats and foreign matters, and dried.

Further, a joining method will be described.
In the bonding, the substrates of the resin to be bonded are heated to a temperature below the plastic deformation temperature, or those subjected to high energy vacuum ultraviolet ray treatment without heating are superposed and pressure bonded. In this way, a strong bond can be obtained. In general, it seems that stronger bonding is obtained when pressure bonding is performed by heating to a temperature below the plastic deformation temperature.

  Examples of the pressure bonding means include a press means and a roll pressure means.

When the substrates in the present invention are pressure bonded, the grooves of the microchannels may be formed on both sides of the resin substrate or only on one side. When forming on both sides, it is necessary to design the groove so that it does not overlap with the groove formed on another substrate when the substrates are stacked. Of course it is good.
In a simple case, a resin substrate formed with a single microchannel groove and a resin lid substrate that forms a groove in the microchannel are polymerized and joined together to form a resin microchannel chemical device. To do.

  When the amount of liquid or gas to be flowed through the microchannel increases, the resin substrate and the resin lid substrate on which a plurality of microchannel grooves are formed are joined and integrated to form a resin microchannel. A channel chemical device. In such a case, the resin substrates serve as a resin lid substrate that forms grooves in the microchannel that should become microchannels formed on the surface of another resin substrate. Then, the lid substrate having the last remaining groove as a minute flow path is polymerized and joined to be integrated. As a sequence in the case of superposing and joining a large number of substrates, all the necessary substrates may be joined and integrated simultaneously, or the substrates may be joined and integrated sequentially, or a plurality of substrates. May be joined together, and several of these may be joined one after the other or simultaneously.

  As the pressing means, any pressing machine can be used as long as it is a type that sandwiches and pressurizes a laminate of a required number of substrates to be joined. Usually, the press machine is roughly classified into a mechanical press and a hydraulic press, and any of them can be used. Depending on the scale to be produced, the size and the pressure applied, a product suitable for the purpose can be used.

  The roll pressurizing means pressurizes and joins through the substrate material to be laminated between the rotating rolls, and can superpose and bond any number of substrates through the rolls and pressurize them in a short time. It is very convenient because it can. In addition, roll lamination means capable of continuous pressure bonding when the material to be bonded is a long sheet or film is particularly convenient. In this roll pressurizing means, a pair of rotating rolls may be arranged side by side and these may be sequentially passed to perform the joining operation.

  In the present invention, a method for producing a resin-made microchannel chemical device by bonding an arbitrary number of resin substrates having microchannel grooves formed on the surface thereof and a resin lid substrate for forming the grooves in the microchannels; Includes all of the above cases.

  As an auxiliary means for enabling connection to the outside of the microchannel chemical device, there is a large groove or hole. The large groove may be provided in advance with a large groove that can be connected to the outside, and subsequently, a groove of a microchannel may be formed on the surface. As the hole, a through hole that allows connection to the outside may be formed in the substrate in advance.

  The production method of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic diagram showing vacuum ultraviolet treatment of the surface of a substrate. Here, 10 is a vacuum ultraviolet light source for generating vacuum ultraviolet light, 11 is a vacuum ultraviolet light 11 irradiated from the light source 10, 3 is a resin substrate on which a groove 5 of a micro flow path is formed, and 4 is a micro groove. The resin lid substrate formed in the flow path, 7 and 8 are the surface modification layers of the resin substrate 3 and the resin lid substrate 4 modified by the vacuum ultraviolet ray 11, and 5 is the groove of the minute flow path.
First, the surface to be bonded between the resin substrate 3 and the resin lid substrate 4 is cleaned with a solvent or the like as necessary, and then the surface of the resin substrate 3 is modified by irradiating the vacuum ultraviolet light 11 from the vacuum ultraviolet light source 10. A surface modification layer 8 is formed on the surface of the quality layer 7 and the resin lid substrate 4.

FIG. 2 is a schematic diagram of a process in the case of bonding both substrates processed in FIG.
The resin substrate 3 and the resin lid substrate 4 processed in FIG. 1 are polymerized with the surface modification layers 7 and 8 facing each other, and then heated and pressurized to join the two substrates. At this time, the groove 5 of the minute channel finally becomes a minute channel by the resin lid substrate.

  FIG. 3 is a schematic view of a cross section in the longitudinal direction of the groove 5 of the microchannel in FIG. In this example, a large channel 6 that enables connection to the outside is formed, followed by the formation of a micro flow channel 5.

  FIG. 4 shows the integrated micro-channel chemical device 1 after the resin substrate and the resin lid substrate are joined by heating and pressurizing, and corresponds to the one shown in FIG.

  FIG. 5 is a conceptual diagram in the case of mass production of a microchannel chemical device using a sheet or film. Here, a sheet-shaped resin substrate provided with a groove for a micro-channel in advance and a sheet-shaped resin lid substrate formed in the micro-channel are each rolled out in order to obtain a vacuum ultraviolet ray from a vacuum ultraviolet light source. Then, they are integrated by joining with both by roll lamination means, and finally cut into each to form a microchannel chemical device. Here, there is shown one case each of a sheet-like material to be a resin substrate and a sheet-like material to be a resin lid substrate, but a plurality of sheet-like materials to be a resin substrate are prepared simultaneously and roll lamination means The two sheets can be laminated and joined together, and two sheets of each sheet are joined first, and then another sheet is joined again to laminate and join the required number of substrates. It is good also as a channel chemical device.

  The effect exerted by the present invention is that the surface to be bonded with the substrate having the micro flow path formed of the resin that can be bonded by the high-pressure vacuum ultraviolet ray and bonded by the pressurizing means and the surface to be bonded with the lid substrate is first a high wavelength of 172 nm. Pretreatment by irradiating energy vacuum ultraviolet rays, then laminating the substrate and heating it to a temperature below the plastic deformation temperature, or pressurizing without heating and joining the two together is easy and easy. This produces the effect that a road chemical device can be manufactured. This manufacturing method enables strong bonding while maintaining the flow channel structure, which has been a concern for resin microchannel chemical devices. Devices can be widely marketed.

  Although the example which actualized this invention is shown below, it is not limited to this.

[Example 1]
A microchannel chemical device using a highly transparent amorphous resin was fabricated for fluorescence analysis.
First, two types of substrates, a substrate on which a microchannel was formed and a lid substrate with a through hole, were manufactured by an injection molding method. The resin used was a polymethyl methacrylate resin (product name: Acrypet VH, manufactured by Mitsubishi Rayon, melting temperature: 245 ° C.), and the molding conditions were standard, with a plate shape having an outer shape of 30 mm × 70 mm and a thickness of 1.0 mm. The substrate was molded. In the case of molding a substrate on which a microchannel was formed, a mold in which a male mold having a desired microchannel pattern was formed in advance was used. Each substrate is a plate having a thickness of 1.0 mm and an outer shape of 30 mm × 70 mm.
First, these two substrates are immersed in isopropyl alcohol and subjected to ultrasonic cleaning, followed by drying by blowing nitrogen gas, and then applying vacuum ultraviolet rays (VUV) using a 172 nm single wavelength dielectric barrier discharge lamp. Irradiated for 2 minutes for pretreatment. The gap between the light source and the substrate to be processed was set to 1.0 mm from the viewpoint of the absorption efficiency of VUV into oxygen and moisture and the efficiency of reaching the surface to be processed.
Then, the two pretreated substrates were pressure-bonded with a jig, heated at an ambient temperature of 80 ° C., and slowly cooled to obtain a highly transparent and strong microchannel chemical device having strong bonding strength. The bonded strength of the two substrates after slow cooling was measured for tensile shear adhesive strength in accordance with JIS K 6850 after standing for 48 hours after bonding. As a result, 6.3 kgf / cm ² ( = 62.1 N / cm ² ) to 6.8 kgf / cm ² (= 66.7 N / cm ² ). Further, the short sides of the substrates after bonding were respectively held by the first and second fingers on the left and right sides, and did not peel off even when twisted. Furthermore, the same result was obtained when a microchannel chemical device having a high transparent and strong bonding strength after heating and slow cooling at 70 ° C. instead of the atmospheric temperature of 80 ° C. was obtained.

[Example 2]
The same member as in Example 1 was prepared, irradiated with vacuum ultraviolet rays for 2 minutes, immediately crimped with a jig in a normal temperature atmosphere, released from the jig and allowed to stand for 48 hours to prepare a sample. Using this sample, the tensile shear bond strength was measured in accordance with JIS K6850, and 5.5 kgf / cm ² (= 53.9 N / cm ² ) to 6.9 kgf / cm ² (= 67.7 N / cm ² ). Further, the short sides of the substrates after bonding were respectively held by the first and second fingers on the left and right sides, and did not peel off even when twisted.

[Comparative Example 1]
The same operation as in Example 1 was repeated except that a substrate that was not subjected to only the vacuum ultraviolet light irradiation treatment was used. The bonded substrate seemed to be bonded at first glance after heating and slow cooling, but when the tensile shear bond strength was measured in accordance with JIS K 6850, it was 0.5 kgf / cm ^2.
The bond strength was not more than (= 4.9 N / cm ² ) and peeled at the moment of twisting.

[Comparative Example 2]
A micro-channel after heating / slow cooling in which the same operation as in Example 1 was repeated except that a substrate that was not subjected to only the vacuum ultraviolet light irradiation treatment was used and the heating temperature (atmosphere temperature) was 90 ° C. The deformation caused partly excessive depth variation. Moreover, although it seemed to be joined at first glance, when the tensile shear adhesive strength was measured in accordance with JIS K 6850, the joint strength was 0.5 kgf / cm ² (4.9 N / cm ² ) or less. It peeled at the moment of twist.

[Comparative Example 3]
The same operation as in Example 1 was repeated except that a substrate that was not subjected only to the vacuum ultraviolet light irradiation treatment was used and the heating temperature (atmosphere temperature) was 120 ° C. The microchannel after heating / slow cooling partially buried an excessive depth variation due to deformation. The microchannel substrate and the lid substrate were completely integrated.

[Example 3]
The same operation as in Example 1 was repeated except that the highly transparent amorphous resin was changed to a cycloolefin polymer (ZEONEX 330R, manufactured by Nippon Zeon Co., Ltd.) and the heating operation temperature (atmosphere temperature) was changed to 90 ° C. When the tensile shear bond strength was measured according to JIS K 6850 after standing still for 48 hours after slow cooling, it was 7.2 kgf / cm ² (= 70.6 N / cm ² ) to 7.8 kgf over 10 specimens. The bonding strength was / cm ² (= 76.5 N / cm ² ). Further, the short sides of the substrates after bonding were respectively held by the first and second fingers on the left and right sides, and did not peel off even when twisted. Further, when the depth dimension of the microchannel was measured, the change rate was 1% or less with respect to a width of 100 μm and a depth of 40 μm. Similar results were obtained when the heating operation temperature (atmosphere temperature) was 90 ° C. instead of 90 ° C.

[Comparative Example 4]
The same operation as in Example 3 was repeated except that a substrate on which only the high energy vacuum ultraviolet light irradiation treatment was not used was used. Although the bonded substrate seemed to be bonded at first glance after heating and slow cooling, when the tensile shear bond strength was measured in accordance with JIS K 6850, 0.4 kgf / cm ² (= 3.9 N / cm ^2). ) It had only the following bonding strength, and peeled off at the moment of twisting.

[Example 4]
For microreactors, a microchannel chemical device with non-transparent semi-crystalline, linear aromatic resin was prepared. Two types of substrates, a substrate with a microchannel and a lid substrate with a through-hole, were manufactured by injection molding under known conditions using polyetheretherketone (PEEK 151G, manufactured by Victorex MC). .
Pretreatment was performed in the same manner as in Example 1 except that the irradiation time of vacuum ultraviolet light was 5 minutes. The pressure bonding conditions are completely different from those of the highly transparent amorphous resin group, and the atmosphere is reduced to 133.32 Pa to 399.96 Pa (= 1 Torr to 3 Torr), and the heating operation temperature (atmosphere temperature) is set to 300 ° C., and the temperature is gradually increased. After that, the temperature is kept for a certain time and then gradually cooled. Thereafter, after standing for 48 hours, the tensile shear bond strength was measured according to JIS K 6850, and 10.2 kgf / cm ² (= 100 N / cm ² ) to 11.0 kgf / cm ² (= 107.9 N / cm). ² ). Further, the short sides of the substrates after bonding were held by the first and second fingers on the left and right sides, respectively, and were not peeled off even when twisted. Moreover, when the depth dimension of the microchannel was measured, the change rate was 10% or less with respect to a width of 100 μm and a depth of 40 μm.

[Comparative Example 5]
The same operation as in Example 4 was repeated except that a substrate that was not subjected to only the vacuum ultraviolet light irradiation treatment was used. As a result, the two substrates were not joined at all.

[Example 5]
The two substrates were each made into a film having a thickness of 125 μm, and a micro-channel film and a lid film in which channels were formed by a known compression molding method were prepared. The films are completed as individual pieces of a film-like resin microchannel chemical device through a process of cutting out the outer shape after joining.
The through hole for connecting the micro channel to the outside may be previously machined, but the micro channel was sealed with a lid film having no through hole. For connection to the outside, the large groove exposed in the cross section functions as a through hole by cutting a large groove portion formed continuously in advance in the micro flow path.
The resin used was a polymethyl methacrylate film (Technoloy S003, manufactured by Sumitomo Chemical Co., Ltd.), and a microchannel and a large channel were formed by a known compression molding method using a male mold prepared by a photolithography method. Then, vacuum ultraviolet rays were irradiated for 30 seconds, and it used for crimping | bonding continuously. For continuous pressure bonding, heat and pressure were applied by roll lamination. For roll lamination, a film laminator equipped with a heating mechanism was used in a roll with rubber lining, and an appropriate pressure and roll surface temperature were set and processed. When the tensile shear bond strength was measured in accordance with JIS K 6850 after standing for 48 hours after bonding at a temperature of 95 ° C. on the roll surface of the roll lamination, the same bonding strength as in Example 1 was obtained. Furthermore, when the roll temperature is operated at room temperature, the bonding strength is reduced by about 15% to 5%, but basically the same effect is recognized.

[Example 6]
The same as Example 5 except that the two substrates were each replaced with a cycloolefin polymer (ZEONOR film ZF14, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 188 μm and the roll lamination roll surface temperature was changed to 105 ° C. The operation was repeated. After standing for 48 hours after roll lamination, the tensile shear bond strength was measured according to JIS K 6850, and the same result as in Example 5 was obtained.

The schematic diagram of the process of the vacuum ultraviolet-ray process of the surface of a board | substrate is shown. The schematic diagram of the process in the case of joining both the board | substrates processed in FIG. 1 is shown. It is a schematic diagram of the cross section of the longitudinal direction of the groove | channel 5 of the microchannel of FIG. The microchannel chemical device 1 obtained by joining in FIG. 2 thru | or FIG. 3 is shown. The conceptual diagram in the case of mass-producing a microchannel chemical device using a sheet form or a film form is shown.

Explanation of symbols

1: Micro-channel chemical device 2: Micro-channel 3: Resin substrate 4: Resin lid substrate 5: Micro-channel groove 6: Large groove 7, 8: Surface modification layer 10: Vacuum ultraviolet light source 11: Vacuum ultraviolet

Claims (10)

In a method of manufacturing a resin-made microchannel chemical device by joining a resin substrate in which grooves of an arbitrary number of microchannels are formed on a surface and a resin lid substrate that forms the grooves in the microchannels,
The resin material is a resin that can be bonded by means of pressurizing means after irradiation with vacuum ultraviolet rays,
The surface of both substrates or one of the substrates is irradiated with vacuum ultraviolet rays, and then the substrates are laminated and heated to a temperature below the plastic deformation temperature, or pressed without heating and bonded to each other. A method of manufacturing a resin microchannel chemical device. The method for producing a resin microchannel chemical device according to claim 1, wherein the pressurizing means is a press means or a roll pressurizing means.   The resin microchannel chemical device according to claim 1 or 2, wherein a substrate in which a through-hole capable of being connected to the outside is formed in either one or both of the substrates in advance is used. How to manufacture.   3. A resin microchannel chemical device according to claim 1 or 2, wherein a resin substrate having a microchannel groove formed on the surface thereof following a large groove capable of being connected to the outside is used. How to manufacture.   The method for producing a resin microchannel chemical device according to any one of claims 1 to 4, wherein the wavelength of the vacuum ultraviolet ray is 200 to 120 nm.   6. The method for producing a resin microchannel chemical device according to claim 5, wherein the wavelength of the vacuum ultraviolet ray is 172 nm.   The resin according to any one of claims 1 to 6, wherein either or both of the groove of the microchannel and the through hole enabling connection to the outside are formed by photolithography. A method of manufacturing a manufactured microchannel chemical device.   A resin substrate having a micro-channel groove formed on the surface and a resin-cover substrate that forms the groove in the micro-channel, supplied as a long roll, and cut into a resin micro-channel chemical device after bonding A method for producing a resin microchannel chemical device according to any one of claims 1 to 7.   9. The resin microchannel chemical device according to claim 1, wherein the substrate resin is a resin selected from the group consisting of polymethyl methacrylate, cycloolefin polymer, and polyether ether ketone. how to. A resin microchannel chemical device manufactured by the method according to any one of claims 1 to 9.

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