WO2014103842A1 - マイクロ流路の製造方法およびマイクロ流路 - Google Patents
マイクロ流路の製造方法およびマイクロ流路 Download PDFInfo
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- WO2014103842A1 WO2014103842A1 PCT/JP2013/083951 JP2013083951W WO2014103842A1 WO 2014103842 A1 WO2014103842 A1 WO 2014103842A1 JP 2013083951 W JP2013083951 W JP 2013083951W WO 2014103842 A1 WO2014103842 A1 WO 2014103842A1
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- WIPO (PCT)
- Prior art keywords
- curable resin
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- flow path
- microchannel
- manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00055—Grooves
- B81C1/00071—Channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/0048—Local deformation of formed objects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B1/00—Devices without movable or flexible elements, e.g. microcapillary devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/02—Form or structure of the vessel
- C12M23/16—Microfluidic devices; Capillary tubes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N37/00—Details not covered by any other group of this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00833—Plastic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00858—Aspects relating to the size of the reactor
- B01J2219/0086—Dimensions of the flow channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/12—Specific details about materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2203/00—Basic microelectromechanical structures
- B81B2203/03—Static structures
- B81B2203/0323—Grooves
- B81B2203/0338—Channels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24744—Longitudinal or transverse tubular cavity or cell
Definitions
- the present invention relates to a method for manufacturing a microchannel and a microchannel.
- a microfluidic device that performs a biochemical reaction or a physicochemical separation operation by flowing a liquid or the like through a microchannel having a diameter of about several ⁇ m to several hundred ⁇ m is known.
- Such microfluidic devices require a channel with a semi-circular or circular cross section.
- the cross section of the manufactured flow path is often rectangular, so a method for manufacturing a flow path having a semicircular or circular cross section has been proposed. ing.
- Patent Document 1 includes a pair of halves that have a long plate shape, are formed on one side thereof, and have a groove that opens in a semicircular shape on one end surface, and the halves are joined to each other. A method of manufacturing a microchannel device is described.
- Non-Patent Document 1 describes a method for producing a circular cross-sectional flow path.
- a mold is prepared by directly drawing an ultraviolet curable resin or the like in a flow path pattern on a substrate using a dispenser robot that automatically applies an adhesive or the like to be used when manufacturing electronic equipment.
- a semicircular cross-sectional flow path is created by mold-making with PDMS (polydimethylsiloxane) using the created mold.
- a circular cross-section flow path is produced by bonding semicircular cross-section flow paths together.
- Non-Patent Document 2 discloses a method of manufacturing a circular PDMS microchannel that simulates microvessels in a living body and is suitable for visualization of microflow such as confocal ⁇ PIV / PTV (Particle Image Velocimetry / Particle Tracking Velocimetry). Is described. In this method, a circular flow path is formed by solidifying PDMS in a state where the wire is embedded and then pulling out the wire.
- Non-Patent Document 3 describes a method of forming a microvascular network having a circular cross section from a polystyrene sheet.
- a silicon semi-circular master is formed by an electroplating process, embossed on a polystyrene sheet, and the obtained two sheets are joined to form a flow path having a circular cross section.
- Non-Patent Document 2 In the method of Non-Patent Document 2, a circular flow path is formed without bonding a semicircular flow path in cross section, but there is a process of pulling out a wire, so a flow path without an inlet cannot be formed. Only a simple flow path such as a straight line can be formed. In addition, in the method of Non-Patent Document 2, in order to obtain a flow channel in a state where liquid is injected into the inside, a step of injecting liquid into the inside after the flow channel is formed is necessary.
- an object of the present invention is to provide a method for manufacturing a microchannel having a substantially circular cross section with a smaller number of processes than the conventional method and having no joint surface and no injection port.
- the microchannel manufacturing method includes a step of forming an uncured curable resin layer on a substrate, a step of inserting a needle body into which liquid can be injected into the curable resin, and moving the needle body, A step of injecting a liquid into the curable resin through the needle body into a tubular shape, a step of extracting the needle body from the curable resin, and a hardening of the curable resin to flow into the tubular region into which the liquid has been injected. And a step of forming a path.
- the flow path is preferably a flow path having no joint surface and a substantially circular cross section.
- the above manufacturing method further includes a step of cutting out a part of the cured curable resin and extracting the liquid confined in the curable resin.
- the liquid is preferably liquid crystal.
- micro flow path is manufactured by any one of the above manufacturing methods.
- a microchannel having a substantially circular cross section with a smaller number of processes than in the past and having no joint surface and no injection port.
- FIG.3 (B) are schematic views for explaining a method of manufacturing a microchannel. It is the flowchart which showed the manufacturing method of the microchannel.
- (A) And (B) is a photograph which shows the experimental result by the manufacturing method of FIG. It is a schematic diagram for demonstrating the formation position and magnitude
- FIGS. 1 (A) to 1 (C) are schematic diagrams for explaining a method of manufacturing a microchannel.
- FIG. 2 is a flowchart showing a method for manufacturing a microchannel. Each step of the manufacturing method will be described with reference to FIGS.
- a substrate 1 is prepared, and an uncured curable resin 2 layer is formed on the substrate 1 (S1). Since the curable resin 2 has fluidity in an uncured state, a frame (not shown) surrounding the periphery is prepared, and the curable resin 2 is injected into the frame.
- the curable resin 2 for example, an ultraviolet curable resin such as an acrylic resin or an epoxy resin is used.
- the curable resin 2 may be a thermosetting resin such as a urea resin, a melamine resin, or a phenol resin.
- the thickness d of the curable resin 2 may be about 1000 ⁇ m.
- a needle (needle body) 3 capable of injecting liquid is inserted into the curable resin 2 (S2).
- the needle 3 is hollow and has a sharp shape toward the tip like an injection needle, and has an opening (not shown) at the tip.
- the depth at which the needle 3 is inserted is, for example, about half of the thickness d of the curable resin 2.
- the liquid 4 is injected into the curable resin 2 through the needle 3 while moving the needle 3 (S3).
- the needle 3 is translated along the X direction shown in FIG.
- the liquid 4 is injected into the layer of the curable resin 2 from the opening at the tip of the needle 3 by applying pressure from the top of the needle 3.
- the liquid 4 has a substantially circular cross section perpendicular to the X direction due to surface tension.
- liquid 4 is a liquid crystal.
- liquid crystal refers to a substance that has fluidity like a liquid and has a certain regularity like a crystal in molecular orientation.
- the liquid 4 a liquid corresponding to the use of the flow path to be formed may be used.
- the injected liquid 4 may float on the surface of the resin layer depending on the viscosity of the curable resin 2 or the difference in density between the curable resin 2 and the liquid 4. For this reason, as the liquid 4, it is necessary to select a liquid that can be injected into the inside of the curable resin 2 in a tubular manner because of the relationship between viscosity and density.
- the needle 3 is removed from the curable resin 2 (S4).
- the hole made in the curable resin 2 is closed by the needle 3.
- the liquid 4 is confined in the curable resin 2 and is placed in a tubular shape.
- the curable resin 2 is cured and the liquid 4 is confined in the curable resin 2, whereby the portion where the liquid 4 exists is defined as a liquid flow path 4A (S5).
- a liquid flow path 4A S5
- an ultraviolet curable resin is used as the curable resin 2
- the curable resin 2 is cured by irradiating ultraviolet rays.
- a thermosetting resin is used as the curable resin 2
- the curable resin 2 is cured by heating.
- a channel 4A having a substantially circular cross section is formed in the tubular region into which the liquid 4 has been injected.
- the liquid 4 when the curable resin 2 is cured, the liquid 4 may permeate into the resin layer, and the flow path 4A may be hollow. If a hollow channel is required when the liquid 4 remains in the channel 4A after the curable resin 2 is cured, a part of the cured curable resin is excised and the curable resin is removed. The liquid 4 confined in 2 may be extracted. Thereby, a hollow flow path is obtained.
- a flow path having a substantially circular cross section is formed without bonding a flow path having a semicircular cross section. For this reason, in this manufacturing method, it is possible to form a circular flow path having a smooth inner wall without a joint surface with fewer steps compared to a conventional manufacturing method that does not include this configuration. In addition, since the opening does not exist when the flow path is formed, it is possible to form a closed flow path without an injection port.
- the liquid 4 injected into the layer of the curable resin 2 has a substantially circular cross section perpendicular to the direction in which the liquid 4 extends due to surface tension.
- the finally obtained flow path has a substantially circular shape with no cross section, no dents, and no sharp part.
- the “substantially circular” described above refers to a shape having no sharply protruding portion like a rectangle and a ratio of the difference between the maximum diameter and the minimum diameter with respect to the maximum diameter being, for example, 10% or less.
- a circular flow path close to an actual biological structure is preferable in order to more accurately reproduce the behavior of the biological structure such as a blood vessel.
- the flow path obtained by this production method can also be used for such bio-related systems.
- a hollow channel can be formed by allowing the liquid confined inside the channel to flow out, and another liquid can be injected after the liquid has flowed out. For this reason, the inside of the formed flow path can be filled with an arbitrary liquid regardless of the viscosity of the curable resin 2 and the density difference between the curable resin 2 and the liquid 4.
- FIG. 3 (A) and 3 (B) are photographs showing the experimental results of the manufacturing method of FIG.
- FIG. 3A is a photograph of the acrylic resin 12 in a state where the above two types of P-type liquid crystals 14 are respectively injected (dispensed), as viewed from above.
- FIG. 3B is a cross-sectional photograph of the flow path 4A taken after the acrylic resin 12 is cured by ultraviolet irradiation.
- the P-type liquid crystal 14 was dispensed into two linear lines inside the acrylic resin 12.
- FIG. 4 is a schematic diagram for explaining the formation position and size of the flow path 4A shown in FIG. 3 (B).
- the acrylic resin 12 was formed in a thickness of 1000 ⁇ m, and the needle 3 was inserted into the acrylic resin 12 to a depth of 500 ⁇ m. Then, while moving the needle 3 linearly along the surface direction of the acrylic resin 12 at a speed of 20 mm / sec, a dispensing pressure of 10 kPa is applied to change the P-type liquid crystal 14 so that the cross section becomes a circle having a diameter of 200 ⁇ m. I dispensed.
- the flow path 4A having a cross section as shown in FIG. 3B was obtained by extracting the needle 3 and then curing the acrylic resin 12 with ultraviolet rays.
- FIG. 3B also shows the outline of the cross section of the flow path 4A.
- the difference between the maximum diameter and the minimum diameter is about 20 ⁇ m, and the ratio of the difference between the maximum diameter and the minimum diameter with respect to the maximum diameter of the cross section is about several percent.
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Abstract
Description
2 硬化性樹脂
3 ニードル
4 液体
4A 流路
Claims (5)
- 基板の上に未硬化の硬化性樹脂の層を形成する工程と、
液体を注入可能な針体を前記硬化性樹脂内に差し込む工程と、
前記針体を移動させながら、当該針体を介して当該硬化性樹脂内に管状に液体を注入する工程と、
前記針体を前記硬化性樹脂内から抜き取る工程と、
前記硬化性樹脂を硬化させることにより、前記液体が注入された管状の領域に流路を形成する工程と、
を有することを特徴とする、マイクロ流路の製造方法。 - 前記流路は、接合面がなく断面が略円形の流路である、請求項1に記載の製造方法。
- 硬化させた前記硬化性樹脂の一部を切除して当該硬化性樹脂内に閉じ込められている前記液体を抜き取る工程をさらに含む、請求項1または2に記載の製造方法。
- 前記液体は液晶である、請求項1~3のいずれか1項に記載の製造方法。
- 請求項1~4のいずれか1項に記載の製造方法で製造されたマイクロ流路。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380068579.9A CN104955768B (zh) | 2012-12-28 | 2013-12-18 | 微流路的制造方法及微流路 |
US14/655,239 US9725307B2 (en) | 2012-12-28 | 2013-12-18 | Method for producing microchannel, and microchannel |
JP2014554362A JP6138159B2 (ja) | 2012-12-28 | 2013-12-18 | マイクロ流路の製造方法およびマイクロ流路 |
EP13867007.0A EP2939976B1 (en) | 2012-12-28 | 2013-12-18 | Method for producing microchannel and microchannel |
Applications Claiming Priority (2)
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JP2012288628 | 2012-12-28 | ||
JP2012-288628 | 2012-12-28 |
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WO2014103842A1 true WO2014103842A1 (ja) | 2014-07-03 |
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PCT/JP2013/083951 WO2014103842A1 (ja) | 2012-12-28 | 2013-12-18 | マイクロ流路の製造方法およびマイクロ流路 |
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US (1) | US9725307B2 (ja) |
EP (1) | EP2939976B1 (ja) |
JP (1) | JP6138159B2 (ja) |
CN (1) | CN104955768B (ja) |
WO (1) | WO2014103842A1 (ja) |
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US8156273B2 (en) * | 2007-05-10 | 2012-04-10 | Freescale Semiconductor, Inc. | Method and system for controlling transmission and execution of commands in an integrated circuit device |
GB2556751B (en) | 2015-07-27 | 2022-07-27 | Univ Pennsylvania | Systems and methods for immobilizing extracelluar matrix material on organ on chip, multilayer microfluids microdevices, and three-dimensional cell culture |
USD838864S1 (en) * | 2016-09-07 | 2019-01-22 | EMULATE, Inc. | Opaque microfluidic chip without pressure features for use with a fluid perfusion module |
CN112155828A (zh) * | 2020-10-12 | 2021-01-01 | 吕修波 | 注射成型式骨折断肢固定装置 |
KR102594790B1 (ko) * | 2022-01-10 | 2023-10-30 | 동의대학교 산학협력단 | 광경화성 폴리머 재료의 3차원 마이크로 채널 제작을 위한 버블 보조 제조 방법 |
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JP2003311697A (ja) * | 2002-02-19 | 2003-11-05 | Sumitomo Bakelite Co Ltd | 中空デバイス及びその製造方法並びに中空デバイスを有する反応装置 |
JP2007216086A (ja) * | 2006-02-14 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | 混合器の作製方法 |
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TWI296711B (en) * | 2005-10-11 | 2008-05-11 | Ind Tech Res Inst | Biochip with microchannels |
CN100528736C (zh) * | 2007-11-20 | 2009-08-19 | 东南大学 | 圆片级mems微流道的制造方法 |
US20110033348A1 (en) * | 2008-04-11 | 2011-02-10 | Hiroshi Hirayama | Microchip and Method for Manufacturing Microchip |
JP2010228174A (ja) * | 2009-03-26 | 2010-10-14 | Panasonic Electric Works Co Ltd | 微細樹脂構造体の製造方法、その製造方法により製造された微細樹脂構造体、光導波路、マイクロレンズ、マイクロレンズアレイ、及びマイクロ流体デバイス |
WO2013002013A1 (ja) | 2011-06-27 | 2013-01-03 | 学校法人 慶應義塾 | 光導波路及びその製造方法 |
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2013
- 2013-12-18 JP JP2014554362A patent/JP6138159B2/ja active Active
- 2013-12-18 US US14/655,239 patent/US9725307B2/en active Active
- 2013-12-18 WO PCT/JP2013/083951 patent/WO2014103842A1/ja active Application Filing
- 2013-12-18 CN CN201380068579.9A patent/CN104955768B/zh not_active Expired - Fee Related
- 2013-12-18 EP EP13867007.0A patent/EP2939976B1/en not_active Not-in-force
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JP2003311697A (ja) * | 2002-02-19 | 2003-11-05 | Sumitomo Bakelite Co Ltd | 中空デバイス及びその製造方法並びに中空デバイスを有する反応装置 |
JP2007216086A (ja) * | 2006-02-14 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | 混合器の作製方法 |
JP2012137325A (ja) | 2010-12-24 | 2012-07-19 | Sumitomo Bakelite Co Ltd | マイクロ流路デバイスの製造方法およびマイクロ流路デバイス |
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JP6138159B2 (ja) | 2017-05-31 |
EP2939976A4 (en) | 2016-10-12 |
EP2939976A1 (en) | 2015-11-04 |
US20150329354A1 (en) | 2015-11-19 |
EP2939976B1 (en) | 2017-10-18 |
CN104955768B (zh) | 2016-11-09 |
US9725307B2 (en) | 2017-08-08 |
CN104955768A (zh) | 2015-09-30 |
JPWO2014103842A1 (ja) | 2017-01-12 |
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