Bonded body and method for manufacturing the same

Abstract

The object of the present invention is to provide a bonding body that suppresses deformation caused by heating during bonding, facilitates re-peeling of the bonding body, suppresses protein adsorption, and obtains a low-haze bonding body, and a method for manufacturing the same. The bonding body of the present invention is a bonding body [3] formed by bonding at least one molded body [1] via a bonding layer [2] having a material composition different from that of the molded body. The bonding layer [2] contains a softener [5] and 100 parts by weight of a cyclic olefin resin [4]. The content of the softener [5] in the bonding layer [2] is 6 to 99 parts by weight of the softener [5] relative to 100 parts by weight of the cyclic olefin resin [4]. The haze of the bonding layer [2] is 1.0 or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a bonded body and a method for manufacturing the same. BACKGROUND

[0002] A method for manufacturing a bonded body by bonding substrates to each other can be used for manufacturing, for example, a microchannel chip (Microchannel chip) in which a microchannel of a micron order is formed on a bonding surface of a substrate. Such a microchannel chip can be used for various fields such as analysis and examination of biological substances such as DNA, RNA, and proteins, drug research and pharmaceutical development, organic synthesis, water quality analysis, and the like.

[0003] Further, a resin-made microchannel chip is manufactured by sandwiching a bonding layer between a resin-made substrate in which a fine channel is formed on at least one surface and a resin-made cover substrate as a cover material and bonding them by heating (for example, refer to Patent Documents 1 to 4).

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] Patent Document 1: Japanese Patent No. 5948248;

[0007] Patent Document 2: International Publication No. 2014 / 178439;

[0008] Patent Document 3: International Publication No. 2011 / 083809;

[0009] Patent Document 4: Japanese Patent No. 5948248. SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] For example, in the case of manufacturing a bonded body such as a microchannel chip by bonding molded bodies such as substrates to each other with a bonding layer interposed therebetween, there are the following requirements: prevention of deformation caused by heating at the time of bonding; recycling or the like; ease of re-peeling of the bonded body to enable recovery of cells and drugs after testing (post-bonding workability); suppression of adsorption of proteins to channels used for analysis and examination of biological substances or the like; reduction of haze of the bonding layer and improvement of transparency of the bonding layer for the purpose of improving the accuracy of optical signal detection.

[0012] Therefore, an object of the present application is to provide a bonded body and a method for manufacturing the same, in which molded bodies are bonded to each other at a lower temperature, whereby deformation caused by heating at the time of bonding is suppressed, re-peeling of the bonded body is facilitated, adsorption of proteins is suppressed, and the haze is reduced.

[0013] SOLUTION TO PROBLEM

[0014] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that by incorporating a softening agent into the bonding layer, the molded bodies can be bonded to each other at a lower temperature, whereby deformation caused by heating at the time of bonding is suppressed and re-peeling of the bonded body becomes easy, and furthermore, by using a prescribed softening agent, protein adsorption is suppressed and the haze is reduced, thereby completing the present application.

[0015] Thus, according to the present application, a microchannel chip and a method for manufacturing the same are provided as shown below.

[0016] [1] A bonded body [3] which is a bonded body [3] in which at least one or more molded bodies [1] are bonded via a bonding layer [2] having a material composition different from that of the molded bodies,

[0017] The bonding layer [2] contains a softening agent [5] and 100 parts by weight of a cyclic olefin resin [4],

[0018] The content of the softening agent [5] in the bonding layer [2] is 6 to 99 parts by weight of the softening agent [5] with respect to 100 parts by weight of the cyclic olefin resin [4],

[0019] The haze of the bonding layer [2] is 1.0 or less.

[0020] [2] The bonded body [3] according to the above [1], characterized in that the number average molecular weight of the cyclic olefin resin [4] is 12500 or more.

[0021] [3] The bonded body [3] according to the above [1] or [2], characterized in that the glass transition temperature of the cyclic olefin resin [4] is 100°C or less.

[0022] [4] The bonded body [3] according to any one of the above [1] to [3], characterized in that the softening agent [5] is composed of a hydrogenated product of liquid paraffin.

[0023] [5] The bonded body [3] according to any one of the above [1] to [4], characterized in that the cyclic olefin resin [4] has an alkoxysilyl group.

[0024] [6] The bonded body [3] according to any one of the above [1] to [5], characterized in that the molded body [1] is an organic substance, and at least one treatment selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge, and flame spraying is performed on the surface of the molded body [1].

[0025] Inventive Effects

[0026] According to the present application, a bonded body in which deformation caused by heating at the time of bonding is suppressed, re-peeling of the bonded body is facilitated, protein adsorption is suppressed, and low haze is obtained, and a method for producing the same can be provided. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a conceptual diagram showing a method for producing a bonded body of the present application.

[0028] Figure 2 is an example of a bonded body of the present application. DETAILED DESCRIPTION

[0029] The embodiments of the present application are described in detail below.

[0030] (Bonded body)

[0031] The bonded body [3] of the present application is characterized in that it is a bonded body [3] in which at least one or more molded bodies [1] are bonded via a bonding layer [2] having a material composition different from that of the molded body, the bonding layer [2] having a material composition in which 6 to 99 parts by weight of a softening agent [5] is compounded with 100 parts by weight of a cyclic olefin resin [4] in such a manner that the haze is 1.0 or less.

[0032] The bonded body [3] of the present application is used, for example, in microchannel chips, inspection containers, and image display panels.

[0033] Molded body

[0034] In the present application, the molded body [1] has a function as a substrate. In the present application, the molded body [1] generally has the shape of a flat plate. In the bonded body [3], the molded body [1] is usually one pair (two pieces), but can be three or more pieces. In the case where the bonded body [3] is used as a microchannel chip, the molded body [1] can have a fine channel formed on at least one surface. The formation of a fine channel in the molded body [1] can be performed using, for example, a microfabrication technique such as photolithography, hot embossing, or the like, cutting, injection molding, or the like.

[0035] Each molded body [1] is formed from at least one material. That is, each molded body [1] may be formed from the same material or from different materials. The material of the molded body [1] may be an organic or an inorganic material. Examples of organic materials include cyclic olefin resins, polycarbonate resins, aromatic polyetherketone resins, (meth)acrylic resins, vinyl alicyclic hydrocarbon resins, and aromatic vinyl resins. Here, "(meth)acrylic acid" means acrylic acid and / or methacrylic acid. Examples of inorganic materials include metals (e.g., iron alloys such as stainless steel) and metal oxides (glass, ceramics). When the bonding body [3] is used as a microchannel chip, from the viewpoint of obtaining a microchannel chip with less time-related decrease in bonding strength and optical stability due to moisture absorption and excellent durability, the resin used as the substrate is preferably a cyclic olefin resin, and more preferably a cyclic olefin resin with a water absorption rate of 0.01% by mass or less.

[0036] Furthermore, monomers of cyclic olefin resins used as materials for molding bodies [1] are preferably norbornene monomers. Norbornene monomers are monomers containing a norbornene ring. Examples of norbornene monomers include, for example, bicyclic [2.2.1]hept-2-ene (common name: norbornene), 5-ethylidene-bicyclic [2.2.1]hept-2-ene (common name: ethylidene norbornene), and their derivatives (those with substituents on the ring), etc., which are dicyclic monomers; tricyclic [5.2.1.0]hept-2-ene (common name: ethylidene norbornene), etc. 2,6 [Dec-3,8-diene (common name: dicyclopentadiene), and its derivatives, etc., are tricyclic monomers; tetracyclic [7.4.0.0] 2,7 .1 10,13 [Tetradecane-2,4,6,11-tetraene (common name: bridged methylenetetrahydrofluorene), tetracyclic [6.2.1.1] 3,6 .0 2,7 Dodecyl-4-ene (common name: tetracyclic dodecylene), 9-ethylidene tetracyclo[6.2.1.1] 3,6 .0 2,7 Tetracyclic monomers such as dodecyl-4-ene and their derivatives. These monomers may have substituents at any position. Furthermore, the cyclic olefin resins used as materials for molding bodies [1] may be addition polymers, ring-opening polymers, or their hydrides, preferably ring-opening polymers or ring-opening polymer hydrides. Cyclic olefin resins may be amorphous or crystalline, preferably amorphous.

[0037] The aforementioned ring-opening polymer can be manufactured by, for example, the method described in International Publication No. 2010 / 110323 using a ruthenium carbene complex catalyst or other translocation reaction catalyst (ring-opening polymerization catalyst), and the method described in Japanese Patent Application Publication No. 2015-54885 using a tungsten tetrachloride (phenylimide)-tetrahydrofuran complex, tungsten hexachloride or other ring-opening polymerization catalyst.

[0038] Furthermore, as a method for hydrogenating a ring-opening polymer to produce a ring-opening polymer hydride containing an alicyclic structure, examples include the method using a hydrogenation catalyst described in International Publication No. 2010 / 110323. Alternatively, for example, the aforementioned ruthenium carbene complex catalyst can be used as a ring-opening polymerization catalyst to produce a polymer containing an alicyclic structure, and then the ruthenium carbene catalyst can be directly used as a hydrogenation catalyst to hydrogenate the ring-opening polymer containing an alicyclic structure to produce a ring-opening polymer hydride containing an alicyclic structure.

[0039] The number-average molecular weight of the cyclic olefin resin used as the molding material [1] can be, for example, 5000 or more, preferably 7500 or more, and more preferably 10000 or more. Furthermore, the number-average molecular weight of the cyclic olefin resin can be, for example, 200000 or less, preferably 100000 or less, and more preferably 80000 or less. The molecular weight distribution (Mw / Mn) of the cyclic olefin resin can be, for example, 1.2 or more, preferably 1.5 or more, and more preferably 2.0 or more. Furthermore, the molecular weight distribution (Mw / Mn) of the cyclic olefin resin can be, for example, 6.0 or less, preferably 5.0 or less, and more preferably 4.5 or less.

[0040] The molecular weight (number-average molecular weight Mn) can be determined by gel permeation chromatography (GPC) as described in the examples of this specification, and the equivalent value for standard polyisoprene can be obtained. The molecular weight can also be determined by GPC using, for example, cyclohexane as the eluent, and the equivalent value for standard polyisoprene can be obtained. If the sample is insoluble in cyclohexane, it can be determined by GPC using tetrahydrofuran (THF) as the eluent, and the equivalent value for standard polystyrene can be obtained.

[0041] The glass transition temperature (Tg) of the cyclic olefin resin used as the molding material [1] is preferably 80°C or higher, more preferably 100°C or higher. By keeping the Tg in such a range, dimensional stability becomes good. In addition, the glass transition temperature (Tg) is preferably 170°C or lower, more preferably 160°C or lower. By keeping the Tg in such a range, oxidation during processing and molding is suppressed, scorching and yellowing are reduced, and the appearance becomes good.

[0042] The glass transition temperature in this invention can be determined by differential scanning calorimetry (DSC) based on JIS-K7121.

[0043] The glass transition temperature of cyclic olefin resins can be appropriately adjusted according to the type of monomers used in polymerization, the proportion, average molecular weight, and molecular weight distribution.

[0044] When the molded body [1] is an organic material, the surface of the molded body [1] (at least the surface of the mating side) may be subjected to at least one treatment selected from plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying.

[0045] <Joint Layer>

[0046] The bonding layer [2] is a component used to join the molded bodies [1] together, and can be formed on at least one molded body [1]. The bonding layer [2] has a material composition of 100 parts by weight of cyclic olefin resin [4] combined with 6 to 99 parts by weight of a softener [5] to achieve a haze of 1.0 or less. The haze of the bonding layer [2] is 1.0 or less, preferably 0.8 or less, and more preferably 0.5 or less. The haze can be measured by, for example, the method described in the embodiments of this specification (using a haze meter (NDH-7000SP; manufactured by Nippon Denshoku Kogyo Co., Ltd.) or a measuring device).

[0047] When the conjugate [3] of the present invention is used as a microchannel chip for analyzing and examining biological substances such as DNA, RNA, and proteins, it is preferable that the conjugate layer [2] is formed of a material that does not adsorb such biological substances.

[0048] As a cyclic olefin resin [4] used for bonding layer [2], examples of cyclic olefin resins used as materials for molding body [1] can be cited.

[0049] Cyclic olefin resins [4] may contain alkoxysilanes. The introduction of alkoxysilanes into cyclic olefin resins [4] can be achieved through graft polymerization, end-modification, or by adhering an alkoxysilane compound and a peroxide to particles while stirring the cyclic olefin resin [4]. Examples of alkoxysilane compounds include, for instance, trimethoxyvinylsilane, vinyltriethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane. The presence of alkoxysilanes in cyclic olefin resins [4] results in good adhesion.

[0050] The number average molecular weight of the cyclic olefin resin [4] is preferably 12,500 or more, more preferably 13,000 or more. Furthermore, the number average molecular weight of the cyclic olefin resin [4] is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 80,000 or less. When the number average molecular weight of the cyclic olefin resin [4] is within the above range, it enables good flowability during melt molding and good strength after molding.

[0051] The glass transition temperature of the cyclic olefin resin [4] is preferably below 100°C, more preferably below 90°C, and even more preferably below 85°C. Furthermore, the glass transition temperature of the cyclic olefin resin [4] is preferably above 50°C, more preferably above 60°C, and even more preferably above 65°C. When the glass transition temperature of the cyclic olefin resin [4] is within the above range, it enables good low-temperature moldability and shape retention in the operating temperature range.

[0052] The softening agent [5] is a substance that lowers the softening temperature of the mixed resin, and is a substance that reduces the haze of the mixture to 1.0 or less by mixing it with the cyclic olefin resin used in the bonding layer. When the bonding agent [3] of the present invention is used as a microchannel chip for analyzing and examining biological substances such as DNA, RNA, and proteins, the softening agent [5] is preferably a substance that does not adsorb such biological substances. Examples of softening agents [5] include, for example, hydrides of liquid paraffin, low molecular weight olefins such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, and ethylene-α-olefin copolymers and their hydrides; low molecular weight conjugated dienes such as polyisoprene and polyisoprene-butadiene copolymers and their hydrides, and preferably hydrides of liquid paraffin. The density of the hydride of liquid paraffin is preferably 0.82 to 0.89 g / cm³. 3 The preferred kinematic viscosity of the hydride of liquid paraffin is 4.0–89.0 mm⁻¹. 2 / S. The preferred SUS viscosity of the liquid paraffin hydride is 38 to 420. As a commercially available liquid paraffin hydride, commercially available products such as HICALL K-350 (manufactured by KANEDA Corporation) and HICALL K-140N (manufactured by KANEDA Corporation) can be used. By using a softener [5], the glass transition temperature of the bonding layer [2] can be lowered, and the molded parts can be bonded together at a lower temperature. Therefore, it is advantageous that deformation caused by heating during bonding is suppressed and that the re-peeling of the bonded parts becomes easier. In addition, by using a liquid paraffin hydride as a softener [5], the adsorption of proteins to the bonding layer is suppressed, and a low haze of the bonding layer can be obtained.

[0053] The thickness of the bonding layer is preferably, for example, 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The thinner the bonding layer, the thinner it becomes, thus suppressing channel deformation during steam sterilization when used, for example, in a microchannel chip. Furthermore, the thickness of the bonding layer is only required to ensure the minimum adhesion between the channel substrate and the cover substrate; for example, it can be 0.1 μm or more, preferably 0.5 μm or more, and even more preferably 1.0 μm or more.

[0054] (Manufacturing method of the joint)

[0055] The assembly of the present invention [3] can be manufactured by, for example, the manufacturing method described below (hereinafter referred to as "the manufacturing method of the present invention").

[0056] The manufacturing method of the present invention includes joining molded bodies [1] to each other via a bonding layer [2] by thermal fusion. More specifically, the manufacturing method of the present invention includes: a step of forming a bonding layer [2] on at least one molded body [1]; a step of overlapping the molded bodies [1] to form a temporarily fixed joint body via the bonding layer [2]; and a step of heating the temporarily fixed joint body to thermally fuse it.

[0057] Examples of apparatus for heat fusion welding include autoclaves, vacuum plate presses, vacuum diaphragm laminators, and hot roller presses. The heat fusion welding temperature is preferably 25°C or higher, more preferably 35°C or higher. Furthermore, the heat fusion welding temperature is preferably 100°C or lower, more preferably 60°C or lower. Before heat fusion welding, it is preferable to remove any air mixed in from the temporarily fixed joint before pressing. In the case of a decompression method such as a vacuum plate press, a small amount of air bubbles are expelled during processing. In the case of a pressurization method such as an autoclave, a small amount of air bubbles diffuse during processing; therefore, as long as a large amount of air is not mixed in, there is no problem.

[0058] When the bonding body [3] of the present invention is a microchannel chip, the manufacturing method of the present invention can be carried out in the following order: after forming a bonding layer [2] on the entire surface of the molded body [1], a channel is formed on the molded body [1]. That is, the manufacturing method of the present invention can be carried out in the following steps.

[0059] (1) A process of forming an bonding layer [2] on at least one molded body [1],

[0060] (2) A process of forming a channel on a molded body [1] with a bonding layer [2] or a molded body [1] without a bonding layer [2] by cutting, photolithography or hot stamping.

[0061] (3) A process of joining a molded body [1] with a channel formed with other molded bodies [1] via a bonding layer [2] by heat fusion.

[0062] Alternatively, if the bonding body [3] of the present invention is a microchannel chip, the manufacturing method of the present invention can be carried out in the following order: after fabricating a molded body [1] with channels formed, a bonding layer [2] is formed on the surface of the molded body [1] excluding the portion corresponding to the channels. That is, the manufacturing method of the present invention can be carried out in the following steps.

[0063] (1) The process of forming a molded body with channels[1];

[0064] (2) A process of forming an bonding layer [2] on the surface of a molded body [1] with or without channels, except for the portion corresponding to the channels.

[0065] (3) A process in which the molded bodies [1] are joined together by heat fusion via a bonding layer [2], wherein a channel is formed on at least one molded body [1] and a bonding layer [2] is formed on at least one molded body [1].

[0066] In the assembly [3] of the present invention, when the molded body [1] is an organic material other than a cyclic olefin resin, such as a polycarbonate resin or an acrylic resin, the manufacturing method of the present invention may further include a step of performing at least one treatment on the surface of the molded body [1] selected from plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying.

[0067] (Re-peeling of the joint)

[0068] The bond [3] of the present invention can be re-peeled for example for recycling. The re-peeling of the bond [3] can be carried out under conditions such as placing the bond [3] in an oven that heats the bonding layer to a softening temperature for a specified time, or heating the bond [3] with a dryer or the like.

[0069] Example

[0070] The present invention will now be described in detail based on embodiments, but the present invention is not limited to these embodiments.

[0071] <Methods for Determination and Evaluation of Physical Properties>

[0072] The determination and evaluation of various physical properties shall be carried out according to the following methods.

[0073] (Method for determining number-average molecular weight Mn)

[0074] The number-average molecular weight (Mn) was determined by gel permeation chromatography (GPC) using cyclohexane as the eluent, and the conversion value was obtained as a standard polyisoprene. Standard polyisoprene manufactured by Tosoh Corporation was used as the standard polyisoprene. In cases where the sample is insoluble in cyclohexane, the molecular weight can be determined by GPC using tetrahydrofuran (THF) as the eluent, and the conversion value was obtained as a standard polystyrene. Standard polystyrene manufactured by Tosoh Corporation was used as the standard polystyrene.

[0075] (Method for determining glass transition temperature)

[0076] The glass transition temperature (Tg) was determined using a differential scanning calorimeter (manufactured by Nanotechnology Co., Ltd., product name: DSC6220SII) based on JIS-K7121, at a heating rate of 10℃ / min.

[0077] [1. Manufacturing of Cyclic Olefin Polymers (COP)]

[0078] <Manufacturing of COP-Tg156>

[0079] (1-1) Manufacturing of ring-opening polymers:

[0080] In a nitrogen-purified glass reactor, 200 parts by weight of dehydrated cyclohexane, 0.75 mol% of 1-hexene, 0.15 mol% of diisopropyl ether, and 0.44 mol% of triisobutylaluminum were added to the reactor at room temperature, relative to 100 parts by weight of the total monomers described later, and mixed. Then, while maintaining at 45°C, 40 parts by weight of brittlemethylenetetrahydrofluorene (MTF), 56 parts by weight of tetracyclododecene (TCD), 4 parts by weight of dicyclopentadiene (DCPD), and 0.02 mol% of tungsten hexachloride (0.65 mol% toluene solution) were added to the reactor in parallel over 2 hours to carry out polymerization. Next, 0.2 mol% of isopropanol was added to the polymerization solution to deactivate the polymerization catalyst and terminate the polymerization reaction. In the above description, the amounts expressed in "mol%" are values ​​with the total monomers as 100 mol%. The number-average molecular weight (Mn) of the obtained norbornene ring-opening polymer was 1.33 x 10⁻⁶. 4 The weight-average molecular weight (Mw) is 2.8 × 10⁻⁶. 4 The molecular weight distribution (Mw / Mn) is 2.1. Furthermore, the monomer-to-polymer conversion rate is 100%.

[0081] (1-2) Preparation of hydrogenated norbornene-based cyclic olefin polymer (COP-Tg156):

[0082] Next, 300 parts of the reaction solution containing the ring-opening polymer obtained in the above step (1-1) were transferred to a high-pressure reactor with a stirrer, and 3 parts of diatomaceous earth-supported nickel catalyst ("T8400RL" manufactured by Nichih Chemical Co., Ltd., with a nickel loading rate of 57%) were added. The hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and a temperature of 160°C for 4 hours.

[0083] After the hydrogenation reaction was completed, the resulting solution was pressure filtered at 0.25 MPa using a Radiolite #500 filter bed (Ishikawajima-Harima Heavy Industries, Ltd. "FUNDABAC Filter") to remove the hydrogenation catalyst, yielding a colorless and transparent solution. This solution was then injected into a large amount of isopropanol, causing the norbornene-based cyclic olefin polymer (COP-Tg156), the hydride of the ring-opening polymer, to precipitate. After filtering off the precipitated norbornene-based cyclic olefin polymer (COP-Tg156), it was dried in a vacuum dryer (220°C, 1 Torr) for 6 hours to obtain the norbornene-based cyclic olefin polymer (COP-Tg156). The number-average molecular weight (Mn) of the norbornene-based cyclic olefin polymer (COP-Tg156) was 1.52 × 10⁻⁶. 4 The weight-average molecular weight (Mw) is 3.5 × 10⁻⁶. 4 The molecular weight distribution Mw / Mn is 2.3.

[0084] The glass transition temperature (Tg) of the obtained norbornene-based cyclic olefin polymer (COP-Tg156) is 156℃.

[0085] The norbornene-based cyclic olefin polymer (COP-Tg156) obtained in steps (1-2) above is fed into a twin-screw extruder and formed into a wire-shaped molded body through hot melt extrusion molding. The molded body is then shredded using a wire cutter to obtain particles of thermoplastic norbornene resin containing the norbornene-based cyclic olefin polymer (COP-Tg156).

[0086] <Manufacturing of COP-Tg68 (Twin-Screw Compounding Reaction)>

[0087] As monomers, 31 parts by weight of tetracyclododecene (TCD), 33 parts by weight of dicyclopentadiene (DCPD), and 36 parts by weight of norbornene (NB) were used. Otherwise, the process was the same as that used in the manufacture of COP-Tg156 to obtain a norbornene-based cyclic olefin polymer (COP-Tg68) and particles of a thermoplastic norbornene-based resin containing COP-Tg68. COP-Tg68 has a number-average molecular weight (Mn) of 13,000 and a glass transition temperature (Tg) of 68°C.

[0088] <Manufacturing of Silane-Modified COP-Tg68>

[0089] Relative to 100 parts by weight of thermoplastic norbornene resin containing COP-Tg68, 2 parts by weight of trimethoxyvinylsilane (KBM-1003; manufactured by Shin-Etsu Silicone) and 0.1 parts by weight of peroxide (PERHEXA25B; manufactured by Nippon Oil Co., Ltd.) were metered and agitated in a Henschel mixer (Super Mixer SMV manufactured by Kawada Co., Ltd.) to adhere it to the granules. Externally lubricated COP-Tg68 resin was added to the metering hopper of a twin-screw extruder (TEM-37B; manufactured by Shibaura Machinery Co., Ltd.) and melt-mixed at a screw barrel temperature of 220°C, a screw speed of 150 rpm, and a residence time of 90 seconds. The extracted filament was cooled in a water bath and granulated using a granulator (Fan Cutter; manufactured by Hoshi Plastic) to produce silane-modified COP-Tg68 (hereinafter referred to as "Si-COP-Tg68"). The number-average molecular weight (Mn) of Si-COP-Tg68 is 12700, and the glass transition temperature (Tg) is 65℃.

[0090] <Manufacturing of COP-Tg138>

[0091] As monomers, 27 parts by weight of bridged methylene tetrahydrofluorene (MTF), 35 parts by weight of tetracyclododecene (TCD), and 38 parts by weight of dicyclopentadiene (DCPD) were used. Otherwise, the process was the same as that used in the manufacture of COP-Tg156 to obtain a norbornene-based cyclic olefin polymer (COP-Tg138) and particles of a thermoplastic norbornene-based resin containing COP-Tg138. COP-Tg138 has a number-average molecular weight (Mn) of 13000 and a glass transition temperature (Tg) of 138°C.

[0092] [2. Manufacturing of the substrate molded body]

[0093] <Manufacturing of substrate molded articles using injection molding>

[0094] COP-Tg156 resin granules were dried at Tg-20℃ for 5 hours. Then, using a conventional injection molding machine (FANUC ROBOSHOT α100B, manufactured by FANUC Corporation), the granules were injection molded at a resin temperature of Tg+150℃, a mold temperature of Tg-10℃, and a holding pressure of 80MPa to produce a flat plate of 100mm×100mm×2mm, thus obtaining the substrate molded body (hereinafter referred to as "injection molded body").

[0095] <Manufacturing of substrate molded bodies using sheet forming>

[0096] COP-Tg156 resin is fed into the hopper of a single-screw extruder (single-layer extruder; manufactured by GSI Corporation) equipped with a T-die. Extrusion is carried out at a barrel temperature of 260°C and a screw speed of 80 rpm. While being cooled and fixed with mirror-finished cooling rollers, the resin is wound up to form a sheet with a thickness of 125 μm, thus obtaining a substrate molded body (hereinafter referred to as "sheet molded body").

[0097] <Molded body based on stainless steel>

[0098] SUS304 (manufactured by Nippon Metals Corporation) was used as the stainless steel material. The stainless steel material was cut into flat plates of 100mm × 100mm × 2mm to obtain the substrate molded body.

[0099] <Molded body based on corona discharge polycarbonate resin>

[0100] As a corona discharge polycarbonate resin, Panlite pc-2151#125 (manufactured by Teijin Corporation) was subjected to corona discharge treatment on one side to produce a corona discharge polycarbonate resin. The corona discharge polycarbonate resin was cut into flat plates of 100mm×100mm×2mm to obtain a substrate molded body.

[0101] [3. Formation of the bonding layer on the release film]

[0102] Weigh a specified amount of softener relative to 100 parts by weight of resin, and take the total amount as the solid component. Relative to 20 parts by weight of this solid component, seal 80 parts by weight of cyclohexane (premium grade: manufactured by Wako Pure Chemical Industries, Ltd.) in a sealed glass container (Pyrex culture medium bottle: manufactured by Corning Incorporated), and dissolve it by shaking at 60°C to prepare a cyclohexane solution with a solid component concentration of 20 parts by weight relative to 100 parts by weight of the solution.

[0103] The obtained solution was cast onto the silicon side of a PET50μm silicon-coated film (spacer SP-PET; manufactured by Mitsui Chemicals Tosel Co., Ltd.) fixed on a glass plate, and wet-coated using a coating machine (scalpel film coating machine; manufactured by AllGood Co., Ltd.) with a 300μm gap. The coated film was allowed to dry at room temperature for about 10 minutes, and then heated and dried in an oven at 80°C for 1 hour to obtain a bonding layer coated film with a 30μm thick bonding layer formed on the PET50μm silicon-coated film (release film).

[0104] [4. Bonding of substrate molded parts to each other via bonding layers]

[0105] For the molding plate (3mm thick × 26mm × 76mm), the sheet molding body (125μm thick × 26mm × 76mm) and the bonding layer coating film (80μm thick × 26mm × 76mm) are cut to their respective dimensions. The bonding layer coating film is overlapped on the cut molding plate facing the bonding layer side and aligned. After alignment, it is pressed several times with a rubber roller to expel any air trapped in the mixture, and then pressed together. After pressing, only the silicone coating PET (release film) is peeled off to create a temporary fixed bonding body A with the bonding layer on the molding plate. A 125μm thick sheet molding body is overlapped on this temporary fixed bonding body A in a positional manner, and pressed several times with a rubber roller to expel air bubbles, creating a temporary fixed bonding body B. Furthermore, a small amount of air bubbles diffuses during autoclave processing, so as long as a large amount of air is not introduced, there is no problem.

[0106] The temporarily fixed joint B was inserted into a sterilization soft bag (manufactured by Meiwa Pax Co., Ltd.) and degassed using a vacuum packaging machine (TECHNOVAC T1000; manufactured by Nippon Hoso-Kikai Co., Ltd.). The degassed package was then placed in an autoclave (Tandelaion DL-2010; manufactured by Hanyuda Iron Works Co., Ltd.) and subjected to bonding and defoaming treatment at 30°C, 0.5 MPa, and a heating and pressurization time of 15 minutes to obtain the joint.

[0107] [5. Evaluation]

[0108] <Adhesion strength>

[0109] The bond strength was determined according to JIS K 6854-2 (180° peel). Figure 2 As shown, a 10mm wide cut is made on the sheet-molded side of the bonded body, penetrating both the sheet-molded body and the bonded layer. The 10mm wide portion with the cut is peeled off from the end using a chuck-locked method. The injection-molded body side is fixed in the lower chuck of a universal testing machine with an oven (Autograph AGS-X10kN; manufactured by Shimadzu Corporation), and the sheet-molded body side is fixed in the upper chuck. The oven temperature is set to 38°C, and the temperature is maintained at 38°C ± 1°C for 5 minutes. After this period, a 180° peel is performed at a peel width of 10mm and a peel speed of 100mm / min. The peel strength is then determined and used as the bond strength. Similarly, the measurement at 80°C only changes the oven temperature; all other operations are performed in the same manner.

[0110] <Haze>

[0111] The bonding layer coating film was cut to the same size as a 28mm × 48mm microscope slide (S3132; made by Matsunami Glass), and overlapped with the bonding surfaces facing the microscope slide, aligning them in position. After alignment, it was pressed several times with a rubber roller to expel any trapped air, and then pressed together. After pressing, only the silicone coating PET was peeled off, and a microscope slide (S3132; made by Matsunami Glass) of the same size was overlapped on the peeled bonding layer and aligned in position. After alignment, it was pressed together while expelling any trapped air with a rubber roller to obtain a temporarily fixed bond C.

[0112] The temporarily fixed conjugate C was inserted into a sterile soft bag (manufactured by Meiwa Pax Co., Ltd.) and degassed using a vacuum packaging machine (TECHNOVAC T1000; manufactured by Nippon Hoso-Kikai Co., Ltd.). The degassed package was then placed in an autoclave (Tandelaion DL-2010; manufactured by Hanyuda Iron Works Co., Ltd.) and subjected to bonding and defoaming treatment at 30°C, 0.5 MPa, and a heating and pressurization time of 15 minutes to obtain a conjugate for haze measurement.

[0113] The obtained haze measurement was performed using a haze meter for the assembly (NDH-7000SP; manufactured by Nippon Denshoku Kogyo Co., Ltd.). At this time, the haze measurement value of the microscope slide unit was less than 0.1, and the value obtained by subtracting this value from the blank value was taken as the haze.

[0114] <BSA adsorption capacity>

[0115] As a protein adsorption assay, fetal bovine serum albumin (BSA) was used to determine the adsorption amount on the junction layer using the following method (micro-BCA method).

[0116] (1. Preparation of adhesive solution)

[0117] Weigh a specified amount of softener relative to 100 parts by weight of resin, and take the total amount as the solid component. Relative to 20 parts by weight of this solid component, seal 80 parts by weight of cyclohexane (premium grade: manufactured by Wako Pure Chemical Industries, Ltd.) in a sealed glass container (Pyrex culture medium bottle: manufactured by Corning Incorporated), and dissolve it by shaking at 60°C to prepare a cyclohexane solution with a solid component concentration of 20 parts by weight.

[0118] (2. Preparation of the adsorbed sample)

[0119] In each 35mm petri dish (Nunc petri dish 150460; manufactured by Thermo Fisher Scientific), add 1mL of the cyclohexane solution prepared in step 1 above, ensuring it covers the entire bottom surface of the dish. After drying at room temperature for about 10 minutes, heat and dry in an 80°C oven for 1 hour to prepare the adhesive coating dish.

[0120] (3. Protein adsorption treatment and extraction)

[0121] Add 2.5 mL of BSA solution, adjusted to 1 mg / mL with phosphate buffer, to the adhesive coating dish and incubate at 37°C for 2 hours to allow BSA adsorption. Remove the sample from the incubator, extract the BSA solution, and wash with PBS solution while cleaning. Next, add 1 wt% sodium dodecyl sulfate (SDS) solution to a 2.5 mL dish and extract using an ultrasonic cleaner for 5 minutes.

[0122] (4. Quantification of protein)

[0123] In a 96-well plate, 150 μL of 20 mg / mL BSA solution (including blank PBS only) was added as a standard curve. For the assay, 150 μL of the extraction solution obtained in step 3 above was added. Next, using a micro-BCA assay kit (Mini-BCA Assay Kit; Thermo Fisher Scientific), 150 μL of the kit reagents were added to each well of the 96-well plate, and the mixture was slowly stirred with a plate shaker for approximately 30 seconds. The 96-well plate was sealed to prevent evaporation and incubated at 37°C for 2 hours. After the reaction, the absorbance at 562 nm was measured using a microplate reader, and the amount of protein adsorbed was calculated from the standard curve.

[0124] <Warp>

[0125] With the same content as described above in [4. Adhesion of substrate molded bodies to each other via bonding layer], for the injection molded body (3mm thick × 15mm × 100mm), the dimensions are set as a sheet molded body (125μm thick × 15mm × 100mm) and a bonding layer coating film (80μm thick × 15mm × 76mm), and it is manufactured in the same manner.

[0126] The method for determining warpage is as follows: after bonding in an autoclave, the removed joint is placed on a horizontal plate such as a glass plate, and the warpage at both ends is measured with vernier calipers.

[0127] [7. Results]

[0128] The manufacturing conditions and evaluation results are shown in Table 1.

[0129] [Table 1-1]

[0130]

[0131] [Table 1-2]

[0132]

[0133] Industrial availability

[0134] According to the present invention, it is possible to provide a method for manufacturing a joint that suppresses deformation caused by heating during bonding, facilitates the re-peeling of the joint, suppresses protein adsorption, and yields a joint with low haze.

Claims

1. A microchannel chip comprising bonding at least one or more molded bodies [1] via a bonding layer [2] having a material composition different from that of the molded bodies, wherein the molded bodies [1] have channels formed on at least one surface, The bonding layer [2] comprises a softener [5] and 100 parts by weight of a cyclic olefin resin [4]. The content of softener [5] in the bonding layer [2] is 6 to 99 parts by weight of softener [5] relative to 100 parts by weight of cyclic olefin resin [4]. The haze of the bonding layer [2] is below 1.

0. The softener [5] is composed of a hydride of liquid paraffin, the kinematic viscosity of which is 4.0–89.0 mm. 2 / S.

2. The microchannel chip according to claim 1, characterized in that, The number-average molecular weight of the cyclic olefin resin [4] is 12,500 or higher.

3. The microchannel chip according to claim 1 or 2, characterized in that, The glass transition temperature of the cyclic olefin resin [4] is below 100°C.

4. The microchannel chip according to claim 1 or 2, characterized in that, The cyclic olefin resin [4] has alkoxysilyl groups.

5. The microchannel chip according to claim 1 or 2, characterized in that, The molded body [1] is an organic material, and the surface of the molded body [1] is subjected to at least one treatment selected from plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying.

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