Microfluidic system, reaction method for employing microfluidic system, and method for producing polymer

Abstract

A microfluidic system includes a plurality of microfluidic devices having a microchannel formed therein, wherein the microfluidic system comprises a plurality of reaction means that include: an introducing unit for introducing one or more of a plurality of dissimilar fluids into a prescribed processing channel in order to mix the plurality of the dissimilar fluids within the prescribed processing channel; a reaction channel that is disposed downstream of the introducing unit and that is formed in the microfluidic device as the microchannel constituting a portion of the prescribed processing channel, the reaction channel causing a chemical reaction to proceed among reactants contained in a mixed fluid of the plurality of the dissimilar fluids. The plurality of reaction means are arranged in series such that the reaction channels communicate with each other. The volume of the reaction channel in one or more of the plurality of reaction means is different from the volume of the reaction channel in the other reaction means.

Description

Microfluidic system, reaction method using the microfluidic system, and polymer production method

[0001] The present disclosure relates to a microfluidic system, a reaction method using a microfluidic system, and a method for producing a polymer.

[0002] In recent years, in the fields of chemical synthesis and chemical analysis, the use of microfluidic devices has been increasing as a means of mixing fluids and promoting reactions (chemical reactions). A microfluidic device is a device that has a minute flow path (microchannel) with a flow path width on the order of μm and performs chemical processing within the minute flow path. In particular, a microfluidic device intended to perform chemical reactions within the minute flow path is also called a microreactor.

[0003] A microreactor mixes multiple different types of fluids (heterogeneous fluids) introduced into a microchannel and brings them into contact with each other, resulting in a chemical reaction. In a microreactor, the microchannel serves as the reaction site, allowing the multiple heterogeneous fluids to form thin laminar flows, and molecular diffusion at the contact interface allows the fluids to mix and react quickly. Furthermore, compared to conventional batch-type reactors using large tanks, a microreactor offers the advantage of high heat transfer and conduction efficiency due to its greater surface area relative to the fluid volume.

[0004] As a technique using a microreactor, Patent Document 1 discloses a technique for controlling the uniformity (particularly, molecular weight distribution) of a polymer obtained by using a microreactor that includes a first inlet for introducing a monomer component and another inlet located downstream of the first inlet, and that can introduce monomer components into the first inlet and the other inlet.

[0005] Japanese Patent Application Laid-Open No. 2020-29518

[0006] In microfluidic systems including microfluidic devices, in order to increase the production amount of reaction products, it is important to sufficiently advance the chemical reaction in the reaction system and increase the reaction rate of the reactants. However, for example, when the flow rate of the reaction system is high or the reactivity of the reactants is low, the residence time of the fluid containing the reactants in the reaction channel may be insufficient, and the chemical reaction in the reaction system may not proceed sufficiently. As a result, problems such as an inability to ensure the production amount of the reaction product may occur.

[0007] The technology of the present disclosure has been made in consideration of the above-mentioned circumstances, and its purpose is to provide a microfluidic system including a microfluidic device, which can ensure the required residence time of a reactant-containing fluid in a microchannel.

[0008] In order to solve the above problems, the present inventors have conducted extensive research. As a result, they have found that the above problems can be solved by arranging multiple reaction means in series, each with a volume adjusted according to the target chemical reaction. That is, the gist of the present disclosure is as follows.

[0009] [1] A microfluidic system including a plurality of microfluidic devices formed with microchannels, comprising a plurality of reaction means each having an inlet part for introducing at least one of a plurality of different fluids into a predetermined processing channel to mix the plurality of different fluids in the predetermined processing channel, and a reaction channel formed in the microfluidic device as a microchannel arranged downstream of the inlet part and constituting a part of the predetermined processing channel, the reaction channel causing a chemical reaction of reactants contained in the mixed fluid of the plurality of different fluids to proceed, the plurality of reaction means being arranged in series so that the reaction channels are in communication with each other, and the volume of the reaction channel in at least one of the plurality of reaction means is different from the volume of the reaction channel in the other reaction means. [2] The microfluidic system according to [1], wherein the volumes of the reaction channel in at least two of the plurality of reaction means are set so that the volume of the reaction channel in the reaction means located further downstream is larger. [3] The microfluidic system according to [1] or [2], wherein at least two of the plurality of reaction means have volumes set so that the volumes of the reaction channels are equal. [4] The microfluidic system according to [1] or [2], wherein the volumes of the plurality of reaction means are set so that the volume of the reaction channel of the reaction means located further downstream is larger. [5] The microfluidic system according to any of [1] to [4], wherein the plurality of different fluids include at least a fluid containing a polymerization initiator and a fluid containing one or more monomers, the fluid containing the one or more monomers is introduced into the processing channel from the inlet, and the one or more monomers are polymerized in the reaction channel in the presence of the polymerization initiator. [6] The microfluidic system according to [5], wherein the volumes of the reaction channels in the plurality of reaction means are set so that the polydispersity Mw / Mn (Mw and Mn are the weight average molecular weight and number average molecular weight of the polymer, respectively) of the polymer produced by the microfluidic system is 1.3 or more and 3.0 or less.[7] The microfluidic system according to any one of [1] to [6], further comprising a reaction promotion means for promoting a chemical reaction of reactants contained in the mixed fluid in the reaction channel. [8] The microfluidic system according to [7], wherein the reaction promotion means includes at least one of a heating means, a light irradiation means, a vibration energy applying means, or a voltage applying means. [9] The microfluidic system according to any one of [1] to [8], wherein the reaction channel has a channel width of 1000 μm or less.

[10] A reaction method using a microfluidic system including a plurality of microfluidic devices formed with microchannels, wherein the microfluidic system comprises a plurality of reaction means each having an inlet part that introduces at least one of a plurality of different fluids into a predetermined processing channel to mix the plurality of different fluids within the predetermined processing channel, and a reaction channel that is located downstream of the inlet part and formed in the microfluidic device as a microchannel that constitutes part of the predetermined processing channel, and that causes a chemical reaction of reactants contained in the mixed fluid of the plurality of different fluids, wherein the plurality of reaction means are arranged in series so that the reaction channels are in communication with each other, and the volume of the reaction channel in at least one of the plurality of reaction means is made different from the volume of the reaction channel in the other reaction means.

[11] The reaction method according to

[10] , wherein the volumes of the reaction channels are set so that the volume of the reaction channel in at least two of the plurality of reaction means is larger the more downstream the reaction means is located.

[12] The reaction method according to

[10] or

[11] , wherein the volumes are set so that the volumes of the reaction channels are equal in at least two of the plurality of reaction means.

[13] The reaction method according to

[10] or

[11] , wherein the volumes are set so that the volume of the reaction channel of a reaction means located further downstream in the plurality of reaction means is larger.

[14] The reaction method according to any one of

[10] to

[13] , wherein the plurality of different fluids include at least a fluid containing a polymerization initiator and a fluid containing one or more types of monomers, the fluid containing the one or more types of monomers is introduced into the processing flow path from the inlet, and the one or more types of monomers are polymerized in the presence of the polymerization initiator in the reaction flow path.

[15] The reaction method according to

[14] , wherein the volumes of the reaction flow paths in the plurality of reaction means are set so that the polydispersity Mw / Mn (Mw and Mn are the weight average molecular weight and number average molecular weight of the polymer, respectively) of the polymer produced by the microfluidic system is 1.3 or more and 3.0 or less.

[16] The reaction method according to any one of

[10] to

[15] , wherein the microfluidic system further comprises a reaction promotion means for promoting a chemical reaction of reactants contained in the mixed fluid in the reaction flow path.

[17] The reaction method according to

[16] , wherein the reaction promoting means includes at least one of a heating means, a light irradiation means, a vibration energy applying means, and a voltage applying means.

[18] The reaction method according to any one of

[10] to

[17] , wherein the reaction channel has a channel width of 1000 μm or less.

[19] A method for producing a polymer using a microfluidic system including a plurality of microfluidic devices formed with microchannels, wherein the microfluidic system comprises a plurality of reaction means having an inlet part for introducing at least one monomer from a plurality of different fluids into a predetermined processing flow path in order to mix the plurality of different fluids, the at least one monomer being one of the plurality of different fluids, into the predetermined processing flow path, and a reaction flow path formed in the microfluidic device as a microchannel that is arranged downstream of the inlet part and constitutes a part of the predetermined processing flow path, the reaction flow path allowing a polymerization reaction of the one or more monomers to proceed in the presence of the polymerization initiator using the mixed fluid of the plurality of different fluids, wherein the volume of the reaction flow path in at least one of the plurality of reaction means is made different from the volume of the reaction flow path in the other reaction means.

[20] The method for producing a polymer according to

[19] , wherein, in at least two of the plurality of reaction means, the volume of the reaction channel is set so that the volume of the reaction means located more downstream is larger.

[21] The method for producing a polymer according to

[19] or

[20] , wherein, in at least two of the plurality of reaction means, the volumes of the reaction channel are set to be equal.

[22] The method for producing a polymer according to

[19] or

[20] , wherein, in the plurality of reaction means, the volume is set so that the volume of the reaction channel is larger in the reaction means located more downstream.

[0010] According to the technology disclosed herein, it is possible to provide a microfluidic system including a microfluidic device, which can ensure the required residence time of a reactant-containing fluid in a microchannel.

[0011] Fig. 1 is a configuration diagram of a polymer production system according to this embodiment, and Fig. 2 is a plan view of a reaction device according to this embodiment.

[0012] Each configuration and combination thereof in each embodiment is merely an example, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope of the gist of this disclosure. The present disclosure is not limited by the embodiments, but only by the claims. Furthermore, each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, and "A to B" means greater than or equal to A and less than or equal to B.

[0013] One embodiment of the present disclosure is a microfluidic system including a plurality of microfluidic devices each having a microchannel formed therein, the microfluidic system comprising a plurality of reaction means each having an inlet portion that introduces at least one of a plurality of different fluids into a predetermined processing channel in order to mix the plurality of different fluids within the predetermined processing channel, and a reaction channel that is disposed downstream of the inlet portion and formed in the microfluidic device as a microchannel that constitutes part of the predetermined processing channel, the reaction channel causing a chemical reaction of reactants contained in the mixed fluid of the plurality of different fluids to proceed, the plurality of reaction means being disposed in series such that the reaction channels are connected to each other, and the volume of the reaction channel in at least one of the plurality of reaction means is different from the volume of the reaction channel in the other reaction means.

[0014] <Microfluidic Device> A microfluidic device is a device in which minute flow channels (microchannels) with a flow channel width on the order of μm are formed. The microfluidic device according to the present disclosure is not particularly limited and may be a chip-type microfluidic device in which a microchannel is formed inside or on the surface of a substrate, or a tube-type microfluidic device in which a microchannel is formed inside a tube. Furthermore, depending on the purpose, the microfluidic device may be called a micromixer if the purpose is mixing, or a microreactor if the purpose is chemical reaction. The microfluidic device according to the present disclosure processes at least a reaction process as a unit operation. The reaction processes that can be processed by the microfluidic device are not particularly limited, but examples include solid-phase reactions, slurry mixing / reactions, liquid-phase reactions, liquid-phase mixing, and gas-liquid reactions.

[0015] The microchannel may be formed inside the substrate or on the surface of the substrate. The cross-sectional shape of the microchannel is not particularly limited and can be appropriately selected depending on the purpose, and examples include circular, rectangular, semicircular, and triangular shapes. The width (inner diameter) and cross-sectional area of ​​the microchannel are also not particularly limited as long as they do not impair the effects of the technology disclosed herein and can be appropriately selected depending on the purpose. For example, the channel width is preferably 15 mm or less, more preferably 20 μm to 1000 μm, even more preferably 100 μm to 500 μm, and particularly preferably 300 μm to 500 μm. If the channel width exceeds 15 mm, the surface area per unit volume decreases, which may make rapid mixing and removal of reaction heat difficult. If the channel width is greater than 1000 μm, the molecular diffusion distance increases, reducing mixing efficiency and reducing the functionality of the microfluidic device. Furthermore, if the width of the flow channel is less than 20 μm, the pressure loss of the liquid flowing through the flow channel increases, and a pump with high pressure resistance is required for the liquid transfer, which may increase the manufacturing cost. ２ 225mm or more ２ It is preferable that the thickness is 0.0003 mm or less. ２ More than 1 mm ２ It is more preferable that the thickness is 0.01 mm or less. ２ 0.25mm or more ２It is more preferable that the channel length be 10 mm or less, more preferably 20 mm or less and 10,000 mm or less, even more preferably 50 mm or less and 5,000 mm or less, and particularly preferably 80 mm or less and 1,500 mm or less. In addition, the length of the channel formed in the microfluidic device (channel length) is not particularly limited and can be set appropriately depending on the mixing time and reaction time. For example, in the production of a polymer, the channel length of the reaction channel is preferably 10 mm or more and 500 m or less, more preferably 20 mm or more and 10,000 mm or less, even more preferably 50 mm or more and 5,000 mm or less, and particularly preferably 80 mm or more and 1,500 mm or less. In addition, in order to obtain a polymer with a smaller polydispersity Mw / Mn in the production of a polymer, in addition to the channel length of the reaction channel being within the above range, the channel depth is preferably 0.1 mm or more and 1.0 mm or less, more preferably 0.3 mm or more and 0.8 mm or less, and even more preferably 0.5 mm or more and 0.6 mm or less, and the channel width is preferably 0.2 mm or more and 1.0 mm or less, more preferably 0.3 mm or more and 0.8 mm or less, and even more preferably 0.5 mm or more and 0.6 mm or less. Furthermore, to obtain a polymer with a smaller polydispersity index Mw / Mn, the ratio of channel width to channel depth is preferably 1.0 to 2.5, more preferably 1.0 to 2.0, even more preferably 1.0 to 1.5, and particularly preferably 1.0. The flow rate of the liquid flowing through the microchannel of the microfluidic device is not particularly limited and can be selected appropriately depending on the purpose. For example, in the production of a polymer, the flow rate is preferably 0.000001 mL / min to 10 mL / min, more preferably 0.00001 mL / min to 0.1 mL / min, and even more preferably 0.0001 mL / min to 0.05 mL / min. A flow rate within the above range tends to achieve rapid mixing of the monomer component and the polymerization initiator, and also tends to suppress pressure loss. Note that the above refers to the flow rate of the fluid immediately after introduction into the microchannel.

[0016] <Reaction Promotion Means> The reaction promotion means is not particularly limited and can be appropriately selected depending on the desired chemical reaction. Examples of the reaction promotion means include heating means, light irradiation means, vibration energy imparting means, voltage application means, etc. Examples of the heating means include heaters and microwave irradiation devices, examples of the light irradiation means include LEDs, organic light-emitting devices (OLEDs), lasers, arc lamps, etc. Examples of the vibration energy imparting means include ultrasonic generators and piezoelectric transducers, etc. Examples of the voltage application means include electrodes, etc. The reaction promotion means may include at least one of the various means described above, or may be a combination of multiple means. For example, the reaction promotion means may heat the fluid in the reaction flow channel using a microwave irradiation device as heating means, or may irradiate the fluid in the reaction flow channel with light using an illumination device as light irradiation means using various light sources.

[0017] <Heterogeneous Fluids> In the microfluidic system according to this embodiment, a chemical reaction of reactants contained in a mixed fluid (i.e., a reaction system) of multiple heterogeneous fluids proceeds in the reaction flow path of the reaction means. In this embodiment, the multiple heterogeneous fluids are mixed by circulating the multiple heterogeneous fluids through predetermined processing flow paths in the reaction means. The multiple heterogeneous fluids may be liquids or gases, but are preferably liquids.

[0018] Each of the multiple heterogeneous fluids is a fluid for supplying components necessary for the progress of a chemical reaction to the reaction system. The components necessary for the progress of a chemical reaction include one or more reactants and, if necessary, may include other components necessary for the progress of the chemical reaction (hereinafter simply referred to as "other components"). Preferably, the multiple heterogeneous fluids include one or more of the other components necessary for the progress of the chemical reaction. In other words, one of the multiple heterogeneous fluids contains one or more reactants, and the other one or more fluids each contain one or more reactants and / or one or more other components. Note that, among the multiple heterogeneous fluids mixed in another reaction means arranged immediately downstream of one reaction means, one or more fluids are fluids containing a reaction product obtained by the chemical reaction in the one reaction means. This reaction product may be a reactant to be subjected to a chemical reaction in the other reaction means, but it may also be a component that is not reactive and does not undergo a chemical reaction (i.e., a component other than the component necessary for the progress of the chemical reaction).

[0019] When any of the multiple different fluids contains other components necessary for the progress of a chemical reaction, the other components necessary for the progress of the chemical reaction may be contained in the one fluid, or may be contained in both the one fluid and the one or more other fluids, but it is preferable that the other components be contained in the one or more other fluids.

[0020] Other components necessary for the progress of the chemical reaction may be appropriately selected as needed from known or commonly used components for the target chemical reaction, including, for example, initiators, catalysts, catalyst assistants, solvents, reaction reagents such as acids, bases, and water, and additives such as surfactants.

[0021] The fluid that supplies each of the multiple different fluids may be determined based on the convenience of mixing (for example, various conditions such as the properties of the reactants, the properties of the other components, and the number of components necessary for the chemical reaction to proceed). The number of components contained in one fluid is not particularly limited, and is usually 1 to 5, preferably 1 to 4, and more preferably 2 to 3. The number of multiple different fluids is not particularly limited as long as it is 2 or more, but is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2.

[0022] More specifically, when compound A and compound B are reacted in solvent A in the presence of catalyst A, compound A and compound B correspond to reactants, and solvent A and catalyst A correspond to other components necessary for the progress of the chemical reaction. The types and numbers of components contained in the multiple different fluids are not particularly limited as long as each contains one or more of these components. For example, the multiple different fluids may be three fluids: a solution in which compound A is dissolved in solvent A, a solution in which compound B is dissolved in solvent A, and a solution in which catalyst A is dissolved in solvent A. Furthermore, for example, the multiple fluids may be two fluids: a fluid consisting of compound A and compound B, and a solution in which catalyst A is dissolved in solvent A.

[0023] When a chemical reaction proceeds in the absence of other components necessary for the chemical reaction to proceed, the mixed fluid of multiple different fluids does not contain any other components necessary for the chemical reaction to proceed. Such a case is, for example, when a chemical reaction between reactant A and reactant B proceeds in a reaction system consisting only of reactant A and reactant B. In this case, in the reaction means, one of reactant A, which is one fluid, and reactant B, which is another fluid, is circulated through a predetermined processing flow path, and the other is introduced from an introduction part.

[0024] Examples of chemical reactions include synthesis reactions such as synthesis reactions of organic compounds, synthesis reactions of inorganic compounds, and synthesis reactions of organic-inorganic hybrid materials; as well as decomposition reactions of organic compounds, decomposition reactions of inorganic compounds, and decomposition reactions of organic-inorganic hybrid materials. Of these, the chemical reaction is preferably a synthesis reaction, more preferably a synthesis reaction of an organic compound, and even more preferably a synthesis reaction of a polymer. These chemical reactions maximize the benefits of the microfluidic system according to the present embodiment, namely, the ability to ensure the quality of the reaction product by ensuring sufficient progress of the chemical reaction. However, since ensuring an appropriate residence time in the reaction channel allows the reaction to proceed sufficiently regardless of the type of chemical reaction, the effects of the technology according to the present disclosure can also be achieved with chemical reactions other than those described above. Therefore, the chemical reaction is not limited to the above-described chemical reactions.

[0025] In the microfluidic system according to this embodiment, by ensuring an appropriate residence time in the reaction channel, the chemical reaction can proceed sufficiently and consume most of the raw materials. Therefore, the microfluidic system according to this embodiment is an effective system for efficiently obtaining the target reaction product. In particular, in the production of polymers, since the monomers are sufficiently consumed in the subsequent reaction means, it is possible to produce polymers with a small polydispersity index Mw / Mn (Mw: weight-average molecular weight, Mn: number-average molecular weight). Therefore, the microfluidic system according to this embodiment is suitable for the production of polymers, and even more suitable for the production of photoresist polymers. Below, an example of multiple heterogeneous fluids used in the production of polymers by radical polymerization of monomers is described.

[0026] In this example, a microfluidic device is used in which two reaction means, a first reaction means and a second reaction means, are arranged in series from the upstream side, and a polymer is produced according to the following steps (i) to (v).

[0027] (i) An initiator solution in which a radical polymerization initiator is dissolved in a solvent is circulated through a predetermined processing flow path of a first reaction means, and a monomer solution in which a monomer is dissolved in a solvent is introduced from an inlet of the first reaction means, and radical polymerization of the monomer is carried out in the reaction flow path. Here, the monomer corresponds to the reactant, and the solvent and radical polymerization initiator correspond to the other components. Furthermore, the monomer solution and initiator solution correspond to multiple different fluids. In the reaction flow path of the first reaction means, most of the monomer is consumed, and the reaction mixture obtained after the polymerization reaction contains a small amount of monomer, the radical polymerization initiator (and / or radicals generated from the radical polymerization initiator; in this specification, "radical polymerization initiator" also includes radicals generated from the radical polymerization initiator), the solvent, and a polymer as the reaction product.

[0028] (ii) Next, the reaction mixture obtained in (i) above is circulated through a predetermined processing flow path of the second reaction means, and a monomer solution in which a monomer is dissolved in a solvent is introduced from the inlet of the second reaction means, and radical polymerization of the monomer is carried out in the reaction flow path. Here, the monomer corresponds to the reactant, and the solvent and radical polymerization initiator correspond to the other components. Furthermore, the monomer solution and the reaction mixture correspond to the multiple different fluids.

[0029] (iii) A polymer is recovered from the reaction mixture discharged from the reaction channel in (ii) above.

[0030] As in the above example, in a multi-stage polymer synthesis, when a monomer solution is introduced into a reaction mixture obtained in a previous stage, the monomer introduced into one reaction means and the monomer introduced into one or more other reaction means (in the above example, the monomer introduced into the first reaction means in (i) and the monomer introduced into the second reaction means in (ii)) may be the same or different, but from the viewpoint of mass production of the same polymer, it is preferable that they are the same. Also, in the above example, in a multi-stage polymer synthesis, a monomer solution is introduced into the mixed reaction product obtained in a previous stage, but the monomer solution introduced in any stage may be replaced with an initiator solution, or an initiator solution may be introduced in addition to the monomer solution in any stage. In this case, the radical polymerization initiator introduced into one reaction means and the radical polymerization initiator introduced into one or more other reaction means may be the same or different, but it is preferable that they are the same.

[0031] In the microfluidic system used in the above example, two reaction means are arranged in series, but in a modified example using a microfluidic system in which three or more reaction means are arranged in series, a polymer can be produced by repeating the same operation as in (ii) above. In another modified example in which the monomer solution introduced into the reaction means in (ii) above is replaced with a fluid containing a chemical modifier, a polymer can be obtained in which one or more of the terminals, main chain, and side chains of the polymer obtained in (i) above are modified.

[0032] In the production of a polymer, a solution of a chain transfer agent dissolved in a solvent may be further introduced into the reaction means to prepare a mixed fluid containing the chain transfer agent, which allows the production of a polymer with a smaller polydispersity index Mw / Mn.

[0033] The quality of a polymer can be evaluated, for example, by the polydispersity index Mw / Mn. Generally, the narrower the molecular weight distribution of a polymer, i.e., the smaller the polydispersity index Mw / Mn, the smaller the variation in molecular weight of the polymer, making it easier to obtain a polymer with desired properties. The polydispersity index Mw / Mn is calculated by measuring the weight average molecular weight Mw and number average molecular weight Mn of a polymer by gel permeation chromatography (GPC) and dividing the former by the latter. The following conditions are used as the GPC measurement conditions.

[0034] Apparatus: GPC system (Shimadzu Corporation) System controller: SIL-20A (Shimadzu Corporation) Pump: LC-20AD (Shimadzu Corporation) Degasser: DGU-20A3R (Shimadzu Corporation) Column oven: CTO-20AC (Shimadzu Corporation) RI detector: RID-20A (Shimadzu Corporation) Column: GPC KF-806L (column size: 8.0 mm (ID) × 300 mm (L), manufactured by Resonac Corporation) × 3 Guard column: KF-G (column size: 4.6 mm (ID) × 10 mm (L), manufactured by Resonac Corporation) Column temperature: 40°C Cell temperature: 40°C Eluent: tetrahydrofuran Eluent flow rate: 0.8 mL / min Injection volume: 35 μL Analysis time: 60 minutes Sample: 5 wt% tetrahydrofuran solution Sample for creating calibration curve: Polystyrene calibration kit S-M-10 (manufactured by Agilent Technologies, Inc.)

[0035] The monomers, radical polymerization initiators, solvents, and chain transfer agents used in the radical polymerization reaction of the above-mentioned monomers will be described in more detail below.

[0036] (Monomer) The type of monomer, the number of monomer types, and the mixing ratio of the monomers when two or more monomer types are used are selected depending on the polymer to be produced. Therefore, a single monomer may be used, or two or more types may be used in any combination and ratio. When a copolymerization reaction is performed using two or more monomers, the type of copolymerization sequence is not particularly limited, and examples include random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization. The structure of the resulting polymer is also not particularly limited, and may be linear, branched, or cyclic.

[0037] The type of monomer is not particularly limited as long as it is a polymerizable monomer (hereinafter also referred to as "polymerizable monomer"). For example, polymerizable monomers disclosed in JP 2018-149791 A and JP 2010-194983 A, specifically, (meth) polymerizable monomers containing an acryloyl group, polymerizable monomers containing an isocyanate group, polymerizable monomers containing a carboxyl group, polymerizable monomers containing a hydroxyl group, polymerizable monomers containing an epoxy group, polymerizable monomers containing an oxazoline group, polymerizable monomers containing a maleimide group, polymerizable monomers containing an amino group, styrene-based monomers, fluorine-containing vinyl monomers, silicon-containing vinyl-based monomers, conjugated diene-based monomers, aromatic vinyl monomers, vinyl carboxylic acid vinyl esters, olefin-based monomers, vinyl halides, vinylidene halides, allyl halides, and vinyl ethyl ether. At least one monomer selected from the group consisting of.

[0038] These monomers may be used alone or in combination of two or more. The monomers listed below may be derivatives thereof. The monomers may be synthesized or commercially available. In this specification, the terms "(meth)acryloyl", "meth(acrylic)", and "(meth)acrylate" mean "acryloyl and / or methacryloyl", "methacrylic and / or acrylic", and "acrylate and / or methacrylate", respectively.

[0039] Examples of polymerizable monomers containing a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, Examples include 3-methoxybutyl acrylate, stearyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. In addition to the above, examples include monomers having a chemical structure exhibiting photosensitivity, which will be described later.

[0040] Examples of aromatic vinyl monomers include styrene; alkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-ethylstyrene, p-isopropylstyrene, p-n-butylstyrene, p-tert-butylstyrene, α-methylstyrene, and α-methyl-p-methylstyrene; alkoxystyrenes such as o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and p-tert-butoxystyrene; halostyrenes such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and p-bromostyrene; hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and 3,5-dihydroxystyrene; and styrenesulfonic acid or an alkali metal salt thereof.

[0041] Examples of vinyl carboxylates include vinyl carboxylates having 3 to 10 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl pivalate.

[0042] Examples of conjugated diene monomers include conjugated dienes having 4 to 16 carbon atoms, such as butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, and 1-phenyl-1,3-butadiene.

[0043] Examples of the olefin monomer include alkenes having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 2-butene, and isobutene.

[0044] Examples of vinyl halides include vinyl fluoride, vinyl chloride, and vinyl bromide.

[0045] Examples of the vinylidene halides include vinylidene fluoride, vinylidene chloride, and vinylidene bromide.

[0046] When the polymer to be produced is a photoresist polymer, a monomer having a photosensitive chemical structure is used instead of or in addition to the above-mentioned monomer. For example, when producing a polymer for a chemically amplified photoresist using a photoacid generator, the monomer preferably contains a monomer having a group that generates a polar group by partial elimination under the action of acid (sometimes referred to as an "acid-decomposable group"). The polarity of the photoresist polymer increases under the action of acid, thereby increasing its solubility in an alkaline developer and enabling pattern formation.

[0047] Examples of polar groups include acidic groups and alcoholic hydroxyl groups. Examples of acidic groups include phenolic hydroxyl groups; carboxy groups; fluorinated alcohol groups such as hexafluoro-2-hydroxyisopropyl groups; sulfonic acid groups; sulfonamide groups, sulfonylimide groups; (alkylsulfonyl)(alkylcarbonyl)methylene groups; (alkylsulfonyl)(alkylcarbonyl)imide groups; bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups; bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups; acidic groups such as tris(alkylcarbonyl)methylene groups and tris(alkylsulfonyl)methylene groups; and the like. Of these, the polar group is preferably a carboxy group, a fluorinated alcohol group, or a sulfonic acid group.

[0048] The acid-decomposable group is preferably a group in which the hydrogen atom of the polar group is substituted with a group that is cleaved by an acid. Examples of the acid-decomposable group include -C(R Ｉ ) (R ＩＩ ) (R ＩＩＩ ) and a group represented by —C(R ＩＶ ) (R Ｖ ) (OR ＶＩ In the above formula, R Ｉ ~R ＩＩＩ and R ＶＩ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ＩＶ and R ＶR each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Ｉ ~R ＩＩＩ At least two of the groups may be bonded to each other to form a ring. ＩＶ and R Ｖ may be bonded to each other to form a ring.

[0049] The lower limit of the number of carbon atoms in the acid-decomposable group is not particularly limited, but is preferably at least 4, more preferably at least 5. The upper limit of the number of carbon atoms in the acid-decomposable group is not particularly limited, but is preferably 20 or less.

[0050] R Ｉ ~R ＶＩ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, and an octyl group.

[0051] R Ｉ ~R ＶＩ The cycloalkyl group represented by the formula (I) may be a monocyclic hydrocarbon group or a polycyclic (bridged ring) hydrocarbon group. Preferred examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Preferred examples of the polycyclic hydrocarbon group include cycloalkyl groups having 6 to 20 carbon atoms, such as an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an androstanyl group. In the cycloalkyl group, a carbon atom other than the first carbon atom among the carbon atoms constituting the cycloalkane ring may be substituted with a heteroatom such as an oxygen atom. In this case, the number of carbon atoms substituted with a heteroatom is not particularly limited.

[0052] R Ｉ ~R ＶＩPreferred examples of the aryl group represented by the formula (I) include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group, and an anthryl group.

[0053] R Ｉ ~R ＶＩ Preferred examples of the aralkyl group represented by the formula (I) include aralkyl groups having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, and a naphthylmethyl group.

[0054] R Ｉ ~R ＶＩ Preferred examples of the alkenyl group represented by the formula (I) include alkenyl groups having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

[0055] R Ｉ ~R ＩＩＩ a ring formed by bonding at least two groups selected from the group consisting of R ＩＶ and R Ｖ The ring formed by bonding is preferably a cycloalkane ring. Preferred examples of the cycloalkane ring include monocyclic cycloalkane rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring; and polycyclic cycloalkane rings such as a norbornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.

[0056] In addition, R Ｉ ~R ＶＩ The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by the formula (I) and the cycloalkane ring may each have a substituent within the range that does not inhibit the radical polymerization reaction.

[0057] Of these, the acid-decomposable group is preferably a tert-butyl group, a tert-amyl group, or a group represented by the following formulae (I) to (IV).

[0058]

[0059] R in formulas (I) to (IV) ２ ~R ７ , R ａ , n, p, and ring Z １respectively represent R in the formulas (a1) to (a4) described below. ２ ~R ７ , R ａ , n, p, and ring Z １ is synonymous with.

[0060] The acid-decomposable group may be bonded to the radically polymerizable functional group via a spacer, such as a linking group represented by A in formula (1) described below.

[0061] Examples of the monomer having an acid-decomposable group include a monomer represented by the following formula (1).

[0062]

[0063] In formula (1), R １ represents an acid-decomposable group. In addition, in formula (1), R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. Examples of the halogen atom in the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, sec-amyl, tert-amyl, and hexyl groups. Examples of the alkyl group having 1 to 6 carbon atoms which has a halogen atom include trifluoromethyl and 2,2,2-trifluoroethyl groups.

[0064] In formula (1), A represents a single bond or a linking group. Examples of the linking group include a carbonyl group (-C(=O)-), an ether bond (-O-), an ester bond (-C(=O)-O-), an amide bond (-C(=O)-NH-), a carbonate bond (-O-C(=O)-O-), a group in which a plurality of these are linked together, and a group in which an alkylene group is linked to these. Examples of the alkylene group include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups; and divalent alicyclic hydrocarbon groups (particularly divalent cycloalkylene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups.

[0065] Preferred examples of the monomer represented by formula (1) include one or more monomers selected from the group consisting of monomers represented by the following formulas (a1) to (a4). Hereinafter, "one or more monomers selected from the group consisting of monomers represented by formulas (a1) to (a4)" may be referred to as "monomer a."

[0066]

[0067] In formulas (a1) to (a4), R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, similar to R in formula (1), and A represents a single bond or a linking group. A in formulas (a1) to (a4) is preferably a single bond or a group in which an alkylene group and a carbonyloxy group are bonded (an alkylene-carbonyloxy group). R ２ ~R ４ R each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent. ２ and R ３ may be bonded to each other to form a ring. ５ and R ６ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ７ Is -COOR ｃ represents a group.ｃ represents a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group, which may have a substituent; n represents an integer of 1 to 3; when n is 2 or 3, two or three R ７ may be the same or different. ａ is Ring Z １ and each independently represents an oxo group, an alkyl group, a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a carboxy group which may be protected by a protecting group. p represents an integer of 0 or more and 3 or less. Z １ represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms. When p is 2 or 3, two or three R ａ may be the same or different.

[0068] R ａ Examples of the alkyl group represented by the formula (I) include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isoamyl, sec-amyl, tert-amyl, and n-hexyl groups.

[0069] R ａ Examples of the hydroxyalkyl group represented by the formula (I) include hydroxyalkyl groups having 1 to 6 carbon atoms, such as hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and 6-hydroxyhexyl groups.

[0070] R ａ Examples of the protecting group that the hydroxy group and hydroxyalkyl group may have include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and tert-butyl groups; groups that form an acetal bond together with the oxygen atom constituting the hydroxy group (for example, C １－４ Alkyl-O-C １－４alkyl groups); groups that form an ester bond together with the oxygen atom constituting the hydroxy group (for example, an acetyl group, a benzoyl group, etc.); and the like.

[0071] R ａ Examples of the protecting group for a carboxy group represented by the formula (I) include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isoamyl, sec-amyl, tert-amyl, and hexyl groups; 2-tetrahydrofuranyl groups; 2-tetrahydropyranyl groups; and 2-oxepanyl groups.

[0072] R ２ ~R ６ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (R) include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, sec-amyl, tert-amyl, and hexyl groups. ２ ~R ６ The number of carbon atoms in the alkyl group having 1 to 6 carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.

[0073] R ２ ~R ６ Examples of the substituent that an alkyl group having 1 to 6 carbon atoms, represented by the formula (I), may have include a halogen atom, a hydroxy group, a substituted hydroxy group (for example, an alkoxy group having 1 to 4 carbon atoms, such as a methoxy, ethoxy, or propoxy group), and a cyano group. Examples of the alkyl group having 1 to 6 carbon atoms and having a substituent include a haloalkyl group having 1 to 6 carbon atoms, such as a trifluoromethyl or 2,2,2-trifluoroethyl group; a hydroxyalkyl group having 1 to 6 carbon atoms, such as a hydroxymethyl or 2-hydroxyethyl group; an alkoxyalkyl group having 1 to 6 carbon atoms, such as a methoxymethyl, 2-methoxyethyl, ethoxymethyl, or 2-ethoxyethyl group; and a cyanoalkyl group having 1 to 6 carbon atoms, such as a cyanomethyl or 2-cyanoethyl group.

[0074] R ２ and R ３ When they are bonded to each other to form a ring, examples of the ring include an alicyclic hydrocarbon ring having from 3 to 12 carbon atoms which may have a substituent.

[0075] R ｃ Examples of the tertiary hydrocarbon group represented by the formula (I) include a tert-butyl group and a tert-amyl group.

[0076] R ｃ Examples of the substituent that the tertiary hydrocarbon group represented by the formula (I) may have include a halogen atom, a hydroxy group, a substituted hydroxy group (for example, an alkoxy group having from 1 to 4 carbon atoms, such as a methoxy, ethoxy, or propoxy group), and a cyano group.

[0077] Z １ Examples of the alicyclic hydrocarbon ring having 3 to 20 carbon atoms and represented by the formula (I) include a monocyclic alicyclic hydrocarbon ring, a ring containing a norbornane ring or a norbornene ring, an adamantane ring, a ring in which a polycyclic aromatic fused ring is hydrogenated (preferably a fully hydrogenated ring), and a bridged cyclic hydrocarbon ring having 2 to 6 rings. Examples of the monocyclic alicyclic hydrocarbon ring include a 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 12-membered) cycloalkane ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring; and a 3- to 20-membered (preferably 3- to 15-membered, particularly preferably 5- to 10-membered) cycloalkene ring such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, and a cyclohexene ring. Examples of the ring containing a norbornane ring or a norbornene ring include a norbornane ring, a norbornene ring, a bornane ring, an isobornane ring, a tricyclo[5.2.1.0 ２，６ ] decane ring, and tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]dodecane ring, etc. Examples of the ring in which the polycyclic aromatic condensed ring is hydrogenated include a perhydroindene ring, a decalin ring, a tricyclo[7.4.0.0 ３，８] tridecane ring, and perhydroanthracene ring. Examples of the bridged cyclic hydrocarbon rings of 2 to 6 ring systems include tricyclo[4.2.2.1 ２，５ ]undecane ring, etc. The carbon number of the bicyclic to hexacyclic bridged hydrocarbon ring is preferably 6 or more and 20 or less.

[0078] The monomers are [-C(=O)-O-] and [-S(=O) ２ It is preferable that the photoresist polymer contains an alicyclic monomer having [—C(═O)—O—], or [—C(═O)—O—C(═O)—]. The use of an alicyclic monomer can impart higher substrate adhesion and etching resistance to the photoresist polymer. Hereinafter, the term “[—C(═O)—O—], [—S(═O) ２ An alicyclic monomer having [—O—] or [—C(═O)—O—C(═O)—] may be referred to as “monomer b.”

[0079] Monomer b is preferably one or more monomers selected from the group consisting of monomers represented by the following formulas (b1) to (b5). In the following formulas (b1) to (b5), R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and A represents a single bond or a linking group. X represents a single bond, a methylene group, an ethylene group, an oxygen atom, or a sulfur atom. Y represents a methylene group or a carbonyl group. Z represents a divalent organic group (for example, an alkylene group exemplified and explained as the alkylene group which may be contained in A in formulas (a1) to (a4) (particularly a linear alkylene group having 1 to 3 carbon atoms)). V １ ~V ３ are each independently —CH ２ -, [-C(=O)-], or [-C(=O)-O-]. However, V １ ~V ３ At least one of the groups is [—C(═O)—O—]. ８ ~R １４each independently represents a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom, a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a carboxy group which may be protected by a protecting group, or a cyano group.

[0080]

[0081] R and A in the formulae (b1) to (b5) have the same meanings as R and A in the formulae (a1) to (a4), respectively.

[0082] R in formulas (b1) to (b5) ８ ~R １４ represents an alkyl group, a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a carboxy group which may be protected by a protecting group. ８ ~R １４ The alkyl group represented by the formula (a1) to (a4), the hydroxy group which may be protected by a protecting group, the hydroxyalkyl group which may be protected by a protecting group, and the carboxy group which may be protected by a protecting group are each represented by R ａ and groups similar to an alkyl group represented by the formula (I), a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, and a carboxy group which may be protected by a protecting group. ８ ~R １４ Examples of the alkyl group represented by the formula (I) include haloalkyl groups having 1 to 6 carbon atoms, such as trifluoromethyl and 2,2,2-trifluoroethyl groups.

[0083] The monomers represented by formulas (b1) to (b4) are each R ８ ~R １１ may have one or more R ８ ~R １１ It is preferable that the monomers represented by formulas (b1) to (b4) have 1 to 3 R ８ ~R １１ When there are two or more R ８ ~R １１ may be the same or different.

[0084] Among these, the monomer b is represented by the formula (b1) and R ８ is a cyano group, a group having an amide group, a group having an imide group, or a fluoro(C １－６ a monomer represented by formula (b2), a monomer represented by formula (b3) in which Y is a carbonyl group, a monomer represented by formula (b4), or a monomer represented by formula (b5). Photoresist polymers obtained by polymerization of these monomers are excellent in substrate adhesion and etching resistance, and also in solubility in alkaline developers, allowing for the formation of fine patterns with high precision.

[0085] In formula (b1), R ８ is an electron-withdrawing group such as a cyano group, a group having an amide group, a group having an imide group, or a fluoroalkyl group having from 1 to 6 carbon atoms, ８ is particularly preferably bonded to at least the carbon atom marked with * in formula (b1).

[0086] The monomer may further contain a monomer c. The monomer c is a monomer represented by the following formula (c1). A photoresist polymer obtained by polymerizing a monomer containing the monomer c has high transparency and excellent etching resistance. In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom. A represents a single bond or a linking group. R ｂ represents a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a carboxy group which may be protected by a protecting group, or a cyano group, and is preferably a hydroxy group or a cyano group. q represents an integer of 1 or more and 5 or less. Z ２ represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. When q is an integer of 2 to 5, 2 to 5 R ｂ may be the same or different.

[0087]

[0088] R and A in formula (c1) have the same meanings as R and A in formulas (a1) to (a4), respectively.

[0089] R in formula (c1) ｂ represents a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a carboxy group which may be protected by a protecting group. ｂ The hydroxy group which may be protected by a protecting group, the hydroxyalkyl group which may be protected by a protecting group, and the carboxy group which may be protected by a protecting group are each represented by R ａ These are synonymous with a hydroxy group which may be protected by a protecting group represented by the following formula:

[0090] Z in formula (c1) ２ represents an alicyclic hydrocarbon ring having from 6 to 20 carbon atoms. Examples of the alicyclic hydrocarbon ring having from 6 to 20 carbon atoms include a monocyclic alicyclic hydrocarbon ring, a ring containing a norbornane ring or a norbornene ring, an adamantane ring, a ring in which a polycyclic aromatic fused ring is hydrogenated (preferably a fully hydrogenated ring), and a bridged cyclic hydrocarbon ring having 2 to 6 rings. Examples of the monocyclic alicyclic hydrocarbon ring include a 6- to 20-membered (preferably 6- to 15-membered, particularly preferably 6- to 12-membered) cycloalkane ring such as a cyclohexane ring and a cyclooctane ring; and a 6- to 20-membered (preferably 6- to 15-membered, particularly preferably 6- to 10-membered) cycloalkene ring such as a cyclohexene ring. Examples of the ring containing a norbornane ring or a norbornene ring include a norbornane ring, a norbornene ring, a bornane ring, an isobornane ring, a tricyclo[5.2.1.0 ２，６ ] decane ring, and tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]dodecane ring, etc. Examples of the ring in which the polycyclic aromatic condensed ring is hydrogenated include a perhydroindene ring, a decalin ring, a tricyclo[7.4.0.0 ３，８ ] tridecane ring, and perhydroanthracene ring. Examples of the bridged cyclic hydrocarbon rings of 2 to 6 ring systems include tricyclo[4.2.2.1 ２，５The carbon number of the 2- to 6-ring bridged cyclic hydrocarbon ring is preferably 6 or more and 20 or less. ２ is preferably a norbornane ring, a ring containing a norbornene ring, or an adamantane ring.

[0091] (Radical polymerization initiator) As the radical polymerization initiator, a known or commonly used radical polymerization initiator can be used. Examples of the known or commonly used radical polymerization initiator include a radical polymerization initiator containing a cyano group and a radical polymerization initiator not containing a cyano group. The radical polymerization initiator may be used alone or in combination of two or more types in any ratio.

[0092] Examples of the radical polymerization initiator containing a cyano group include azo compounds containing a cyano group, such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), and 4,4'-azobis(4-cyanovaleric acid).

[0093] Examples of the radical polymerization initiator not containing a cyano group include azo compounds not containing a cyano group, peroxide compounds not containing a cyano group, and redox compounds not containing a cyano group.

[0094] Examples of azo compounds that do not contain a cyano group include dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), and dibutyl-2,2'-azobisisobutyrate.

[0095] Examples of peroxide compounds not containing a cyano group include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals such as 1,1-bis(tert-hexylperoxy)3,3,5-trimethylcyclohexane and 1,1-bis(tert-hexylperoxy)cyclohexane; hydroperoxides such as p-menthane hydroperoxide; dialkyl peroxides such as 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxides such as isobutyryl peroxide and 3,3,5-trimethylhexanoyl peroxide; peroxyesters such as 1,1,3,3-tetramethylbutylperoxyneodecanate and tert-hexylperoxyneodecanate; and peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate.

[0096] Examples of redox compounds that do not contain a cyano group include hydrogen peroxide and ammonium persulfate.

[0097] (Solvent) Examples of the solvent include glycol-based solvents (glycol-based compounds), ester-based solvents, ketone-based solvents, ether-based solvents, amide-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents. The solvent may be a single solvent or a mixed solvent of two or more solvents mixed at any ratio.

[0098] Examples of glycol solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0099] Examples of ester solvents include lactate ester solvents such as ethyl lactate; propionate ester solvents such as methyl 3-methoxypropionate; acetate ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; and the like.

[0100] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone.

[0101] Examples of ether solvents include chain ethers such as diethyl ether, diisopropyl ether, dibutyl ether, and dimethoxyethane; and cyclic ethers such as tetrahydrofuran and dioxane.

[0102] An example of the amide solvent is N,N-dimethylformamide.

[0103] Examples of sulfoxide solvents include dimethyl sulfoxide.

[0104] Examples of hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0105] Among these, the solvent is preferably a glycol-based solvent such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; an ester-based solvent such as ethyl lactate; a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone; or a mixed solvent thereof.

[0106] (Chain transfer agent) As the chain transfer agent, known or conventional chain transfer agents used in radical polymerization can be used. Examples of known or conventional chain transfer agents include chain transfer agents containing a mercapto group, chain transfer agents containing a thiocarbonylthio group (chain transfer agents containing a cyano group and a thiocarbonylthio group, and chain transfer agents containing a thiocarbonylthio group but not a cyano group), etc. The chain transfer agent may be used alone or in combination of two or more in any ratio.

[0107] Examples of chain transfer agents containing a mercapto group include 1-butanethiol, 2-butanethiol, t-butyl mercaptan, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1-tetradecanethiol, n-lauryl mercaptan, cyclohexanethiol, 1-mercaptoethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, triethylene glycol dimercaptan, p-mercaptophenylmethanol, 2-(p-mercaptophenyl)ethanol, p-(mercaptomethyl)phenylmethanol, 2-(p-(mercaptomethyl)phenyl)ethanol, p-mercaptophenol, p-(mercaptomethyl)phenol, and p-(1-mercaptoethyl)phenol. thiols such as mercaptophenol and p-(2-mercaptoethyl)phenol (preferably a thiol having an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, which may have a substituent, more preferably a thiol having an aliphatic hydrocarbon group having from 6 to 12 carbon atoms, which may have a substituent); thiolic acids such as mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, and thiomalic acid; thiolic acid esters (preferably alkyl thiolates) such as methyl thioglycolate, ethyl thioglycolate, n-butyl thioglycolate, methyl 2-mercaptopropionate, ethyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, methyl p-mercaptobenzoate, ethyl p-mercaptobenzoate, methyl p-(mercaptomethyl)benzoate, and ethyl p-(mercaptomethyl)benzoate;

[0108] Examples of chain transfer agents containing a cyano group and a thiocarbonylthio group include 2-cyano-2-propyl 4-cyanobenzodithioate, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 2-cyano-2-propylbenzodithioate, and 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid. Dithiobenzoate-based chain transfer agents containing a cyano group such as N-succinimidyl ester; 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol, poly(ethylene glycol) methyl ether 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, poly(ethylene glycol) methyl ether (4-cyano-4-pentanoate dodecyltrithiocarbonate), poly(ethylene glycol) methyl ether (4-cyano-4-pentanoate dodecyltrithiocarbonate), poly(ethylene glycol) trithiocarbonate-based chain transfer agents containing a cyano group, such as cyanomethylmethyl (phenyl)carbamodithioate, cyanomethyldiphenylcarbamodithioate, 1-succinimidyl-4-cyano-4-[N-methyl-N-(4-pyridyl)carbamothioylthio]pentanoate, 2-cyanopropan-2-yl-N-methyl-N(pyridin-4-yl)carbamodithioate, and cyanomethylmethyl(4-pyridyl)carbamodithioate; and xanthate-based chain transfer agents containing a cyano group. Among these, the chain transfer agent containing a cyano group and a thiocarbonylthio group is preferably 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 2-cyano-2-propylbenzodithioate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, or 2-cyano-2-propyldodecyltrithiocarbonate, in terms of obtaining a polymer with a smaller polydispersity index Mw / Mn.

[0109] Examples of chain transfer agents that do not contain a cyano group but contain a thiocarbonylthio group include didithiobenzoate-based chain transfer agents that do not contain a cyano group, such as 2-phenyl-2-propylbenzodithioate, 1-(methoxycarbonyl)ethylbenzodithioate, benzylbenzodithioate, ethyl-2-methyl-2-(phenylthiocarbonylthio)propionate, methyl-2-phenyl-2-(phenylcarbonothioylthio)acetate, ethyl-2-(phenylcarbonothioylthio)propionate, and bis(thiobenzoyl)disulfide; 2-(dodecylthiocarbonylthioylthio)propionic acid, 2-(dodecylthiocarbonylthioylthio)-2-methylpropionic acid, methyl-2-(dodecylthiocarbonylthioylthio)-2-methylpropionate, and 2-(dodecylthiocarbonylthioylthio)-2-methylpropionic acid. N-hydroxysuccinimide ester, poly(ethylene glycol) methyl ether (2-methyl-2-propionic acid dodecyltrithiocarbonate), poly(ethylene glycol) bis[2-(dodecylthiocarbonylthioylthio)-2-methylpropionate], 2-(dodecylthiocarbonylthioylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiocarbonylthioylthio)-2-methylpropionic acid pentafluorophenyl ester, poly(ethylene glycol) methyl ether 2-(dodecylthiocarbonylthioylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether 2-(dodecylthiocarbonylthioylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether trithiocarbonate chain transfer agents not containing a cyano group, such as 2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate, poly(ethylene glycol) bis[2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate], and bis(dodecylsulfanylthiocarbonyl) disulfide;Examples of suitable chain transfer agents include dithiocarbamate-based chain transfer agents that do not contain a cyano group, such as benzyl 1H-pyrrole-1-carbodithioate, methyl 2-propionate methyl(4-pyridinyl)carbamodithioate, and N,N'-dimethyl-N,N'-di(4-pyridinyl)thiuram disulfide; and xanthate-based chain transfer agents that do not contain a cyano group. Among these, ethyl-2-methyl-2-(phenylthiocarbonylthio)propionate is preferred as the chain transfer agent that does not contain a cyano group but contains a thiocarbonylthio group, as this allows for the production of polymers with a smaller polydispersity index Mw / Mn.

[0110] Although the radical polymerization reaction of a monomer using a microfluidic system has been described above, the polymerization reaction when polymerizing a monomer using the microfluidic system according to this embodiment is not limited to a radical polymerization reaction, and any known or commonly used polymerization reaction may be appropriately employed. Furthermore, as described above, the fact that a reaction can be sufficiently progressed by ensuring an appropriate residence time in the reaction channel is not limited to a polymerization reaction of a monomer, but also applies to various chemical reactions. Therefore, even if the microfluidic system according to this embodiment is used for a chemical reaction other than a polymerization reaction of a monomer, the chemical reaction will proceed sufficiently and the desired reaction product will be efficiently obtained.

[0111] [Polymer Production System] A polymer production system, which is an example of a microfluidic system according to the present disclosure, will now be described with reference to the drawings. FIG. 1 is a configuration diagram of a polymer production system 100 according to the present embodiment. In this embodiment, as an example of a microfluidic system according to the present disclosure, a polymer production system 100 will be described that polymerizes two types of monomers, monomer B and monomer C, in the presence of a polymerization initiator A to obtain polymer D, which is a reaction product of these two types of monomers. However, the configuration of the embodiment described below is merely an example, and the technology of the present disclosure is not limited to the configuration of this embodiment. In this specification, "directly upstream" means the upstream side in a relationship adjacent to each other in the flow direction, and "directly downstream" means the downstream side in a relationship adjacent to each other in the flow direction.

[0112] [Overall Configuration] First, the overall configuration of the polymer production system 100 will be described. The polymer production system 100 is configured to include multiple chip-type microfluidic devices each having a microchannel formed on a substrate. More specifically, as shown in FIG. 1 , the polymer production system 100 includes multiple reaction devices 10, which are chip-type microfluidic devices, a heater 20, raw material tanks 30a and 30b, liquid delivery pumps 40a and 40b, a product tank 50, and conduits 60a, 60b, 60c, and 60d. In this embodiment, the "upstream side" refers to the raw material tank 30a side of a production flow path F1 (an example of a "predetermined processing flow path") extending from the raw material tank 30a to the product tank 50, and the "downstream side" refers to the product tank 50 side of the production flow path F1. The production flow path F1 is a flow path that continues from the raw material tank 30a, which is a fluid supply source, to the product tank 50, which is a fluid discharge destination.

[0113] The raw material tank 30a contains a solution containing a radical polymerization initiator A (polymerization initiator A solution). The radical polymerization initiator A (hereinafter sometimes simply referred to as "polymerization initiator A") generates radicals when subjected to treatment such as heating or light irradiation, thereby promoting the polymerization reaction of the curable compound. The raw material tank 30b contains a solution containing reactants, monomer B and monomer C (monomer BC solution). Monomer B and monomer C are monomers that undergo radical polymerization with each other in the presence of the radical polymerization initiator A. Monomer B and monomer C may be different types of monomers, in which case they will undergo copolymerization. Alternatively, monomer B and monomer C may be the same type of monomer, in which case they will undergo homopolymerization. The polymerization initiator A solution and the monomer BC solution are each an example of "multiple different fluids" according to the present disclosure.

[0114] As shown in Figure 1, in the polymer production system 100, a plurality of reaction devices 10, which are a plurality of microfluidic devices, are arranged side by side in the flow direction. The reaction devices 10 adjacent to each other in the flow direction are connected by a conduit 60c so that they can communicate with each other. Therefore, in the polymer production system 100, the plurality of reaction devices 10 are arranged in series. In addition, a heater 20, which will be described later, is also provided in each reaction device 10.

[0115] Hereinafter, the number of reaction devices 10 in this embodiment will be referred to as N (N is an integer of 2 or more). The number N (number of series) of reaction devices 10 is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. The number N of reaction devices 10 is preferably in the range of 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. As shown in the examples described below, increasing the number N of reaction devices 10 tends to produce polymers with smaller polydispersities Mw / Mn. Furthermore, of the multiple reaction devices 10 included in the polymer production system 100, the kth reaction device 10 (k is an integer of 1 to N) from the upstream side will be referred to as reaction device 10k. In other words, in the polymer production system 100, reaction device 101, reaction device 102, ..., and reaction device 10N are arranged in order from the upstream side.

[0116] The polymer production system 100 continuously supplies a polymerization initiator A solution and a monomer BC solution to the production flow path F1 via the reaction device 101 located at the most upstream side, and continuously additionally supplies (additionally charges) the monomer BC solution to the production flow path F1 via the reaction device 10 located downstream of the reaction device 101, thereby sequentially producing a polymer D. The polymer D produced by the polymer production system 100 is discharged from the reaction device 10N located at the most downstream side of the multiple reaction devices 10.

[0117] The conduits 60a, 60b, 60c, and 60d are pipes through which fluids can flow. The conduit 60a connects the raw material tank 30a and the reaction device 101 so that they can communicate with each other, and the conduit 60b connects the raw material tank 30b and the reaction device 10 so that they can communicate with each other. The conduit 60c connects the reaction devices 10 adjacent to each other in the flow direction so that they can communicate with each other. The conduit 60d connects the reaction device 10N and the product tank 50 so that they can communicate with each other.

[0118] As described above, the raw material tanks 30a and 30b are containers that contain the polymerization initiator A solution and the monomer BC solution, respectively. The polymerization initiator A solution and the monomer BC solution are supplied to the reaction device 10N via conduits 60a and 60b, respectively. The product tank 50 is a container that stores the polymer D produced by the polymer production system 100. The polymer D is discharged from the reaction device 10N to the product tank 50 via a conduit 60d.

[0119] The conduits 60a and 60b are provided with liquid feed pumps 40a and 40b, respectively. The liquid feed pumps 40a and 40b are liquid feed means for transporting fluids in the raw material tanks 30a and 30b to the reaction device 10. The polymerization initiator A solution in the raw material tank 30a is pressure-fed through the conduit 60a by driving the liquid feed pump 40a and supplied to the reaction device 10. The monomer BC solution in the raw material tank 30b is pressure-fed through the conduit 60b by driving the liquid feed pump 40b and supplied to the reaction device 10. Examples of liquid feed pumps include a syringe pump, a diaphragm pump, and a pressure-controlled pump. In this embodiment, for example, the raw material tanks 30a and 30b may not be used, and the polymerization initiator A solution and the monomer BC solution may be supplied to the reaction device 10 using syringe pumps each containing the polymerization initiator A solution and the monomer BC solution.

[0120] [Reaction Device] Next, the structure of the reaction device 10 will be described. FIG. 2 is a plan view of the reaction device 10 according to this embodiment. The reaction device 10 according to this embodiment is configured as a chip-type microfluidic device in which a microflow path (also called a microchannel) is formed inside a substrate. The reaction device 10 corresponds to an example of the "reaction means" according to the present disclosure. As shown in FIG. 2, the reaction device 10 has a substrate 1, a first flow path 2, and a first introduction flow path 3.

[0121] The substrate 1 is a plate-like member having a rectangular shape in a plan view. The material of the substrate 1 is not particularly limited, but examples thereof include silicon, silica, quartz, glass, resin, and silicon carbide. From the viewpoint of resist polymer production, a glass chip is preferably used as a non-metallic, solvent-resistant material.

[0122] The first flow path 2 and the first inlet flow path 3 are configured as grooves formed on the surface of the substrate 1. The first flow path 2 and the first inlet flow path 3 can be formed by, for example, performing an etching process on the substrate 1.

[0123] The first flow path 2 is formed as a minute flow path constituting part of the production flow path F1. As shown in FIG. 2 , the first flow path 2 has a serpentine shape in a plan view. One end of the first flow path 2 is formed with a supply port 21 for supplying a fluid into the first flow path 2, and the other end of the first flow path 2 is formed with an outlet port 22 for discharging a solution from the first flow path 2. In other words, the first flow path 2 extends continuously in a serpentine shape from the supply port 21 to the outlet port 22. The fluid supplied to the supply port 21 flows through the first flow path 2 and is discharged from the outlet port 22. The first flow path 2 includes a plurality of straight flow paths 23 formed in a straight line and arranged in parallel in a plan view, and a plurality of curved flow paths 24 formed in a curved line and connecting the ends of adjacent straight flow paths 23, 23 in the flow direction. The first flow path 2 is formed in a serpentine shape by these straight flow paths 23 and curved flow paths 24.

[0124] An inlet section 25 for introducing a fluid from the first inlet flow channel 3 into the first flow channel 2 is formed in a midway portion of the first flow channel 2 in the flow direction, more specifically, in a midway portion of the straight flow channel 23 located at the most upstream position in the first flow channel 2. The inlet section 25 introduces the monomer BC solution into the first flow channel 2 in order to mix the polymerization initiator A solution and the monomer BC solution, which are multiple different fluids, in the production flow channel F1 (first flow channel 2 in this example). The inlet section 25 is formed as a confluence section that merges with the first inlet flow channel 3. In other words, the first flow channel 2 merges with the first inlet flow channel 3 at the inlet section 25. As shown in the enlarged view A1 of FIG. 2 , the inlet section 25 has a first inlet port 25a that opens into the first inlet flow channel 3.

[0125] Here, in this specification, a microchannel in a reaction means, through which a chemical reaction of reactants contained in a mixture of multiple different fluids proceeds, is referred to as a "reaction channel." The reaction channel is, in other words, a region in which a chemical reaction of reactants introduced at an inlet portion proceeds. In the polymer production system 100 according to this embodiment, the region of the first channel 2 downstream of the inlet portion 25 corresponds to the "reaction channel." The region of the first channel 2 upstream of the inlet portion 25 is referred to as a transport channel 2a, and the region downstream of the inlet portion 25 is referred to as a reaction channel 2b. That is, the transport channel 2a is the region from the supply port 21 to the inlet portion 25, and the reaction channel 2b is the region from the inlet portion 25 to the outlet 22. As will be described in detail later, a polymerization initiator A solution is transported through the transport channel 2a of the reaction device 101 located at the most upstream of the multiple reaction devices 10, and a product liquid (reaction mixture) containing the polymerization initiator A solution and polymer D is transported through the transport channel 2a of the reaction device 10 located downstream of the reaction device 101. The fluid transported from the transport channel 2a of the first channel 2 and the monomer BC solution transported from the first introduction channel 3 merge at the inlet 25 of the first channel 2 and are mixed while flowing through the reaction channel 2b. Furthermore, as will be described in detail later, the mixed solution flowing through the reaction channel 2b is heated by the heater 20 to a reaction temperature or higher, thereby promoting the polymerization reaction of monomer B and monomer C in the presence of polymerization initiator A. In other words, the reaction channel 2b is a microchannel for mixing multiple different fluids, namely, the polymerization initiator A solution and the monomer BC solution, and promoting a chemical reaction in the mixed solution of the polymerization initiator A solution and the monomer BC solution. The reaction means according to the present disclosure may have multiple inlet ports depending on the types and amounts of the different fluids, the timing of their introduction, and the like. In this case, the reaction channel can be defined as a microchannel located downstream of the inlet port located furthest downstream in the reaction means.

[0126] The channel length (length in the flow direction) of the reaction channel 2b is designated as L1. L1 is the channel length of the first channel 2 downstream of the inlet 25, and can be defined as the channel length from the inlet 25 to the outlet 22. In other words, channel length L1 can be defined as the channel length of the first channel 2 downstream of the position where the mixing of the monomer BC solution and the polymerization initiator A solution introduced from the inlet 25 starts.

[0127] Here, the channel length L1 of the reaction channel 2b in the kth reaction device 10 from the upstream side among the multiple reaction devices 10 included in the polymer production system 100 is denoted as L1k. That is, the channel lengths L1 of the reaction channel 2b in the reaction device 101, reaction device 102, ..., and reaction device 10N, starting from the upstream side, are L11, L12, ..., and L1N. In this case, in the polymer production system 100 according to this embodiment, the channel lengths L1 of the reaction channel 2b in each reaction device 10 are set so that L1k < L1(k+1) while the cross-sectional areas of the channels 2b of the multiple reaction devices 101 to 10N are equal (constant). That is, the channel length L1 of the reaction channel 2b in each reaction device 10 is set so that the channel length L1 of the reaction channel 2b of the reaction device 10 located further downstream among the multiple reaction devices 10 is longer. Therefore, in the polymer production system 100 according to this embodiment, the volume of the reaction channel 2b increases in the reaction device 10 located further downstream. However, the technology of the present disclosure is not limited to this, and the volume can be set appropriately.

[0128] The first inlet flow path 3 is a flow path for introducing the monomer BC solution into the first flow path 2. The first inlet flow path 3 is formed in a straight line. One end of the first inlet flow path 3 is formed with a supply port 31 for supplying a fluid (in this example, the monomer BC solution) into the first inlet flow path 3, and the other end of the first inlet flow path 3 is connected to the inlet section 25 of the first flow path 2. This allows the first inlet flow path 3 to communicate with the first flow path 2 via the first inlet 25a. The transport flow path 2a of the first flow path 2, the first inlet flow path 3, and the reaction flow path 2b form a substantially Y-shape. The monomer BC solution supplied to the supply port 31 flows through the first inlet flow path 3 and is introduced into the first flow path 2 from the first inlet 25a of the inlet section 25.

[0129] In the technology according to the present disclosure, an inlet channel (first inlet channel 3 in this example) for introducing a fluid into the reaction channel is not an essential component. For example, the reaction device 10 may not have the first inlet channel 3, and the monomer BC solution may be introduced directly from the inlet portion 25 of the first channel 2. However, from the viewpoint of efficient mixing, it is preferable that the reaction means has an inlet channel that introduces a fluid to the inlet portion. Furthermore, the reaction means according to the present disclosure may have multiple inlet portions.

[0130] As shown in FIG. 1 , a conduit 60a is connected to the supply port 21 of the first flow path 2 of the reaction device 101 located at the most upstream of the plurality of reaction devices 10, for supplying a polymerization initiator A solution from a raw material tank 30a to the first flow path 2. Furthermore, a conduit 60d is connected to the discharge port 22 of the first flow path 2 of the reaction device 10N located at the most downstream of the plurality of reaction devices 10, for discharging the product liquid from the first flow path 2 to a product tank 50. In the reaction devices 10 adjacent to each other in the flow direction, the discharge port 22 of the first flow path 2 of the upstream reaction device 10 is connected to the supply port 21 of the first flow path 2 of the downstream reaction device 10 via a conduit 60c. As a result, the first flow path 2 constitutes a part of the production flow path F1. The plurality of reaction devices 10 are arranged in series so that their reaction flow paths 2b communicate with each other. Furthermore, a conduit 60 b for supplying the monomer BC solution from a raw material tank 30 b to the first inlet flow path 3 is connected to the supply port 31 of the first inlet flow path 3 in the reaction device 10 .

[0131] [Heater] The heater 20 is a device for accelerating a chemical reaction (a polymerization reaction in this example) by heating the mixed solution flowing through the reaction channel 2b of the reaction device 10. The heater 20 is an example of a "reaction acceleration means" according to the present disclosure. The heating temperature of the heater 20 is not particularly limited and can be set appropriately depending on the reaction temperature. The heater 20 heats the mixed solution in the reaction channel 2b to a temperature equal to or higher than the reaction temperature of the polymerization reaction in order to accelerate the polymerization reaction of monomer B and monomer C in the presence of polymerization initiator A. The reaction temperature here is, for example, the decomposition temperature of polymerization initiator A. The heater 20 is not particularly limited, and a known heater such as an electric heater can be used. In this embodiment, the heater 20 is provided in the reaction device 10 so as to accelerate the chemical reaction of the reactants in the reaction channel 2b. When the reaction-accelerating means is a heating means such as a heater, the heating means is preferably capable of maintaining the difference between the maximum and minimum temperatures during the reaction in one reaction device and / or the temperature difference between each reaction device during the reaction at 10° C. or less, more preferably at 5° C. or less, and even more preferably at 1° C. or less. In particular, when the number N of reaction devices 10 is 4 or less or 5 or less, the temperature difference is more preferably 5° C. or less or 1° C. or less. Use of such a heating means tends to enable the production of a polymer with a small polydispersity Mw / Mn.

[0132] [Polymer Production Method] A polymer production method using the polymer production system 100 according to this embodiment will be described below. Polymer production according to this embodiment is performed by continuously supplying a polymerization initiator A solution and a monomer BC solution to a production flow path F1 including a plurality of first flow paths 2. Specifically, the polymerization initiator A solution is continuously supplied to the first flow path 2 of the reaction device 101 by the liquid supply pump 40a, and the monomer BC solution is continuously supplied to the first flow path 2 of each reaction device 10 by the liquid supply pump 40b. The flow rates and flow velocities of the solutions supplied to the first flow paths 2 are not particularly limited and can be set appropriately depending on the purpose. In the polymer production system 100, a polymer is produced for each reaction device 10. Hereinafter, the product liquid supplied from the reaction device 10k, which is the kth reaction device 10 from the upstream side, to the reaction device 10(k+1) will be referred to as the kth product liquid.

[0133] First, the generation of a polymer in the reaction device 101 located at the most upstream will be described. The polymerization initiator A solution, which flows from the raw material tank 30a through the conduit 60a and is supplied to the reaction device 101 by the liquid feed pump 40a, is introduced into the first flow path 2 via the supply port 21. Meanwhile, the monomer BC solution, which flows from the raw material tank 30b through the conduit 60b and is supplied to the reaction device 101 by the liquid feed pump 40b, is introduced into the first inlet flow path 3 via the supply port 31. The monomer BC solution transported from the first inlet flow path 3 is then introduced into the first flow path 2 via the inlet 25 and merges with the polymerization initiator A solution transported through the transport flow path 2a. This initiates mixing of the polymerization initiator A solution and the monomer BC solution at the inlet 25. The polymerization initiator A solution and the monomer BC solution flow through the reaction flow path 2b due to the pressure of the liquid feed pumps 40a and 40b, and are mixed by diffusion mixing, with the reaction flow path 2b, which is a microchannel, serving as a mixing field. At this time, the mixed solution of the polymerization initiator A solution and the monomer BC solution flows through the reaction channel 2b while being heated by the heater 20 to a temperature equal to or higher than the reaction temperature. This promotes the polymerization reaction of the monomer B and the monomer C in the presence of the polymerization initiator A, and a polymer D is produced. At this time, a portion of the polymerization initiator A, at least a portion of the monomer B, and at least a portion of the monomer C contained in the mixed solution are consumed by the polymerization reaction. All of the monomer B and the monomer C may be polymerized, or only a portion may be left.

[0134] Next, polymer production in a reaction device 10p (p is an integer equal to or greater than 2 and less than N) located downstream of the reaction device 101 will be described. The (p-1)th product liquid, which flows through the conduit 60c from the reaction device 10(p-1) located immediately upstream of the reaction device 10p and is supplied to the reaction device 10p, is introduced into the first flow path 2 via the supply port 21. This (p-1)th product liquid contains a polymerization initiator A and a polymer D. The (p-1)th product liquid may also contain residual monomers B and C that did not react in the reaction devices 10 upstream of the reaction device 10p. Meanwhile, as in the case of the reaction device 101, a monomer BC solution is supplied to the reaction device 10p by the liquid feed pump 40b. The monomer BC solution transported from the first introduction flow path 3 is introduced into the first flow path 2 via the introduction section 25 and merges with the (p-1)th product liquid transported through the transport flow path 2a. As a result, the monomer BC solution is additionally introduced into the production flow path F1, and additional monomers are charged. Then, the (p-1)th product liquid containing the polymerization initiator A and the polymer D and the additionally introduced monomer BC solution begin mixing at the inlet 25 and are mixed while flowing through the reaction flow path 2b. Furthermore, the mixed liquid flowing through the reaction flow path 2b is heated by the heater 20 to a temperature equal to or higher than the reaction temperature, thereby promoting the polymerization reaction of the monomers B and C in the presence of the polymerization initiator A, and a new polymer D is produced. At this time, the monomers B and C may be polymerized in their entirety, or only a portion of them may be polymerized. Furthermore, if any unreacted monomers B or C remain in the mixed liquid in each reaction device 10 upstream of the reaction device 10p, they may also be polymerized. The pth product liquid containing the polymerization initiator A and the polymer D is discharged from the outlet 22, flows through the conduit 60c, and is supplied to the reaction device 10(p+1) located immediately downstream.

[0135] In producing a polymer using the polymer production system 100, it is desirable to adjust the molar ratio of the monomer to the polymerization initiator (hereinafter, sometimes referred to as the "M / I ratio") throughout the reaction time in order to obtain a polymer with a smaller polydispersity index Mw / Mn. The M / I ratio can be adjusted by continuously additionally supplying (additionally charging) the monomer BC solution to the reaction flow path 2b of the reaction device 10N located downstream of the reaction device 101 located at the most upstream side. From the above viewpoint, in the production of a polymer using the polymer production system 100, it is preferable that, among at least two of the multiple reaction devices 10, the reaction device 10 located more downstream has a larger M / I ratio in the introduction section 25, it is more preferable that, among at least three of the multiple reaction devices 10, the reaction device 10 located more downstream has a larger M / I ratio in the introduction section 25, it is even more preferable that, among at least four of the multiple reaction devices 10, the reaction device 10 located more downstream has a larger M / I ratio in the introduction section 25, and it is particularly preferable that the reaction device 10 located more downstream has a larger M / I ratio in the introduction section 25. In this case, from the viewpoint of obtaining a polymer having a smaller polydispersity Mw / Mn, the maximum M / I ratio among the M / I ratios in the inlet sections 25 of the multiple reaction devices 10p (p is an integer of 2 or greater but less than N) is preferably 1.0 to 5.0 times, more preferably 1.0 to 4.0 times, and even more preferably 1.5 to 3.0 times, the M / I ratio in the inlet section 25 of the reaction device 101 arranged at the most upstream. Furthermore, from the viewpoint of obtaining a polymer having a smaller polydispersity Mw / Mn, the M / I ratio in the inlet section 25 of the reaction device 101 arranged at the most upstream is preferably 1.0 to 8.0, more preferably 1.0 to 6.0, even more preferably 1.5 to 4.5, even more preferably 2.0 to 4.0, and particularly preferably 2.5 to 3.5.

[0136] Next, the generation of a polymer in the reaction device 10N arranged at the most downstream side will be described. The reaction process in the reaction device 10N is similar to that in the reaction device 10p, and therefore a detailed description thereof will be omitted. As in the reaction device 10p, in the reaction flow path 2b of the reaction device 10N, an (N-1)th product liquid containing a polymerization initiator A and a polymer D is mixed with an additionally introduced monomer B and C solution, and the mixture is heated by the heater 20 to a temperature equal to or higher than the reaction temperature, thereby accelerating the polymerization reaction and newly generating polymer D. At this time, in the reaction flow path 2b of the reaction device 10N, all of the polymerization initiator A contained in the mixture may be consumed by the polymerization reaction of monomer B and monomer C. Alternatively, all of the monomer B and all of the monomer C contained in the mixture may be consumed by the polymerization reaction.

[0137] The Nth product liquid containing polymer D is discharged from the outlet 22, flows through the conduit 60d, and is discharged into the product tank 50. This allows the polymer D produced in the reaction devices 101, 102, ... 10N to be collected. As described above, in the polymer production method using the polymer production system 100 according to the embodiment, a large amount of polymer D can be produced by additionally charging (N-1) times.

[0138] [Actions and Effects] As described above, the polymer production system 100 according to this embodiment includes a plurality of reaction devices 10 (reaction means), each of which has an inlet 25 for introducing a monomer BC solution into a production flow path F1, and a reaction flow path 2b (reaction flow path) disposed downstream of the inlet 25 and formed in the reaction device 10 as a microflow path constituting part of the production flow path F1. The reaction flow path 2b advances a polymerization reaction between monomer B and monomer C (reactants) contained in a mixture of a polymerization initiator A solution and a monomer BC solution. The reaction devices 10 are disposed in series such that their reaction flow paths 2b communicate with each other, and the flow path length L1 of the reaction flow path 2b is set so that the more downstream the reaction device 10 is located, the longer the flow path length L1 of the reaction flow path 2b.

[0139] Here, in a polymer production system 100 equipped with multiple reaction devices 10, a polymerization initiator A solution and a monomer BC solution are continuously supplied (introduced) into a production flow path F1, which includes multiple reaction flow paths 2b arranged in series. Therefore, the flow rate of the fluid at any position in the production flow path F1 in the flow direction is the sum of the flow rates of all fluids introduced into the production flow path F1 upstream of that position. For example, the reaction device 10 arranged qth (q is an integer between 2 and N) from the upstream side among the multiple reaction devices 10 is designated as reaction device 10q. In this case, the total flow rate (total volume) of the fluid flowing through the reaction flow path of reaction device 10q is approximately the sum of the flow rate (volume) of the fluid flowing through the reaction flow path 2b of the reaction device 101 arranged at the most upstream side and the flow rate (volume) of the fluid additionally introduced into all reaction devices 10 from reaction device 101 to reaction device 10q. Therefore, the total flow rate of the fluid flowing through the production flow path F1 increases from the upstream side to the downstream side as it passes through each reaction flow path 2b. As a result, the total flow rate of the fluid flowing through the reaction channel 2b increases as the reaction device 10 is positioned further downstream among the multiple reaction devices 10. In other words, the total flow rate of the fluid increases as the reaction channel 2b of the reaction device 10 is positioned further downstream. Therefore, from the viewpoint of sufficiently progressing the chemical reaction in the reaction channel 2b and increasing the reaction rate of the monomer, it is preferable to make the residence time longer in the reaction channel 2b of the reaction device 10 positioned further downstream.

[0140] In contrast, in the polymer production system 100 according to this embodiment, the channel lengths L1 of the reaction channels 2b of the multiple reaction devices 10 are set so that the channel lengths L1 of the reaction channels 2b are longer for reaction devices 10 located further downstream. That is, the volumes of the reaction channels 2b of the multiple reaction devices 10 are set so that the volume of the reaction channels 2b is larger for reaction devices 10 located further downstream. Since the fluid residence time in a channel is proportional to the volume of the channel, the fluid residence time in the reaction channels 2b is longer for reaction devices 10 located further downstream. This ensures that the residence time required for the reaction to proceed sufficiently can be ensured even in reaction devices 10 located further downstream. Therefore, a sufficient reaction rate can be ensured in the reaction channels 2b even in reaction devices 10 located further downstream. As a result, the polymer production system 100 according to this embodiment can ensure a sufficient reaction rate in the multiple reaction channels 2b while introducing monomers B and C through the multiple inlet portions 25, thereby increasing the production amount of polymer D.

[0141] From the viewpoint of ensuring sufficient residence time in the multiple reaction channels 2b, it is not necessary for the volume of the reaction device 10 to be larger as the reaction device 10 is located more downstream in all reaction devices 10. It is sufficient that the volumes of the reaction channels 2b of at least two reaction devices 10 are set so that the volume of the reaction channel 2b of the reaction device 10 located more downstream is larger. For example, the volume of any one of the multiple reaction devices 10 may be equal to or smaller than the volume of any one of the reaction devices 10 located upstream of that reaction device 10. Furthermore, the volumes of the reaction channels 2b of at least two reaction devices 10 may be set so that the volumes of the reaction channels 2b are equal to each other. For example, the channel length L1 of the reaction channel 2b may be set as follows, starting from the upstream reaction device 101: L11 = 3 cm, L12 = 5 cm, L13 = 5 cm, L14 = 7 cm, ... In this case, the volumes of the reaction device 102 and the reaction device 103 are equal to each other. However, from the above viewpoint, it is more preferable that all the reaction devices 10 are set so that the volume of the reaction device 10 increases as it approaches the downstream side.

[0142] Furthermore, in the polymer production system 100 according to this embodiment, in which a monomer polymerization reaction is performed, multiple polymerization reaction processes are performed in the production flow path F1 by additionally charging the monomer into the reaction device 10. Therefore, the number of molecules of polymer D flowing through the production flow path F1 increases from the upstream side to the downstream side as it passes through each reaction flow path 2b. In other words, the more upstream the reaction device 10, the lower the concentration of polymer D in the reaction flow path 2b, and the relatively higher the concentration of the monomer reactant. Therefore, in the reaction flow path 2b of the reaction device 10 located further upstream, particularly the most upstream, the higher the concentration of the monomer, the more reaction opportunities there are compared with the reaction flow path 2b of the downstream reaction device 10, and the polymerization reaction is more likely to proceed. As a result, the amount of polymer D, the reaction product, may increase rapidly in the reaction system, resulting in variations in the molecular weight of polymer D. Therefore, from the viewpoint of reducing the polydispersity Mw / Mn of polymer D, it is preferable to shorten the residence time of the reaction flow path 2b of the reaction device 10 located further upstream to suppress variations in the molecular weight of the produced polymer D.

[0143] In contrast, in the polymer production system 100 according to this embodiment, as described above, the volume of the reaction channel 2b increases in the reaction device 10 located further downstream. In other words, the volume of the reaction channel 2b decreases in the reaction device 10 located further upstream. Therefore, the residence time in the reaction channel 2b of the reaction device 10 located further upstream is shorter, and a sufficient reaction rate can be ensured in the reaction channel 2b while suppressing variation in the molecular weight of the produced polymer D. As a result, the polymer production system 100 according to this embodiment can reduce the polydispersity Mw / Mn of the polymer D.

[0144] From the above viewpoint of reducing the polydispersity Mw / Mn of polymer D, it is not essential that the volume of the reaction device 10 be smaller as the reaction device 10 is located more upstream in all reaction devices 10, but it is sufficient that the volumes of the reaction flow channel 2b are set so that the volume of the reaction device 10 located more upstream in at least two reaction devices 10 among the plurality of reaction devices 10. However, from the above viewpoint, it is preferable that the volume of the reaction device 101 located most upstream in all reaction devices 10 is the smallest, and it is more preferable that the volume of the reaction device 10 be set so that the volume of the reaction device 10 located more upstream is smaller.

[0145] From the viewpoint of narrowing the molecular weight distribution of polymer D, it is preferable to set the volume of the reaction channels 2b in the multiple reaction devices 10 so that the polydispersity Mw / Mn is 3.0 or less. It is preferable that the polydispersity Mw / Mn is small, specifically, preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.9 or less, even more preferably 1.8 or less, and particularly preferably 1.7 or less. Furthermore, it is more preferable that the polydispersity Mw / Mn is 1.6 or less, and even more preferably 1.5 or less. Furthermore, the polydispersity Mw / Mn may be 1.3 or more and 3.0 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, or 1.6 or less. Furthermore, it is preferable that the weight average molecular weight Mw of polymer D is 500 or more and 8000 or less.

[0146] The polymer production system 100 may include a microfluidic device of a different type from the reaction device 10. For example, a device that performs extraction or other chemical or physical processes as a unit operation on a fluid flowing through a microchannel may be interposed between the reaction device 10k and the reaction device 10(k+1).

[0147] In view of the above, the inlet 25 may introduce at least one of the multiple different fluids, the polymerization initiator A solution and the monomer BC solution, into the reaction channel 2b so that the mixed solution contains reactants, and may, for example, introduce only the monomer BC solution or only the polymerization initiator A solution into the reaction channel 2b, or may introduce both the monomer BC solution and the polymerization initiator A solution into the reaction channel 2b. The inlet 25 may also introduce a fluid different from the polymerization initiator A solution or the monomer BC solution.

[0148] In addition, the technology disclosed herein does not require all of the volumes of the multiple reaction channels to be equal, and the volume of the reaction channel in at least one reaction means may be different from the volume of the reaction channel in the other reaction means. This allows the residence time in the reaction channel to be set depending on the type of reaction occurring in the reaction channel, the reaction time, etc. In addition, adjusting the residence time for each of the multiple reaction channels can improve the reaction rate. For example, in a reaction means located further downstream, the volume of a mixed fluid of multiple different fluids may be larger than in a reaction means located upstream, which may reduce the frequency of collisions between reactants and reduce the chance of reaction. In this case, while the reaction rate in the reaction means located further downstream is reduced, adjusting the volume of the reaction channel in the reaction means located further downstream to be larger can ensure sufficient residence time, thereby improving the reaction rate. In addition, in the technology disclosed herein, the volume of the reaction channel may be set smaller the more downstream the reaction means is located, depending on various conditions such as the type of reaction and the properties of the reactants.

[0149] In the technology disclosed herein, the volumes of the reaction channels of at least two of the multiple reaction means may be equivalent. For example, if the reaction rate of a chemical reaction in a reaction means located more downstream is higher than that of a chemical reaction in a reaction means located more upstream, the reaction can proceed sufficiently even if the residence time in the reaction channel of the reaction means located more downstream is short. Therefore, in such a case, even if the volumes of both reaction channels are equivalent ("equivalent" includes the same), a good reaction rate can be achieved in both reaction means.

[0150] Furthermore, in this embodiment, the volumes of the reaction channels 2b are made different by making the channel lengths L1 different while keeping the cross-sectional areas of the reaction channels 2b equal in two or more reaction devices 10, but the technology according to the present disclosure is not limited to this. Making the channel lengths different is not essential for making the volumes of the reaction channels in two or more reaction means different. The technology according to the present disclosure may make the volumes of the reaction channels different by making the cross-sectional areas different while keeping the channel lengths of the reaction channels equal in two or more reaction means, or by making both the cross-sectional areas and channel lengths different.

[0151] Furthermore, the polymer production system 100 according to this embodiment is provided with a heater 20 as a reaction promoting means, thereby making it possible to promote the polymerization reaction between the monomer B and the monomer C in the reaction channel 2b.

[0152] In the above-described embodiment, the polymerization initiator A solution and the monomer B and C solutions are mixed as the plurality of different fluids, but the plurality of different fluids may include only a fluid containing a polymerization initiator and a fluid containing one type of monomer. A fluid containing one type of monomer may be introduced into the reaction channel 2b of the reaction device 10 from the inlet 25, and the one type of monomer may be polymerized in the reaction channel 2b of the reaction device 10 in the presence of a polymerization initiator.

[0153] Although the present embodiment described above involves a polymerization reaction between monomer B and monomer C introduced into the reaction device 10, the technology according to the present disclosure is not limited to a reaction between reactants contained in different fluids (such as polymerization between monomers). For example, the technology according to the present disclosure may involve mixing a fluid containing a reactant and a fluid containing a decomposition catalyst as multiple different fluids, and performing a decomposition reaction of the reactants in the reaction device.

[0154] Furthermore, in the above-described embodiment, a chip-type microfluidic device is used as the microfluidic device, but a tube-type microfluidic device or other types of microfluidic devices may also be used. For example, the reaction device 10 may be configured as a tube-type microfluidic device. Furthermore, in the above-described embodiment, the reaction means is configured as a single microfluidic device (reaction device 10), but the technology according to the present disclosure is not limited to this. The reaction means may be configured to include multiple microfluidic devices. For example, the inlet and the reaction channel may be provided in separate microfluidic devices. Furthermore, the inlet does not have to be formed in the microfluidic device.

[0155] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to the aspects of the following examples.

[0156] The weight-average molecular weight Mw and number-average molecular weight Mn of the polymers obtained in the following Examples and Comparative Examples were measured as follows. The polydispersity index Mw / Mn of the obtained polymers was calculated from the measured weight-average molecular weight Mw and number-average molecular weight Mn.

[0157] [Method for measuring weight average molecular weight Mw and number average molecular weight Mn] The weight average molecular weight Mw and number average molecular weight Mn of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.

[0158] Apparatus: GPC system (Shimadzu Corporation) System controller: SIL-20A (Shimadzu Corporation) Pump: LC-20AD (Shimadzu Corporation) Degasser: DGU-20A3R (Shimadzu Corporation) Column oven: CTO-20AC (Shimadzu Corporation) RI detector: RID-20A (Shimadzu Corporation) Column: GPC KF-806L (column size: 8.0 mm (ID) × 300 mm (L), manufactured by Resonac Corporation) × 3 Guard column: KF-G (column size: 4.6 mm (ID) × 10 mm (L), manufactured by Resonac Corporation) Column temperature: 40°C Cell temperature: 40°C Eluent: tetrahydrofuran Eluent flow rate: 0.8 mL / min Injection volume: 35 μL Analysis time: 60 minutes Sample: 5 wt% tetrahydrofuran solution Sample for creating calibration curve: Polystyrene calibration kit S-M-10 (manufactured by Agilent Technologies, Inc.)

[0159] Example 1 A polymer was produced by a radical polymerization reaction of a monomer using a polymer production system 100 (N=5) shown in FIG. 1 . The polymer production system 100 comprises five reaction devices 101-105 arranged in series and connected by a conduit 60c. Each of the reaction devices 101-105 is provided with an inlet 25 for introducing a monomer solution into the reaction channel 2b. The channel design of the reaction devices 101-105 in the polymer production system 100 is shown in Table 1. The liquid feed pumps 40a and 40b of the polymer production system 100 are syringe pumps, and the conduits 60a-60d are polyether ether ketone tubes (inner diameter 500 μm).

[0160] Specific operation and reaction conditions are as follows. The following initiator solution and monomer solution were stored in raw material tanks 30a and 30b of the polymer production system 100. The initiator solution and monomer solution were introduced from these raw material tanks into each of the reaction devices 101 to 105 at the flow rates shown in Table 2, and a chemical reaction was carried out. At this time, in the reaction devices 101 to 105, the reaction flow path 2b was heated by the heater 20 so that the reaction temperature was about 90±1°C. The M / I ratios at the inlet parts 25 of the reaction devices 101 to 105 are shown in Tables 7 and 8.

[0161] Liquid 2a (fluid contained in raw material tank 30a) to be supplied to reaction device 101: A liquid (liquid 2a, solvent concentration: 70.0 mass%) obtained by dissolving dimethyl 2,2'-azobis(2-methylpropionate) (V-601; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; polymerization initiator) in propylene glycol monomethyl ether acetate (MMPGAC; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; boiling point 145°C, melting point less than -10°C, specific gravity 0.97; solvent) so that the concentration of the polymerization initiator is 30.0 mass%. Liquid 2b (fluid contained in raw material tank 30b) to be supplied to reaction device 101: a liquid (liquid 2b, solvent concentration: 67.8 mass%) obtained by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point -48°C, specific gravity 0.94) so ​​that the concentration of methyl methacrylate was 17.4 mass% and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) so that the concentration of phenyl methacrylate was 14.8 mass% in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC); and a liquid 2c (fluid contained in the raw material tank 30b) to be supplied to the reaction device 102. a liquid (liquid 2c, solvent concentration: 70.0 mass%) obtained by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point -48°C, specific gravity 0.94) so ​​that the concentration of methyl methacrylate was 12.7 mass% and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) so that the concentration of phenyl methacrylate was 17.3 mass% in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC); and a liquid 2d (fluid contained in the raw material tank 30b) to be supplied to the reaction device 103. Methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point −48°C, specific gravity 0.94) was added so that the concentration of methyl methacrylate was 9.0% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.;Liquid 2d (solvent concentration: 74.0% by mass) prepared by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point -48°C, specific gravity 0.94) so ​​that the concentration of methyl methacrylate was 9.1% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) in propylene glycol monomethyl ether acetate (similar to MMPGAC described above) (Liquid 2d, solvent concentration: 74.0% by mass). Liquid 2e (fluid contained in raw material tank 30b) supplied to reaction device 104: Liquid 2e (solvent concentration: 73.9% by mass) prepared by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) in propylene glycol monomethyl ether acetate (similar to MMPGAC described above). Liquid 2f (fluid contained in raw material tank 30b) supplied to reaction device 105: A liquid (liquid 2f, solvent concentration: 73.2% by mass) obtained by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point -48°C, specific gravity 0.94) so ​​that the concentration of methyl methacrylate was 9.9% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) so that the concentration of phenyl methacrylate was 16.9% by mass, in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC);

[0162] The weight average molecular weight Mw, number average molecular weight Mn, and polydispersity Mw / Mn of the polymer stored in the product tank 50 from the reaction device 105 through the conduit 60d were determined by the above-mentioned methods. The results are shown in Table 9.

[0163] Example 2 A polymer was produced by a radical polymerization reaction of a monomer using the polymer production system 100 (N=4) shown in FIG. 1 . The polymer production system 100 comprises four reaction devices 101-104 arranged in series and connected by a conduit 60c. Each of the reaction devices 101-104 is provided with an inlet 25 for introducing a monomer solution into the reaction channel 2b. The flow path design of the reaction devices 101-104 in the polymer production system 100 is shown in Table 3. The liquid feed pumps 40a and 40b of the polymer production system 100 are syringe pumps, and the conduits 60a-60d are polyether ether ketone tubes (inner diameter 260 μm).

[0164] Specific operation and reaction conditions are as follows. The following initiator solution and monomer solution were stored in raw material tanks 30a and 30b of the polymer production system 100. The initiator solution and monomer solution were introduced from these raw material tanks into each of the reaction devices 101 to 104 at the flow rates shown in Table 4, and a chemical reaction was carried out. At this time, in the reaction devices 101 to 104, the reaction flow path 2b was heated by the heater 20 so that the reaction temperature was about 75±1°C. The M / I ratios at the inlet parts 25 of the reaction devices 101 to 104 are shown in Table 7.

[0165] Liquid 3a (fluid contained in raw material tank 30a) to be supplied to reaction device 101: A liquid (liquid 3a, solvent concentration: 85.8 mass%) obtained by dissolving dimethyl 2,2'-azobis(2-methylpropionate) (V-601; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; polymerization initiator) in propylene glycol monomethyl ether acetate (MMPGAC; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; boiling point 145°C, melting point less than -10°C, specific gravity 0.97; solvent) so that the concentration of the polymerization initiator was 14.2 mass%. Liquid 3b (fluid contained in raw material tank 30b) to be supplied to reaction device 101: a liquid (liquid 3b, solvent concentration: 79.1% by mass) obtained by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point: 101°C, melting point: -48°C, specific gravity: 0.94) so ​​that the concentration of methyl methacrylate was 9.5% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point: 198°C, melting point: -17°C, specific gravity: 1.06) so that the concentration of phenyl methacrylate was 11.4% by mass in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC); and a liquid 3c (fluid contained in the raw material tank 30b) to be supplied to the reaction devices 102 to 104. A liquid (liquid 3c, solvent concentration: 80.0% by mass) was prepared by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 101°C, melting point -48°C, specific gravity 0.94) so ​​that the concentration of methyl methacrylate was 7.9% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point 198°C, melting point -17°C, specific gravity 1.06) so that the concentration of phenyl methacrylate was 12.1% by mass in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC).

[0166] The weight average molecular weight Mw, number average molecular weight Mn, and polydispersity index Mw / Mn of the polymer stored in the product tank 50 from the reaction device 104 through the conduit 60d were determined by the above-mentioned methods. The results are shown in Table 9.

[0167] Comparative Example 1 A polymer was produced by a radical polymerization reaction of a monomer using the same polymer production system as in Example 2, except that the number N of reaction devices was 1 and the inner diameter of the polyether ether ketone tube serving as the conduit was 500 μm. Table 5 shows the flow path design of the reaction devices in the polymer production system. Table 7 shows the M / I ratios at the inlet of the reaction device. Table 8 also shows the M / I ratios at residence times of 0, 5, 18, 37, and 70, where the residence time in the reaction flow path of the reaction device is taken as 100. Note that when the total residence time in the reaction flow path of reaction devices 101 to 105 in Example 1 is taken as 100, the M / I ratios at residence times of 0, 5, 18, 37, and 70 are the M / I ratios at the inlet of reaction devices 101 to 105, respectively. Therefore, the M / I ratios at residence times of 0, 5, 18, 37, and 70 in Comparative Example 1 correspond to the M / I ratios at the inlet parts of the reaction devices 101 to 105 in Example 1, respectively.

[0168] The specific operation and reaction conditions are as follows: The following initiator solution and monomer solution were placed in the raw material tank of the polymer production system. The initiator solution and monomer solution were introduced from these raw material tanks into the reaction device at the flow rates shown in Table 6, and a chemical reaction was carried out. At this time, the reaction flow path in the reaction device was heated with a heater so that the reaction temperature was about 95±1°C.

[0169] Liquid 4a (fluid contained in raw material tank) to be supplied to the reaction device: A liquid (liquid 4a, solvent concentration: 70.0 mass%) obtained by dissolving dimethyl 2,2'-azobis(2-methylpropionate) (V-601; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; polymerization initiator) in propylene glycol monomethyl ether acetate (MMPGAC; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.; boiling point: 145°C, melting point: less than -10°C, specific gravity: 0.97; solvent) so that the concentration of the polymerization initiator was 30.0 mass%. Liquid 4b (fluid contained in raw material tank) to be supplied to the reaction device: A liquid (liquid 4b, solvent concentration: 71.4% by mass) was prepared by dissolving methyl methacrylate (MMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point: 101°C, melting point: -48°C, specific gravity: 0.94) so ​​that the concentration of methyl methacrylate was 12.0% by mass, and phenyl methacrylate (PhMA; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; boiling point: 198°C, melting point: -17°C, specific gravity: 1.06) so that the concentration of phenyl methacrylate was 16.6% by mass in propylene glycol monomethyl ether acetate (similar to the above-mentioned MMPGAC).

[0170] The weight average molecular weight Mw, number average molecular weight Mn, and polydispersity Mw / Mn of the polymer stored in the product tank from the reaction device through the conduit were determined by the above-mentioned methods. The results are shown in Table 9.

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180] 2b Reaction channel 10 Reaction device 20 Heater (an example of a reaction promotion means) 100 Polymer production system

Claims

1. A microfluidic system including a plurality of microfluidic devices each having a microchannel formed therein, comprising a plurality of reaction means each having an introduction section for introducing at least one of a plurality of different fluids into a predetermined processing flow path in order to mix the plurality of different fluids within the predetermined processing flow path, and a reaction flow path formed in the microfluidic device as a microchannel that is arranged downstream of the introduction section and constitutes part of the predetermined processing flow path, the reaction flow path causing a chemical reaction of reactants contained in the mixed fluid of the plurality of different fluids, wherein the plurality of reaction means are arranged in series so that the reaction flow paths are connected to each other, and the volume of the reaction flow path in at least one of the plurality of reaction means is different from the volume of the reaction flow path in the other reaction means.

2. The microfluidic system according to claim 1, wherein the volumes of at least two of the plurality of reaction means are set such that the volume of the reaction flow channel is larger for the reaction means located further downstream.

3. The microfluidic system according to claim 2, wherein the volumes of at least two of the plurality of reaction means are set so that the volumes of the reaction channels are equal to each other.

4. The microfluidic system according to claim 1, wherein the volumes of the plurality of reaction means are set such that the volume of the reaction flow channel increases as the reaction means is positioned further downstream.

5. A microfluidic system as described in any one of claims 1 to 4, wherein the plurality of different fluids include at least a fluid containing a polymerization initiator and a fluid containing one or more types of monomers, the fluid containing the one or more types of monomers is introduced into the processing flow path from the inlet portion, and the one or more types of monomers are polymerized in the presence of the polymerization initiator in the reaction flow path.

6. The microfluidic system according to claim 5, wherein the volumes of the reaction channels in the plurality of reaction means are set so that the polydispersity Mw / Mn (Mw and Mn are the weight average molecular weight and number average molecular weight of the polymer, respectively) of the polymer produced by the microfluidic system is 1.3 or more and 3.0 or less.

7. The microfluidic system according to any one of claims 1 to 4, further comprising a reaction promotion means for promoting a chemical reaction of reactants contained in the mixed fluid in the reaction channel.

8. The microfluidic system according to claim 7, wherein the reaction promotion means includes at least one of heating means, light irradiation means, vibration energy imparting means, and voltage application means.

9. The microfluidic system according to any one of claims 1 to 4, wherein the reaction channel has a channel width of 1000 μm or less.

10. A reaction method using a microfluidic system including a plurality of microfluidic devices formed with microchannels, wherein the microfluidic system comprises a plurality of reaction means having an inlet part for introducing at least one of a plurality of different fluids into a predetermined processing flow path in order to mix the plurality of different fluids within the predetermined processing flow path, and a reaction flow path formed in the microfluidic device as a microchannel that is arranged downstream of the inlet part and constitutes part of the predetermined processing flow path, the reaction flow path causing a chemical reaction of reactants contained in the mixed fluid of the plurality of different fluids, wherein the plurality of reaction means are arranged in series so that the reaction flow paths are connected to each other, and the volume of the reaction flow path in at least one of the plurality of reaction means is made different from the volume of the reaction flow path in the other reaction means.

11. The reaction method according to claim 10, wherein the volume is set such that the volume of the reaction flow channel is larger for at least two of the plurality of reaction means located further downstream.

12. The reaction method according to claim 11, wherein the volumes of the reaction channels are set so that they are equal in volume in at least two of the plurality of reaction means.

13. The reaction method according to claim 10, wherein the volume is set so that the volume of the reaction flow channel is larger for a reaction means located further downstream among the plurality of reaction means.

14. A reaction method described in any one of claims 10 to 13, wherein the multiple different fluids include at least a fluid containing a polymerization initiator and a fluid containing one or more types of monomers, the fluid containing the one or more types of monomers is introduced into the processing flow path from the inlet portion, and the one or more types of monomers are polymerized in the presence of the polymerization initiator in the reaction flow path.

15. The reaction method according to claim 14, wherein the volume of the reaction flow channels in the plurality of reaction means is set so that the polydispersity Mw / Mn (Mw and Mn are the weight average molecular weight and number average molecular weight of the polymer, respectively) of the polymer produced by the microfluidic system is 1.3 or more and 3.0 or less.

16. The reaction method according to any one of claims 10 to 13, wherein the microfluidic system further comprises a reaction promotion means for promoting a chemical reaction of reactants contained in the mixed fluid in the reaction channel.

17. The reaction method according to claim 16, wherein the reaction promotion means includes at least one of heating means, light irradiation means, vibration energy imparting means, and voltage application means.

18. The reaction method according to any one of claims 10 to 13, wherein the reaction channel has a channel width of 1000 μm or less.

19. A method for producing a polymer using a microfluidic system including a plurality of microfluidic devices formed with microchannels, the microfluidic system comprising a plurality of reaction means having an inlet part for introducing at least one or more monomers from a plurality of heterogeneous fluids into a predetermined processing flow path in order to mix the plurality of heterogeneous fluids including at least a fluid containing a polymerization initiator and a fluid containing one or more monomers in the predetermined processing flow path, and a reaction flow path formed in the microfluidic device as a microchannel that is arranged downstream of the inlet part and constitutes part of the predetermined processing flow path, the reaction flow path causing a polymerization reaction of the one or more monomers in the presence of the polymerization initiator by the mixed fluid of the plurality of heterogeneous fluids, and a volume of the reaction flow path in at least one of the plurality of reaction means is made different from the volume of the reaction flow path in the other reaction means.

20. The method for producing a polymer according to claim 19, wherein the volume of the reaction flow channel is set so that the volume of the reaction channel of at least two of the plurality of reaction means is larger in the reaction means located further downstream.

21. The method for producing a polymer according to claim 20, wherein the volumes of the reaction channels in at least two of the plurality of reaction means are set to be equal to each other.

22. The method for producing a polymer according to claim 19, wherein the volume is set so that the volume of the reaction flow channel is larger in the reaction means located further downstream among the plurality of reaction means.