Method for manufacturing flow path device made of cyclic olefin resin

Abstract

The purpose of the present invention is to provide a method for manufacturing a flow path device made of a cyclic olefin resin, said method being capable of manufacturing a flow path device made of a cyclic olefin resin, said flow path device enabling an aqueous liquid to flow satisfactorily in a fine tubular flow path even after long-term storage. This method for manufacturing a flow path device made of a cyclic olefin resin is characterized by comprising a step in which a cyclic olefin resin member having at least one fine tubular flow path is subjected to ozone treatment such that the CT value becomes 2500 g / m3 min or more.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a flow path device made of a cyclic olefin resin. Background Art

[0002] In recent years, flow path devices having fine tubular flow paths such as microfluidic chips and capillaries have been used in various fields such as DNA detection, biomaterial analysis, drug research and development, pharmaceutical development, organic synthesis, and water quality analysis. Among them, a resin-made microfluidic chip having a micron-sized micro flow path and reaction vessel formed by microfabrication technology has attracted attention.

[0003] Moreover, as materials for flow path devices such as microfluidic chips, cyclic olefin resins such as cyclic olefin polymers (COP) and cyclic olefin copolymers (COC) having excellent durability, optical stability, etc. are used (for example, refer to Patent Documents 1 and 2).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2017 / 056638;

[0007] Patent Document 2: International Publication No. 2010 / 061598. Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] However, since the cyclic olefin resin has high hydrophobicity, in a flow path device made of a cyclic olefin resin such as a microfluidic chip made of a cyclic olefin resin, when a hydrophilic liquid flows in a fine tubular flow path, sometimes the liquid is repelled by the cyclic olefin resin and cannot enter the tubular flow path. In addition, if the liquid is pressurized with a pump or the like in order to force the liquid to flow into the tubular flow path, sometimes air bubbles remain in the flow path.

[0010] In view of such a problem, the present inventor has studied the plasma treatment and corona discharge treatment of the cyclic olefin resin component with a fine tubular flow path for the purpose of making the aqueous liquid flow well in the fine tubular flow path in the cyclic olefin resin flow path device, so that the flow path is hydrophilized. However, it is known that in the plasma treatment and corona discharge treatment, although the outer surface of the cyclic olefin resin component can be hydrophilized, the fine flow path inside is not fully exposed to the plasma and cannot be fully hydrophilized, and sometimes the aqueous liquid cannot flow in the flow path. Therefore, the present inventor has further repeatedly studied and thought of using ozone treatment to hydrophilize the fine tubular flow path inside the cyclic olefin resin component, so as to obtain a cyclic olefin resin flow path device that can make the aqueous liquid flow well in the tubular flow path. However, it is known that when ozone treatment is used, although ozone gas can be made to flow into the fine tubular flow path and the flow path can be made hydrophilic, depending on the conditions of the ozone treatment, sometimes when the resulting cyclic olefin resin flow path device is stored for a long time, the hydrophilicity of the flow path disappears over time, making it impossible for aqueous liquids to flow in the flow path.

[0011] Therefore, an object of the present invention is to provide a method for producing a cyclic olefin resin flow path device capable of producing a cyclic olefin resin flow path device capable of allowing an aqueous liquid to flow well in a fine tubular flow path even after long-term storage.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive research for the purpose of solving the above-mentioned problems. As a result, they have newly found that if ozone treatment is performed under predetermined conditions, the hydrophilicity of the tubular flow path can be maintained for a long time, and as a result, even after the obtained cyclic olefin resin flow path device is stored for a long time, the aqueous liquid can flow well in the fine tubular flow path, thereby completing the present invention.

[0014] That is, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is [1] a method for manufacturing a cyclic olefin resin flow path device, comprising: treating a cyclic olefin resin member having at least one fine tubular flow path with a CT value of 2500 g / m 3 If the CT value is 2500g / m 3 If the ozone treatment is performed for 10 minutes or more, the fine tubular flow path can be sufficiently hydrophilized, and the aqueous liquid can flow well in the tubular flow path of the cyclic olefin resin flow path device even after long-term storage.

[0015] [2] In the method for manufacturing the flow path device made of a cyclic olefin resin as described in [1] above, it is preferable that the ozone treatment is carried out with ozone generated by the silent discharge method. If ozone is generated by the silent discharge method in this way, the ozone treatment can be carried out stably.

[0016] [3] In the method for manufacturing the flow path device made of a cyclic olefin resin as described in [1] or [2] above, it is preferable that both ends of the tubular flow path are open, and when a wetting reagent with a wetting tension of 65 mN / m is dropped excessively compared to the volume inside the flow path at one end of the tubular flow path, the wetting reagent reaches the other end of the tubular flow path. If a reagent with a wetting tension specified in this way can reach from one end to the other end of the tubular flow path, the aqueous liquid can flow well inside the tubular flow path.

[0017] [4] In the method for manufacturing the flow path device made of a cyclic olefin resin as described in [3] above, it is preferable that when the flow path device made of a cyclic olefin resin is stored at 60 °C for 1000 hours and then a wetting reagent with a wetting tension of 70 mN / m is dropped excessively compared to the volume inside the flow path at one end of the tubular flow path, it reaches the other end of the tubular flow path. If a reagent with a specified wetting tension can reach from one end to the other end of the tubular flow path after storing the flow path device made of a cyclic olefin resin at a specified temperature for a specified time in this way, the aqueous liquid can flow well inside the tubular flow path even after storing the flow path device made of a cyclic olefin resin for a long time.

[0018] [5] The method for manufacturing the flow path device made of a cyclic olefin resin according to any one of [1] to [4] above preferably further includes a step of joining at least two cyclic olefin resin molded bodies to obtain the cyclic olefin resin member. If at least two cyclic olefin resin molded bodies are joined in this way, a cyclic olefin resin member having a fine tubular flow path can be easily obtained. In addition, in the case of obtaining a flow path device made of a cyclic olefin resin with a hydrophilized flow path by subjecting the cyclic olefin resin molded body before joining to high-intensity ozone treatment and joining the ozone-treated cyclic olefin resin molded bodies, since oxides are formed on the joint surface of the members due to the high-intensity ozone treatment, it may not be possible to obtain sufficient joint strength. However, if ozone treatment is carried out after joining, a flow path device made of a cyclic olefin resin with excellent joint strength and in which the aqueous liquid can flow well in the fine flow path even after long-term storage can be obtained.

[0019] [6]In the method for manufacturing a flow path device made of a cyclic olefin resin according to [1] to [5] above, it is preferable that the flow path device made of a cyclic olefin resin is a microfluidic chip. The microfluidic chip can be applied to various fields such as DNA detection, biological substance analysis, drug research and development, pharmaceutical development, organic synthesis, and water quality analysis.

[0020] Advantages of the Invention

[0021] According to the present invention, there can be provided a method for manufacturing a flow path device made of a cyclic olefin resin, which can manufacture a flow path device made of a cyclic olefin resin in which an aqueous liquid can flow well in a fine tubular flow path even after long-term storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 (a) of is a plan view showing an example of a flow path substrate of a microfluidic chip as an example of the flow path device made of a cyclic olefin resin of the present invention, and (b) is a plan view showing an example of a cover substrate of the microfluidic chip. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0023] Hereinafter, embodiments of the present invention will be described in detail.

[0024] The flow path device made of a cyclic olefin resin manufactured by the method for manufacturing a flow path device made of a cyclic olefin resin of the present invention is not particularly limited, and can be used in various fields such as DNA detection, biological substance analysis, drug research and development, pharmaceutical development, organic synthesis, and water quality analysis.

[0025] (Method for Manufacturing a Flow Path Device Made of a Cyclic Olefin Resin)

[0026] The method for manufacturing a flow path device made of a cyclic olefin resin of the present invention includes an ozone treatment step (ozone treatment step) of subjecting a cyclic olefin resin member having at least one fine tubular flow path to ozone treatment so that the CT value becomes 2500 g / m 3 ·min or more, and optionally, a bonding step (bonding step) of bonding at least two cyclic olefin resin molded bodies to obtain the cyclic olefin resin member before the ozone treatment step.

[0027] <Cyclic Olefin Resin Member>

[0028] As a cyclic olefin resin member for ozone treatment, as long as it has at least one fine tubular flow path, it is not particularly limited, and examples thereof include: tubular bodies with a small inner diameter such as capillaries; members obtained by integrating a plurality of tubular bodies arbitrarily via an adhesive (bonding layer); a member obtained by arbitrarily bonding, via an adhesive, the surface on the flow path side of a cyclic olefin resin molded body (flow path substrate) having fine flow paths (grooves) formed on at least one surface to another cyclic olefin resin molded body (cover substrate) serving as a cover (hereinafter also referred to as "micro flow path chip precursor"), etc.

[0029] In addition, in the present invention, among the cyclic olefin resin members, in addition to the members composed only of cyclic olefin resin, there are also members obtained by bonding cyclic olefin resin molded bodies using a resin other than cyclic olefin resin as an adhesive.

[0030] Here, the mode of the fine tubular flow path is not particularly limited, and it can be open at both ends, or one end can be open and the other end can be sealed inside the cyclic olefin resin member, or it can also be open at any part of the cyclic olefin resin member.

[0031] In addition, the shape of the cross-section of the tubular flow path (the plane perpendicular to the extending direction of the tubular flow path, the same hereinafter) is not particularly limited, and it can be any shape such as a rectangle, a circle, a semi-circle, an ellipse, a polygon other than a rectangle, etc.

[0032] The size of the tubular flow path can be appropriately changed according to the use of the cyclic olefin resin flow path device. For example, when the cross-sectional shape of the tubular flow path is a rectangle, the size of one side of the cross-section of the tubular flow path is usually below the millimeter level, and can also be at the nanometer level, preferably at the micron level. In addition, when the cross-sectional shape of the tubular flow path is a circle, the size of the diameter of the cross-section of the tubular flow path is usually below the millimeter level, and can also be at the nanometer level, preferably at the micron level.

[0033] Specifically, for example, the width and height (depth) of the tubular flow path are not particularly limited, and can be, for example, 10 μm or more and 800 μm or less.

[0034] In addition, the cross-sectional area of the tubular flow path can be, for example, 3×10 -6 mm 2 or more and 3 mm 2 or less.

[0035] [Tubular body]

[0036] As long as the tubular body has at least one fine tubular flow path, it is not particularly limited, and it can have any outer shape such as a cuboid shape, a triangular prism shape, a cylindrical shape, etc. The tubular body can be a flexible and bendable tubular body.

[0037] Here, the tubular body can be composed of only one cyclic olefin resin molded body, or two or more cyclic olefin resin molded bodies as components can be arbitrarily joined to each other via an adhesive. There is no limitation on the tubular body formed by joining two or more cyclic olefin resin molded bodies. For example, a hollow cylinder formed by joining two rod-shaped cyclic olefin resin molded bodies with a substantially semicircular cross-section; a hollow cylinder formed by joining three or more rod-shaped cyclic olefin resin molded bodies with a fan-shaped cross-section; a hollow rectangular parallelepiped formed by joining two rod-shaped cyclic olefin resin molded bodies with a U-shaped cross-section; a hollow rectangular parallelepiped formed by joining one rod-shaped cyclic olefin resin molded body with a U-shaped cross-section and one rectangular plate-shaped cyclic olefin resin molded body; a hollow rectangular parallelepiped formed by joining four rectangular plate-shaped cyclic olefin resin molded bodies; a hollow triangular prism formed by joining three plate-shaped cyclic olefin resin molded bodies with a trapezoidal cross-section, etc.

[0038] From the viewpoint of manufacturing efficiency and the like, the tubular body is preferably composed of only one cyclic olefin resin molded body.

[0039] There is no limitation on the tubular body composed of only one cyclic olefin resin molded body. For example, it can be obtained by molding a tube with a relatively large inner cavity by injection molding or the like as a precursor, and then heating and stretching a part of the precursor to reduce the inner cavity diameter. Alternatively, the tubular body can also be obtained by, for example, forming fine holes extending in the length direction of the molded body inside a solid rod-shaped cyclic olefin resin molded body obtained by injection molding or the like.

[0040] [Flow path substrate]

[0041] As the flow path substrate, which is a cyclic olefin resin molded body used in the microfluidic chip precursor, a substrate made of cyclic olefin resin having fine flow paths (grooves) formed on at least one surface can be used. Moreover, the flow path substrate is joined to the cover substrate with the surface on which the fine flow paths are formed as the joining surface.

[0042] Here, the width, depth, and shape of the fine flow paths can be appropriately changed according to the use of the cyclic olefin resin flow path device, and are usually below the millimeter level, and can also be at the nanometer level, preferably at the micrometer level. Specifically, the width of the fine flow paths is not particularly limited and can be, for example, 10 μm or more and 800 μm or less.

[0043] Forming fine flow paths on the substrate can be performed using, for example, microfabrication techniques such as photolithography and thermal imprint, cutting, injection molding, etc.

[0044] [Cover substrate]

[0045] As a cover substrate that is a cyclic olefin resin molded body used in a microfluidic chip precursor, a cyclic olefin resin substrate capable of covering the fine flow paths (grooves) formed in the flow path substrate can be used. Specifically, as the cover substrate, a cyclic olefin resin substrate having a bonding surface that adheres to the flow path substrate and optionally having the following through-holes can be used. When forming a cyclic olefin resin flow path device together with the flow path substrate, the through-holes become inlets and outlets for liquid samples and the like in the fine tubular flow paths. In addition, as the cover substrate, a substrate having fine flow paths (grooves) formed on the bonding surface side and / or on the surface opposite to the bonding surface side can also be used.

[0046] The formation of through-holes in the cover substrate can be carried out using, for example, microfabrication techniques such as photolithography and hot embossing, cutting, injection molding, etc.

[0047] [Adhesive]

[0048] The adhesive is a material that is interposed between multiple cyclic olefin resin molded bodies and bonds the cyclic olefin resin molded bodies as components to each other. There is no particular limitation on the adhesive, and generally, the cyclic olefin resin described later can be used.

[0049] From the viewpoints of achieving good bonding strength and appearance and suppressing variations in the optical properties of the tubular flow path portion, the adhesive is preferably selectively applied to the bonding surfaces of the cyclic olefin resin molded bodies. Specifically, it is preferred that the adhesive is selectively applied to the entire portion other than the portion that becomes the tubular flow path, the through-holes (inlets / outlets), and other uneven portions.

[0050] The thickness of the applied adhesive (in the case of applying the adhesive to both bonding surfaces of two adjacent cyclic olefin resin molded bodies, it refers to their total thickness) is not particularly limited. From the viewpoints of suppressing overflow into the flow path when applying the adhesive and ensuring the adhesiveness between the cyclic olefin resin molded bodies, it is preferably 0.1 μm or more, more preferably 0.12 μm or more, further preferably 0.15 μm or more, particularly preferably 0.2 μm or more, preferably 50 μm or less, more preferably 40 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less.

[0051] [Material of cyclic olefin resin member]

[0052] The cyclic olefin resin (cyclic olefin polymer) used as a material for the cyclic olefin resin member is, for example, a polymer or copolymer (hereinafter sometimes collectively referred to as "polymer") obtained by polymerizing monomers as described below, or a hydride thereof. The cyclic olefin polymer may be crystalline or amorphous, and is preferably amorphous. As the monomer of the cyclic olefin polymer, norbornene-based monomers are preferably selected. The norbornene-based monomer is a monomer containing a norbornene ring. Examples of the norbornene-based monomer include bicyclic monomers such as bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: ethylidene norbornene), and their derivatives (having substituents on the ring); tricyclic monomers such as tricyclo[5.2.1.0 2,6 dec-3,8-diene (common name: dicyclopentadiene) and its derivatives; tetracyclic monomers such as tetracyclo[7.4.0.0 2,7 .1 10,13 tetradeca-2,4,6,11-tetraene (common name: methano-tetrahydrofluorene), tetracyclo[6.2.1.1 3,6 .0 2,7 dodec-4-ene (common name: tetracyclododecene), 9-ethylidene-tetracyclo[6.2.1.1 3,6 .0 2,7 dodec-4-ene, and their derivatives. These monomers may have substituents at any position. Examples of the substituents include alkyl, alkylene, vinyl, alkoxycarbonyl, alkylene, etc. The above norbornene-based monomers may have two or more of the above substituents. As derivatives, specifically, 8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodec-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10Dodec-3-ene (ethylidene tetracyclododecene, ETD), etc. These norbornene monomers can be used alone or in combination of two or more. In addition, the cyclic olefin polymer can be an addition polymer, a ring-opening polymer, or a hydride thereof, and preferably a ring-opening polymer or a ring-opening polymer hydride. The cyclic olefin polymer used as the material of the cyclic olefin resin member is preferably a polymer obtained by polymerizing monomers having a content of methano-tetrahydrofluorene (MTF) of 25 parts by mass or more relative to 100 parts by mass of the total monomers. The cyclic olefin polymer mixture used as the material of the binder preferably contains at least a cyclic olefin polymer obtained by polymerizing monomers having a content of dicyclopentadiene (DCPD) of 30 parts by mass or more relative to 100 parts by mass of the total monomers.

[0053] The above ring-opening polymer can be produced by a method using a ring-opening polymerization catalyst. As the ring-opening polymerization catalyst, for example, a catalyst composed of a halide of a metal such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent can be used; or a catalyst composed of a halide or an acetylacetone compound of a metal such as titanium, zirconium, tungsten, or molybdenum and an organoaluminum compound can be used. The ring-opening polymer can be produced, for example, by a method using a metathesis reaction catalyst (ring-opening polymerization catalyst) such as the ruthenium carbene complex catalyst described in International Publication No. 2010 / 110323; and a method using a ring-opening polymerization catalyst such as tungsten tetrachloride (phenylimide)-tetrahydrofuran complex or tungsten hexachloride described in Japanese Patent Application Laid-Open No. 2015-54885.

[0054] The above addition polymer can be obtained by polymerizing monomers using a known addition polymerization catalyst, for example, a catalyst composed of a titanium, zirconium, or vanadium compound and an organoaluminum compound. The addition polymer can be produced, for example, by addition copolymerizing a monomer of a cyclic olefin polymer and, if necessary, a monomer capable of addition copolymerization (other monomers) in the presence of a metallocene catalyst described in International Publication No. 2017 / 199980.

[0055] As other monomers capable of ring-opening copolymerization with norbornene monomers, monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene can be cited.

[0056] These other monomers capable of ring-opening copolymerization with norbornene monomers can be used alone or in combination of two or more. In the case of ring-opening copolymerizing a norbornene monomer with other monomers capable of ring-opening copolymerization with it, the ratio of the structural unit derived from the norbornene monomer to the structural unit derived from other monomers capable of ring-opening copolymerization in the ring-opening polymer is appropriately selected so as to be in the range of usually 70:30 to 99:1, preferably 80:20 to 99:1, and more preferably 90:10 to 99:1 by weight.

[0057] As other monomers capable of undergoing addition copolymerization with norbornene-based monomers, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and their derivatives; cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene and their derivatives; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc. Among these, α-olefins are preferred, and ethylene is particularly preferred.

[0058] These other monomers capable of undergoing addition copolymerization with norbornene-based monomers can be used alone or in combination of two or more. When the norbornene-based monomer and other monomers capable of undergoing addition copolymerization therewith are subjected to addition copolymerization, the ratio of the structural unit derived from the norbornene-based monomer to the structural unit derived from other monomers capable of undergoing addition copolymerization in the addition polymer is appropriately selected so as to be usually in the range of 30:70 to 99:1, preferably 50:50 to 97:3, more preferably 70:30 to 95:5 by weight ratio.

[0059] Furthermore, as a method for hydrogenating a ring-opening polymer to produce a hydrogenated product of a cycloaliphatic ring-opening polymer, for example, a method using a hydrogenation catalyst described in International Publication No. 2010 / 110323 can be cited. In addition, for example, after producing a cycloaliphatic ring-containing polymer using the above ruthenium carbene complex catalyst as a ring-opening polymerization catalyst, the ruthenium carbene catalyst can be directly used as a hydrogenation catalyst to hydrogenate the cycloaliphatic ring-opening polymer to produce a hydrogenated product of a cycloaliphatic ring-opening polymer.

[0060] The glass transition temperature (Tg) of the cycloolefin polymer is not particularly limited and can be appropriately adjusted according to the type and blending ratio of the monomers used in the polymerization, the average molecular weight and molecular weight distribution of the polymer, etc. From the viewpoint of heat resistance, the glass transition temperature of the cycloolefin polymer is preferably 100 °C or higher, more preferably 120 °C or higher. If the glass transition temperature of the cycloolefin polymer is at the above lower limit or higher, a cycloolefin resin flow path device without deformation and having high dimensional accuracy as a microchannel chip, capillary, etc. can be obtained. In addition, the glass transition temperature of the adhesive is preferably 100 °C or lower, more preferably 80 °C or lower. If the glass transition temperature of the adhesive is at the above upper limit or lower, good thermal adhesiveness can be obtained.

[0061] In addition, when the tubular body is composed of two or more cyclic olefin resin molded bodies, the types of cyclic olefin polymers used as the materials for these cyclic olefin resin molded bodies may be the same or different, and preferably the same. Similarly, the types of cyclic olefin polymers used as the materials for the flow path substrate and the cover substrate for manufacturing the microfluidic chip precursor may be the same or different, and preferably the same.

[0062] <Ozone treatment step>

[0063] In the ozone treatment step, ozone is used to treat a cyclic olefin resin member having at least one fine tubular flow path so that the CT value becomes 2500 g / m 3 ·min or more. If the CT value is 2500 g / m 3 ·min or more, the fine tubular flow path can be sufficiently hydrophilized, and after long-term storage of the obtained cyclic olefin resin flow path device, an aqueous liquid can also flow well in the fine tubular flow path. From the viewpoint of enabling an aqueous liquid to flow better in the fine tubular flow path even after long-term storage, the CT value is preferably 2700 g / m 3 ·min or more, more preferably 5000 g / m 3 ·min or more, and further preferably 10000 g / m 3 ·min or more. The upper limit value of the CT value is not particularly limited, and the CT value can generally be 20000 g / m 3 ·min or less.

[0064] In addition, the CT value is the product value of the ozone concentration (g / m 3 ) and the ozone exposure time (min), and can be controlled by adjusting the ozone concentration (g / m 3 ) and / or the ozone exposure time.

[0065] The ozone concentration is not limited, preferably 10 g / m 3 or more, more preferably 60 g / m 3 or more, preferably 1000 g / m 3 or less, more preferably 300 g / m 3 or less. In addition, the ozone exposure time is preferably 5 minutes or more, more preferably 20 minutes or more, preferably 240 minutes or less, and more preferably 60 minutes or less.

[0066] The ozone treatment can be carried out using a known ozone generation device. Here, the ozone treatment only needs to be carried out in such a way that at least one fine tubular flow path of the cyclic olefin resin member is hydrophilized. From the viewpoint of manufacturing efficiency and the like, it is preferably carried out in such a way that the whole (entire surface) of the cyclic olefin resin member including the fine tubular flow path is exposed to ozone for hydrophilization. For example, by housing the cyclic olefin resin member in a container having an ozone gas supply port and an exhaust port and injecting ozone generated by the ozone generation device into the container, the whole (entire surface) of the cyclic olefin resin member including the fine tubular flow path can be hydrophilized. In this way, through the ozone treatment, ozone can flow in the fine tubular flow path inside the cyclic olefin resin member, and the flow path can be hydrophilized well.

[0067] In addition, there is no particular limitation on the ozone generation method, and either a silent discharge type or a surface discharge type can be used. From the aspect that the change in ozone generation amount over time is small and the ozone treatment can be stably carried out, the silent discharge type is preferably used.

[0068] In addition, the ozone treatment can be carried out while irradiating ultraviolet rays (UV) on the cyclic olefin resin member. The ultraviolet irradiation can use a known ultraviolet irradiation device. The ozone gas concentration during ultraviolet irradiation can be the same as described above. In addition, as the irradiation amount of ultraviolet rays, for example, at an irradiation wavelength of 365 nm, it can be 1000 mJ / cm 2 and 5000 mJ / cm 2 or less.

[0069] <Bonding process>

[0070] In the manufacturing method of the present invention, in the bonding process optionally performed before the ozone treatment process, at least two cyclic olefin resin molded bodies are bonded to obtain a cyclic olefin resin member having at least one fine tubular flow path. By performing the bonding process, it is possible to easily obtain a cyclic olefin resin member having a fine tubular flow path for ozone treatment. In addition, in the case of obtaining a cyclic olefin resin flow path device having a hydrophilized flow path by subjecting the cyclic olefin resin molded body before bonding to high-intensity ozone treatment and bonding the ozone-treated cyclic olefin resin molded body, since oxides are formed on the bonding surface of the member due to the high-intensity ozone treatment, it may not be possible to sufficiently obtain the bonding strength. However, by obtaining a cyclic olefin resin member by performing the bonding process before the ozone treatment, a cyclic olefin resin flow path device having excellent bonding strength and capable of allowing a water-based liquid to flow well in the fine flow path even after long-term storage can be obtained. In addition, when the intensity of the ozone treatment before bonding is reduced from the viewpoint of ensuring the bonding strength, the water-based liquid cannot flow well in the fine flow path after the cyclic olefin resin flow path device is stored for a long time.

[0071] As such a cyclic olefin resin molded body, as long as a cyclic olefin resin member having at least one fine tubular flow path can be obtained, there is no particular limitation, and examples thereof include the above-mentioned rod-shaped cyclic olefin resin molded body having a substantially semicircular cross section, a rod-shaped cyclic olefin resin molded body having a fan-shaped cross section, a rod-shaped cyclic olefin resin molded body having a U-shaped cross section, a rectangular plate-shaped cyclic olefin resin molded body, a plate-shaped cyclic olefin resin molded body having a trapezoidal cross section, a flow path substrate, and a cover substrate.

[0072] As the material of the cyclic olefin resin molded body, the above-mentioned cyclic olefin resin (cyclic olefin polymer) can be used.

[0073] The bonding of the cyclic olefin resin molded bodies can be performed by, for example, hot melting. Specifically, for example, the cyclic olefin resin molded bodies can be overlapped or assembled to form a temporarily fixed bonded body, and then the bonded body is arbitrarily placed in a heat-resistant bag and vacuum-packed, and heated to perform hot melting. As the method for performing hot melting, examples include an autoclave, a hot press, a roll press, etc. The temperature for performing hot melting can be, for example, the glass transition temperature of the cyclic olefin resin used in the manufacture of the cyclic olefin resin molded body +20°C or higher and 260°C or lower.

[0074] Bonding can also be performed using an adhesive. Specifically, after applying an adhesive to one or both bonding surfaces (excluding the flow path portion) of the cyclic olefin resin molded bodies adjacent to each other during bonding, the cyclic olefin resin molded bodies are overlapped or assembled via the adhesive to form a temporarily fixed bonded body. Then, bonding can be performed by subjecting this bonded body to the above-mentioned heat fusion bonding.

[0075] As the adhesive, the above-mentioned adhesive can be used. In addition, from the viewpoint of facilitating application by coating, the adhesive may be dissolved in a solvent. The solvent is not particularly limited as long as it dissolves a cyclic olefin resin or the like, which is the material of the adhesive, and is easily removed by evaporation. Examples of such solvents include organic solvents such as cyclohexane, tetrahydrofuran, toluene, xylene, decalin, methylcyclohexane, and ethylcyclohexane, and they may also be used in the form of a mixed solvent. The dissolution concentration of the adhesive (mass% of the adhesive relative to the total amount of the adhesive and the solvent) can be, for example, 1.0 mass% or more, preferably 5.0 mass% or more, more preferably 10.0 mass% or more, and, for example, 40.0 mass% or less, preferably 30.0 mass% or less, more preferably 20.0 mass% or less.

[0076] The coating method of the adhesive is not particularly limited, and examples include screen printing, bar coating, and spraying using a mask. From the viewpoint of ease of coating, bar coating is preferred.

[0077] When the adhesive is dissolved in a solvent, the solvent is removed after coating the adhesive. The removal of the solvent can be performed, for example, by heating at 60 to 100 °C for 5 to 30 minutes.

[0078] <Flow path device made of cyclic olefin resin>

[0079] The flow path device made of cyclic olefin resin manufactured by the manufacturing method of the present invention described above is the flow path device made of cyclic olefin resin obtained by subjecting a cyclic olefin resin member having at least one fine tubular flow path to ozone treatment so that the CT value becomes a specified value or more. The flow path device made of cyclic olefin resin is not limited, and a microfluidic chip obtained by subjecting a microfluidic chip precursor to ozone treatment is preferred.

[0080] The flow path device made of cyclic olefin resin only needs to have at least the fine tubular flow path hydrophilized by ozone treatment, and the flow path device made of cyclic olefin resin preferably has the whole (entire surface) hydrophilized by ozone treatment.

[0081] Moreover, the flow path device made of cyclic olefin resin manufactured in this way preferably has the following properties.

[0082] [Water contact angle]

[0083] The water contact angle of the surface of the flow path device made of cyclic olefin resin is preferably 60° or less, more preferably 50° or less, and still more preferably 45° or less. If the water contact angle of the surface of the flow path device made of cyclic olefin resin is below the above upper limit value, the cyclic olefin resin member including the fine tubular flow path is hydrophilized, and an aqueous liquid can flow well in the fine tubular flow path.

[0084] In addition, the water contact angle of the surface of the flow path device made of cyclic olefin resin after being stored at 60°C for 1000 hours is preferably 50° or less, more preferably 40° or less, and still more preferably 30° or less. If the water contact angle of the surface after being stored at 60°C for 1000 hours is below the above upper limit value, the cyclic olefin resin member including the fine tubular flow path is hydrophilized, and an aqueous liquid can flow well in the fine tubular flow path even after long-term storage. Here, generally, the hydrophilicity of the fine tubular flow path decreases with time, but in the present invention, by performing ozone treatment so as to be above a specified CT value, the water contact angle can be reduced compared to before long-term storage, and as a result, the hydrophilicity can be improved compared to before long-term storage.

[0085] In addition, the difference between the water contact angle of the flow path device made of cyclic olefin resin after being stored at 60°C for 1000 hours and the water contact angle before being stored at 60°C for 1000 hours is preferably 5° or more, more preferably 15° or more.

[0086] In addition, in the present invention, the water contact angle of the surface of the flow path device made of cyclic olefin resin can be measured by the method described in the examples.

[0087] [Liquid passing property]

[0088] When the flow path device made of cyclic olefin resin preferably has openings at both ends of the tubular flow path, when a wetting reagent with a wetting tension of 65 mN / m is dropped into one end of the tubular flow path in an amount excessive compared to the volume inside the flow path, the wetting reagent reaches the other end of the tubular flow path. If the reagent with the above-specified wetting tension can reach from one end to the other end of the tubular flow path, an aqueous liquid can flow well in the tubular flow path.

[0089] In addition, when the flow path device made of cyclic olefin resin preferably has openings at both ends of the tubular flow path, after being stored at 60°C for 1000 hours, when a wetting reagent with a wetting tension of 70 mN / m is dropped into one end of the tubular flow path in an amount excessive compared to the volume inside the flow path, it reaches the other end of the tubular flow path. If, after the flow path device made of cyclic olefin resin is stored at 60°C for 1000 hours, the reagent with the above-specified wetting tension can reach from one end to the other end of the tubular flow path, the flow path device made of cyclic olefin resin can make an aqueous liquid flow well in the tubular flow path even after long-term storage.

[0090] In addition, as long as the dropping amount of each of the above wetting reagents is larger than the volume (capacity) of the tubular flow path, there is no particular limitation, and it can be, for example, 0.2 ml, but it is not limited thereto. In addition, when performing the measurement, in a situation where the temperature of the flow path device made of cyclic olefin resin is changing, such as immediately after taking it out of the oven, the measurement of wettability may deviate. Therefore, for example, if the room temperature is 30°C, the flow path device made of cyclic olefin resin is kept in the room for 30 minutes or more, and the measurement is carried out at the stage when the temperature of the flow path device becomes constant. As the measurement ambient temperature, if it is in the range of 20°C to 35°C, the deviation of the measurement can be reduced.

[0091] When evaluating the liquid passing property, the arrival time of the wetting reagent varies depending on the shape and length of the flow path. For a flow path length of 10 mm, when the wetting reagent does not reach the other end even after 1 second or more, it is judged as "cannot reach (poor liquid passing property)".

[0092] Examples

[0093] Hereinafter, the present invention will be described in further detail using examples, but the present invention is not limited to these examples.

[0094] The physical properties and performances of the cyclic olefin polymers and the flow path devices (microfluidic chips) made of cyclic olefin resin manufactured in the examples and comparative examples were measured and evaluated by the following methods respectively.

[0095] <Weight-average molecular weight Mw of cyclic olefin polymer>

[0096] The weight-average molecular weight Mw was measured by gel permeation chromatography (GPC) using cyclohexane as the eluent and was determined in the form of a standard polyisoprene conversion value. As the standard polyisoprene, the standard polyisoprene manufactured by Tosoh Corporation was used. In the case where the sample was insoluble in cyclohexane, tetrahydrofuran (THF) was used as the eluent and measured by GPC, and was determined in the form of a standard polystyrene conversion value. As the standard polystyrene, the standard polystyrene manufactured by Tosoh Corporation was used.

[0097] <Glass transition temperature of cyclic olefin polymer>

[0098] Regarding the glass transition temperature (Tg), a differential scanning calorimeter (DCS7000X manufactured by Hitachi) was used, and based on JIS-K7121, the measurement was carried out at a heating rate of 10°C / min, and the glass transition temperature was determined from the temperature of the inflection point of the DSC curve.

[0099] <Water contact angle>

[0100] Remove the static electricity on the surface of the microfluidic chip using a motor, and measure the water contact angle of the surface of the microfluidic chip using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM0-501Hi).

[0101] <Peeling>

[0102] Set a three-point bending fixture on a universal testing machine (manufactured by Instron Corporation, model 5966), set the distance between the fulcrums to 64 mm, set the cyclic olefin resin member, press it in at 50 mm / min, and confirm whether peeling occurs on the cyclic olefin resin member at the stage of 3 mm of press-in. In the case of no peeling, the bonding strength between the flow path substrate and the cover substrate is excellent.

[0103] <Liquid flow property>

[0104] [After hydrophilic treatment]

[0105] Drop 0.2 mL of a wetting reagent with a wetting tension of 65 mN / m (Mixed solution for wetting tension test No. 65.0; manufactured by Fujifilm Wako Pure Chemical Corporation) into one end (inlet) of the tubular flow path of the microfluidic chip using a dropper, confirm whether the wetting reagent quickly reaches the other end (outlet), and evaluate the liquid flow property according to the following criteria.

[0106] The wetting reagent quickly reaches the other end (outlet): "Good"

[0107] The wetting reagent does not reach the other end (outlet): "Poor"

[0108] [After storing at 60 °C for 1000 hours]

[0109] Place the microfluidic chip on a stainless steel sample stage in a manner that the surface and the tubular flow path are not blocked, and store it in an oven (manufactured by Espec Corporation, small environmental test machine SH-242) at 60 °C for 1000 hours. Then, drop 0.2 mL of a wetting reagent with a wetting tension of 70 mN / m (Mixed solution for wetting tension test No. 70.0; manufactured by Fujifilm Wako Pure Chemical Corporation) into one end (inlet) of the tubular flow path of the microfluidic chip using a dropper, confirm whether the wetting reagent quickly reaches the other end (outlet), and evaluate the liquid flow property according to the following criteria.

[0110] The wetting reagent quickly reaches the other end (outlet): "Good"

[0111] The wetting reagent does not reach the other end (outlet): "Poor"

[0112] In each of the above measurements, the volume within the flow path varies depending on the pattern and dimensions of the flow path of the microfluidic chip. Therefore, the amount of the wetting reagent is adjusted to an amount in excess compared to the volume within the flow path. In addition, regarding the measurement ambient temperature, in an environment where the temperature changes, such as immediately after taking out the microfluidic chip from a heating oven, there may be a deviation in the determination of the wetting reagent. Therefore, the microfluidic chip is stored in a constant temperature environment for, for example, 30 minutes to make the temperature constant before measurement. The measurement is performed in the range of 20°C to 35°C of the ambient temperature.

[0113] In addition, when evaluating the fluidity, the arrival time of the wetting reagent varies depending on the shape and length of the flow path. A case where it takes more than 1 second for the wetting reagent to move 10 mm within the flow path is recorded as "poor".

[0114] (Production Example)

[0115] (Production of Cyclic Olefin Polymer (COP))

[0116] [Production Example 1: Production of COP-1]

[0117] (1-1) Production of Ring-Opening Polymer:

[0118] At room temperature, 200 parts by mass of dehydrated cyclohexane, 0.75 mol% of 1-hexene, 0.15 mol% of diisopropyl ether, and 0.44 mol% of triisobutylaluminum were added to a glass reaction vessel purged with nitrogen inside, and mixed. Then, while maintaining 45°C, 28 parts by mass of methano-tetrahydrofluorene (MTF), 35 parts by mass of tetracyclododecene (TCD), 37 parts by mass of dicyclopentadiene (DCPD), and 0.02 mol% of tungsten hexachloride (0.65 mass% toluene solution) as a polymerization catalyst were continuously added to the reaction vessel over 2 hours for polymerization. Next, 0.2 mol% of isopropyl alcohol was added to the polymerization solution to deactivate the polymerization catalyst and terminate the polymerization reaction. In the above description, the amounts represented by the unit "mol%" are all values based on setting the total amount of the monomers to 100 mol%. The resulting norbornene-based ring-opening polymer had a weight-average molecular weight (Mw) of 2.8×10 4 , and a number-average molecular weight (Mn) of 1.3×10 4 , and a molecular weight distribution (Mw / Mn) of 2.1. In addition, the conversion rate of the monomers to the polymer was 100%.

[0119] (1-2) Production of Hydrogenated Norbornene-Based Cyclic Olefin Polymer (COP-1):

[0120] Next, transfer 300 parts by mass of the reaction solution containing the ring-opening polymer obtained in the above step (1-1) to an autoclave equipped with a stirrer, add 3 parts by mass of a diatomaceous earth-supported nickel catalyst (manufactured by Nippon Kayaku Co., Ltd., "T8400RL", nickel loading rate 57%) as a hydrogenation catalyst, and perform an autoclave treatment at a hydrogen pressure of 4.5 MPa and 160 °C for 4 hours to carry out a hydrogenation reaction.

[0121] After the hydrogenation reaction is completed, use RADIOLITE #500 as a filter bed to pressurize and filter the obtained solution at a pressure of 0.25 MPa (manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd., "FUNDABAC Filter") to remove the hydrogenation catalyst, obtaining a colorless and transparent solution. Inject the obtained solution into a large amount of isopropyl alcohol to precipitate a norbornene-based cyclic olefin polymer (COP-1), which is a hydride of the ring-opening polymer. After filtering to obtain the precipitated norbornene-based cyclic olefin polymer (COP-1), dry it with a vacuum dryer (220 °C, 1 Torr) for 6 hours to obtain a norbornene-based cyclic olefin polymer (COP-1). The weight-average molecular weight (Mw) of the norbornene-based cyclic olefin polymer (COP-1) is 3.3×10 4 , and the number-average molecular weight (Mn) is 1.5×10 4 , and the molecular weight distribution (Mw / Mn) is 2.2. The glass transition temperature Tg of the obtained norbornene-based cyclic olefin polymer (COP-1) is 136 °C.

[0122] Put the norbornene-based cyclic olefin polymer (COP-1) obtained in the above step (1-2) into a twin-screw extruder and form it into a strand-shaped molded body by hot melt extrusion molding. Use a wire cutter to cut the molded body into pieces to obtain particles of a thermoplastic norbornene-based resin containing the norbornene-based cyclic olefin polymer (COP-1).

[0123] [Production Example 2: Production of COP-2]

[0124] As monomers, use 60 parts by mass of methylene tetrahydrofluorene (MTF) and 40 parts by mass of tetracyclododecene (TCD). Otherwise, carry out the same operations as in the production of COP-1 to obtain a norbornene-based cyclic olefin polymer (COP-2) and particles of a thermoplastic norbornene-based resin containing COP-2. The weight-average molecular weight (Mw) of the hydrogenated COP-2 is 3.2×10 4 , and the number-average molecular weight (Mn) is 1.9×10 4 , and the molecular weight distribution (Mw / Mn) is 1.7, and the glass transition temperature Tg is 163 °C.

[0125] [Production Example 3: Production of COP-3]

[0126] As monomers, 85 parts by mass of dicyclopentadiene (DCPD) and 15 parts by mass of 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (ETD) were used. Otherwise, the production was carried out in the same manner as for the production of COP-1 to obtain a norbornene-based cyclic olefin polymer (COP-3) and particles of a thermoplastic norbornene-based resin containing COP-3. The weight-average molecular weight (Mw) of COP-3 was 40,700, the number-average molecular weight (Mn) was 13,300, the molecular weight distribution (Mw / Mn) was 3.07, and the glass transition temperature Tg was 100°C.

[0127] [Production Example 4: Production of COP-4]

[0128] As monomers, 31 parts by mass of tetracyclododecene (TCD), 33 parts by mass of dicyclopentadiene (DCPD), and 36 parts by mass of norbornene (NB) were used. Otherwise, the production was carried out in the same manner as for the production of COP-1 to obtain a norbornene-based cyclic olefin polymer (COP-4) and particles of a thermoplastic norbornene-based resin containing COP-4. The glass transition temperature Tg of COP-4 was 68°C.

[0129] (Example 1)

[0130] <Manufacture of cyclic olefin resin molded body (flow path substrate and cover substrate)>

[0131] A mold for a 2 mm thickness × 25 mm × 75 mm was installed in an injection molding machine (FANUC, ROBOSHOT S2000i100A), and the particles of the thermoplastic norbornene-based resin containing the norbornene-based cyclic olefin polymer (COP-1) obtained in Production Example 1 were injection molded at a mold temperature of 110°C and a barrel temperature of 270°C to produce an injection molded plate (2 mm thickness × 25 mm × 75 mm). Then, on one side of the injection molded plate, Figure 1 Four flow paths 11 (width: 50 μm, depth 50 μm) were formed in the pattern shown in (a) to produce a flow path substrate 10.

[0132] Similarly, the particles of the thermoplastic norbornene-based resin obtained in Production Example 1 were injection molded to produce an injection molded plate (2 mm thickness × 25 mm × 75 mm). Then, as Figure 1 Eight through holes 21 (inlet ports) with a diameter of 2.0 mm were formed as shown in (b) to produce a cover substrate 20. In addition, the positions of the through holes 21 were set to positions corresponding to the ends 12 of the flow paths 11 of the flow path substrate 10.

[0133] <Manufacture of cyclic olefin resin member (joining of cyclic olefin resin molded body)>

[0134] The granules of the thermoplastic norbornene-based resin containing the norbornene-based cyclic olefin polymer (COP-4) obtained in Production Example 4 were dissolved in cyclohexane so as to have a concentration of 10% by mass. The resulting solution was applied to the entire surface of the above-obtained cover substrate 20 using a wire bar No. 6 and dried by heating at 80°C for 30 minutes to form a bonding layer on the surface of the cover substrate 20. Next, the cover substrate 20 and the flow path substrate 10 were overlapped so that the bonding layer of the cover substrate 20 faced the side of the flow path substrate 10 where the flow path was formed, and a laminate was obtained. The obtained laminate was put into a heat-resistant bag and vacuum-packaged. The vacuum-packaged laminate was put into an autoclave device (manufactured by Haneda Iron Works, DANDELION), and heated and pressurized at a temperature of 90°C and a pressure of 0.8 MPa for 30 minutes to bond the flow path substrate 10 and the cover substrate 20, thereby obtaining a cyclic olefin resin member.

[0135] <Manufacture of a cyclic olefin resin flow path device (microfluidic chip)>

[0136] [Ozone treatment (hydrophilic treatment)]

[0137] The above-obtained cyclic olefin resin member was suspended on a stainless-steel bracket with a clip and stored in a covered stainless-steel container having a gas supply port and an exhaust port. Next, using an ozone gas generation device (manufactured by EcoDesign Co., Ltd., Labozon 40LOG-LC40G; silent discharge method), ozone gas with a concentration of 90 g / m 3 was injected into the stainless-steel container under the conditions of a temperature of 20°C to 25°C and an ozone gas flow rate of 2 L / min. Then, the cyclic olefin resin member was treated with ozone so that the CT value became 10000 g / m 3 ·min. In addition, the ozone gas discharged from the exhaust side was passed through a catalyst to be made harmless and then discharged. Then, various evaluations were performed on the obtained microfluidic chip. The results are shown in Table 1.

[0138] (Example 2)

[0139] In the manufacture of the microfluidic chip, the cyclic olefin resin member was treated with ozone so that the CT value became 5000 g / m 3 ·min. Except for this, the microfluidic chip was manufactured in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 1.

[0140] (Example 3)

[0141] In the manufacture of the microfluidic chip, the cyclic olefin resin member was treated with ozone so that the CT value became 2700 g / m 3·The microfluidic chip was manufactured in the same manner as in Example 1 except that ozone treatment was carried out in the way of ·min, and various evaluations were carried out. The results are shown in Table 1.

[0142] (Example 4)

[0143] In the manufacture of the cyclic olefin resin molded body, the granules of the thermoplastic norbornene-based resin containing the norbornene-based cyclic olefin polymer (COP-3) obtained in Production Example 3 were used, and the mold temperature was changed to 80 °C and the barrel temperature was changed to 250 °C. Except for this, the microfluidic chip was manufactured in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 1.

[0144] (Example 5)

[0145] In the manufacture of the cyclic olefin resin molded body, the granules of the thermoplastic norbornene-based resin containing the norbornene-based cyclic olefin polymer (COP-2) obtained in Production Example 2 were used, and the mold temperature was changed to 120 °C and the barrel temperature was changed to 285 °C. Except for this, the microfluidic chip was manufactured in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 1.

[0146] (Example 6)

[0147] In the manufacture of the cyclic olefin resin molded body, the granules of the cyclic olefin copolymer (TOPAS 8007S-04, manufactured by Polyplastics Co., Ltd.) were used, and the mold temperature was changed to 80 °C and the barrel temperature was changed to 250 °C. And in the manufacture of the microfluidic chip, the cyclic olefin resin member was treated with ozone in such a way that the CT value became 5000 g / m 3 ·min, and except for this, the microfluidic chip was manufactured in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 1.

[0148] (Comparative Example 1)

[0149] In the manufacture of the microfluidic chip, the following corona discharge treatment was carried out instead of ozone treatment, and except for this, the microfluidic chip was manufactured in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 2.

[0150] [Corona Discharge Treatment]

[0151] The cyclic olefin resin member was set on the workbench of the bench-type corona discharge treatment device (CTW-0212, manufactured by WEDGE Co., Ltd.), and corona discharge treatment was carried out for 5 reciprocations at an output power of 0.3 kW, a treatment speed (table speed) of 3 m / min, and an electrode distance of 12 mm. After the corona discharge treatment, the obtained microfluidic chip was taken out and degaussed with an ion generator.

[0152] (Comparative Example 2)

[0153] In the production of a cyclic olefin resin molded body, pellets of a thermoplastic norbornene-based resin containing a norbornene-based cyclic olefin polymer (COP-3) obtained in Production Example 3 were used, the mold temperature was changed to 80°C, and the barrel temperature was changed to 250°C. Otherwise, a microchannel chip was produced in the same manner as in Comparative Example 1, and various evaluations were performed. The results are shown in Table 2.

[0154] (Comparative Example 3)

[0155] In the production of a cyclic olefin resin molded body, pellets of a thermoplastic norbornene-based resin containing a norbornene-based cyclic olefin polymer (COP-2) obtained in Production Example 2 were used, the mold temperature was changed to 120°C, and the barrel temperature was changed to 285°C. Otherwise, a microchannel chip was produced in the same manner as in Comparative Example 1, and various evaluations were performed. The results are shown in Table 2.

[0156] (Comparative Example 4)

[0157] In the production of a microchannel chip, the cyclic olefin resin member was treated with ozone such that the CT value became 300 g / m 3 ·min. Otherwise, a microchannel chip was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2.

[0158] (Comparative Example 5)

[0159] In the production of a microchannel chip, the cyclic olefin resin member was treated with ozone such that the CT value became 600 g / m 3 ·min. Otherwise, a microchannel chip was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2.

[0160] (Comparative Example 6)

[0161] In the production of a cyclic olefin resin molded body, pellets of a thermoplastic norbornene-based resin containing a norbornene-based cyclic olefin polymer (COP-3) obtained in Production Example 3 were used, the mold temperature was changed to 80°C, and the barrel temperature was changed to 250°C. In the production of a microchannel chip, the following plasma treatment was performed instead of the ozone treatment. Otherwise, a microchannel chip was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2.

[0162] [Plasma treatment]

[0163] A cyclic olefin resin member is set on the workbench of an air plasma device (manufactured by Kasuga Electric Co., Ltd., APW-602f), and atmospheric pressure plasma treatment is performed at an output power of 0.6 kw, a processing speed (table speed) of 20 mm / sec, and a distance of 25 mm between the member and the plasma generation part.

[0164] (Comparative Example 7)

[0165] In the manufacture of a cyclic olefin resin molded body, granules of a thermoplastic norbornene-based resin containing a norbornene-based cyclic olefin polymer (COP-2) obtained in Production Example 2 are used, the mold temperature is changed to 120°C, and the barrel temperature is changed to 285°C. Otherwise, a microchannel chip is manufactured in the same manner as in Comparative Example 6, and various evaluations are performed. The results are shown in Table 2.

[0166] (Comparative Example 8)

[0167] In the manufacture of a cyclic olefin resin member, the following UV ozone treatment is performed on the cyclic olefin resin molded body (flow path substrate and cover substrate) before forming the bonding layer, and the cyclic olefin resin member obtained by bonding the molded body is not subjected to ozone treatment. Otherwise, a microchannel chip is manufactured in the same manner as in Example 1, and various evaluations are performed. The results are shown in Table 2.

[0168] [UV Ozone Treatment]

[0169] An ozone gas generation device (manufactured by EcoDesign Co., Ltd., Labozon 40LOG-LC40G) is connected to a UV cleaning surface modification device (manufactured by ASUMI GIKEN, Limited, ASM1101N). Then, while irradiating ultraviolet rays at an output power of 10 mW / cm 2 , ozone is used to treat the cyclic olefin resin molded body so that the CT value becomes 100 g / m 3 ·min. In addition, the ozone gas discharged from the exhaust side is passed through a catalyst to be made harmless and then discharged.

[0170] (Comparative Example 9)

[0171] In the manufacture of a cyclic olefin resin member, while irradiating ultraviolet rays at an output power of 20 mW / cm 2 , ozone is used to treat the cyclic olefin resin molded body so that the CT value becomes 3000 g / m 3 ·min. Otherwise, a microchannel chip is manufactured in the same manner as in Comparative Example 8, and various evaluations are performed. The results are shown in Table 2. In addition, peeling occurred in the microchannel chip (the flow path substrate and the cover substrate were separated), so the water contact angle after storage and the liquid passing property before and after storage could not be evaluated.

[0172] [Table 1]

[0173]

[0174] [Table 2]

[0175]

[0176] As can be seen from the results shown in Tables 1 and 2, for a cyclic olefin resin member (microchannel chip precursor) having at least one fine tubular flow path, the cyclic olefin resin flow path devices (microchannel chips) of Examples 1 to 6 obtained by ozone treatment such that the CT value becomes 2500 g / m 3 ·min or more can allow an aqueous liquid to flow well in the fine tubular flow path even after long-term storage.

[0177] Industrial applicability

[0178] According to the present invention, a method for manufacturing a cyclic olefin resin flow path device can be provided, which can manufacture a cyclic olefin resin flow path device that can allow an aqueous liquid to flow well in a fine tubular flow path even after long-term storage.

[0179] Explanation of reference numerals

[0180] 10: Flow path substrate

[0181] 11: Flow path

[0182] 12: End

[0183] 20: Cover substrate

[0184] 21: Through hole

Claims

1. A method for producing a cyclic olefin resin flow path device, comprising: treating a cyclic olefin resin member having at least one fine tubular flow path with a CT value of 2500 g / m 3 ·min or more of the ozone treatment process.

2. The method for producing a cyclic olefin resin flow path device according to claim 1, wherein: The ozone treatment is performed by generating ozone by silent discharge.

3. The method for producing a cyclic olefin resin flow path device according to claim 1, wherein: The two ends of the tubular flow path are open, In the cyclic olefin resin flow channel device, when a wetting agent having a wetting tension of 65 mN / m is dropped to one end of the tubular flow channel in excess of the volume in the flow channel, the wetting agent reaches the other end of the tubular flow channel.

4. The method for producing a cyclic olefin resin flow path device according to claim 3, wherein: After the cyclic olefin resin flow channel device was stored at 60° C. for 1000 hours, when a wetting agent having a wetting tension of 70 mN / m was dripped onto one end of the tubular flow channel in excess of the volume inside the flow channel, the wetting agent reached the other end of the tubular flow channel.

5. The method for producing a cyclic olefin resin flow path device according to claim 1, wherein: The method for producing a cyclic olefin resin flow path device further includes a step of joining at least two cyclic olefin resin molded bodies to obtain the cyclic olefin resin member.

6. The method for producing a flow path device made of a cyclic olefin resin according to any one of claims 1 to 5, wherein: The cyclic olefin resin flow path device is a micro flow path chip.

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