Processing apparatus, processing method, and method for producing polymer

Abstract

The invention provides a novel processing device suitable for taking out contents from a pressure-resistant container. This processing device (100) is provided with a pressure-resistant container (10) and a processing container (20) for accommodating an object to be processed. The processing container (20) is detachably disposed inside the pressure-resistant container (10). A processing method using the processing device (100) according to the present invention includes a step of processing an object in a state in which a fluid supplied to the inside of the processing container (10) is brought into contact with the object inside the processing container (10).

Description

Technical Field

[0001] The present invention relates to a processing device, a processing method and a method for producing a polymer. Background Art

[0002] In the past, pressure vessels were used to process objects under high pressure. Depending on the gas introduced into the pressure vessel, a supercritical fluid is sometimes formed by sufficient pressurization and heating. Supercritical fluids have lower viscosity and higher diffusivity than liquids, and are capable of dissolving organic matter. Using supercritical fluids, it is possible to perform chemical reactions (e.g., polymerization reactions) on an object, extract components contained in the object, and perform other processes, all with minimal use of organic solvents.

[0003] For example, Patent Document 1 describes the use of a stainless steel high-pressure container filled with high-pressure carbon dioxide to carry out a polymerization reaction of a monomer group. It is presumed that the carbon dioxide is in a supercritical state within the high-pressure container.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 4368710 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] Typically, pressure-resistant containers are relatively large in size and are fixed to a location for use. Therefore, after processing the object, it is difficult to fully remove the contents from the top of the pressure-resistant container. In order to remove the contents from the pressure-resistant container, a solution may be considered in which a discharge port for discharging the contents is provided at the bottom of the pressure-resistant container. However, from the perspective of fully ensuring the durability of the pressure-resistant container under high pressure, the inner diameter of the discharge port is often adjusted to be smaller, for example, less than about 1 mm. At a discharge port with a small inner diameter of this extent, clogging is likely to occur when discharging the contents. This problem occurs particularly significantly when the object is a solid object such as a powder or when a solid object is obtained from the object by processing.

[0009] Therefore, an object of the present invention is to provide a new processing device suitable for taking out the contents from a pressure-resistant container.

[0010] Solutions for solving problems

[0011] The present invention provides a processing device, wherein:

[0012] The processing device has:

[0013] pressure vessels; and

[0014] A processing container for storing objects to be processed.

[0015] The processing container is detachably disposed inside the pressure container.

[0016] Furthermore, the present invention provides a processing method using the above-mentioned processing device, wherein:

[0017] The processing method includes the step of processing the object in the processing container while a fluid supplied into the processing container is in contact with the object.

[0018] Furthermore, the present invention provides a method for producing a polymer using the above-mentioned processing apparatus, wherein:

[0019] The manufacturing method includes the step of causing a polymerization reaction of the monomer group to proceed in the processing container while a fluid supplied into the processing container is in contact with the monomer group.

[0020] Effects of the Invention

[0021] According to the present invention, a new processing device suitable for taking out the contents from a pressure-resistant container can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic cross-sectional view of a processing device according to one embodiment of the present invention.

[0023] Figure 2 yes Figure 1 An exploded perspective view of a processing container included in the processing apparatus shown.

[0024] Figure 3 It is a schematic cross-sectional view showing a modified example of the processing device.

[0025] Figure 4 This is a schematic structural diagram of a processing system including the processing device of the present invention.

[0026] Figure 5 It is a schematic configuration diagram showing a modified example of the processing system.

[0027] Figure 6 This is an image of the inside of the pressure container showing the results of Example 1.

[0028] Figure 7 This is an image of the inside of the pressure container showing the results of Comparative Example 1.

[0029] Figure 8 This is a schematic cross-sectional view of a conventional processing device. DETAILED DESCRIPTION

[0030] A processing device according to a first aspect of the present invention includes:

[0031] pressure vessels; and

[0032] A processing container for storing objects to be processed.

[0033] The processing container is detachably disposed inside the pressure container.

[0034] In the second aspect of the present invention, for example, according to the processing apparatus of the first aspect, the processing container has: a cylindrical body having a first end face and a second end face facing each other; and a bottom covering an opening surrounded by the first end face.

[0035] In a third aspect of the present invention, for example, in the processing apparatus according to the second aspect, the bottom portion has a supply port for supplying a fluid into the interior of the processing container.

[0036] In the fourth aspect of the present invention, for example, in the processing apparatus according to the third aspect, a check valve is arranged at the supply port, which allows the fluid to flow from the outside to the inside of the processing container and prevents the fluid from flowing from the inside to the outside of the processing container.

[0037] In a fifth aspect of the present invention, for example, in the processing apparatus according to any one of the second to fourth aspects, the bottom portion is detachable from the main body portion.

[0038] In a sixth aspect of the present invention, for example, in the processing apparatus according to any one of the second to fifth aspects, the second end surface of the main body has a connection portion connectable to another member.

[0039] In a seventh aspect of the present invention, for example, the processing apparatus according to any one of the second to sixth aspects further includes a sealing member attached to the periphery of the main body.

[0040] In an eighth aspect of the present invention, for example, in the processing apparatus according to any one of the first to seventh aspects, the pressure-resistant container includes a container body and a lid.

[0041] In a ninth aspect of the present invention, for example, in the processing apparatus according to the eighth aspect, the bottom of the container body has a supply port for supplying a fluid into the interior of the pressure-resistant container.

[0042] In a tenth aspect of the present invention, for example, in the processing apparatus according to the eighth aspect or the ninth aspect, the lid has a discharge port for discharging the fluid from the interior of the pressure container.

[0043] In an eleventh aspect of the present invention, for example, in the treatment apparatus according to any one of the first to tenth aspects, the object includes a monomer group, and the treatment causes a polymerization reaction of the monomer group to proceed.

[0044] In the twelfth aspect of the present invention, for example, the processing apparatus of any one of the first to eleventh aspects processes the object in the processing container while a fluid supplied into the processing container contacts the object.

[0045] In the thirteenth aspect of the present invention, for example, the processing apparatus according to the twelfth aspect performs the processing in a state where the fluid in a supercritical state is in contact with the object.

[0046] The processing method according to the fourteenth aspect of the present invention is a processing method using the processing apparatus according to any one of the first to thirteenth aspects, wherein:

[0047] The processing method includes the step of processing the object in the processing container while a fluid supplied into the processing container is in contact with the object.

[0048] In a fifteenth aspect of the present invention, for example, according to the treatment method of the fourteenth aspect, the treatment is performed in a state where the fluid in a supercritical state is in contact with the object.

[0049] In a sixteenth aspect of the present invention, for example, according to the treatment method of the fourteenth or fifteenth aspect, the fluid contains carbon dioxide.

[0050] In a seventeenth aspect of the present invention, for example, according to the treatment method of any one of the fourteenth to sixteenth aspects, the object includes a monomer group, and the treatment causes a polymerization reaction of the monomer group to proceed.

[0051] The 18th aspect of the present invention is a method for producing a polymer using the processing apparatus of any one of the 1st to 13th aspects, wherein:

[0052] The manufacturing method includes the step of causing a polymerization reaction of the monomer group to proceed in the processing container while a fluid supplied into the processing container is in contact with the monomer group.

[0053] Hereinafter, the present invention will be described in detail, but the following description is not intended to limit the present invention to specific embodiments.

[0054] <Embodiment of Processing Device>

[0055] like Figure 1As shown, the processing apparatus 100 of this embodiment includes a pressure vessel 10 and a processing vessel 20. The processing vessel 20 is used to store objects to be processed and is disposed within the pressure vessel 10 in a removable manner. As used herein, "removable" means that the processing vessel 20 can be placed in and removed from the pressure vessel 10 without damaging the pressure vessel 10 and the processing vessel 20. While the processing vessel 20 is disposed within the pressure vessel 10, it can be secured to the pressure vessel 10 using fasteners such as bolts, but preferably, it is not secured.

[0056] According to the processing apparatus 100 of this embodiment, by removing the processing container 20 from the pressure-resistant container 10 after processing the object, the processed content can be easily taken out.

[0057] (Pressure Container)

[0058] The pressure vessel 10 is, for example, a container (pressure vessel) capable of withstanding an internal pressure exceeding 0.1 MPa. In particular, the pressure vessel 10 is preferably capable of withstanding an internal pressure of 1.0 MPa or greater, 5.0 MPa or greater, 7.0 MPa or greater, 10 MPa or greater, 15 MPa or greater, or even 20 MPa or greater. The pressure vessel 10 is, for example, fixed to the location where the processing apparatus 100 is installed.

[0059] The pressure-resistant container 10 includes, for example, a container body 11 and a lid 15. The container body 11 is tubular (particularly cylindrical) with a bottom and can accommodate a processing container 20 therein. The lid 15 is a member that is mounted on top of the container body 11 to seal the interior of the container body 11. When processing objects, the lid 15 and the container body 11 can be secured to each other using fasteners such as screws or bolts, or by threading the lid 15 onto the container body 11 using a screw mechanism.

[0060] The bottom 11a of the container body 11 has, for example, a supply port 12 for supplying fluid into the interior of the pressure container 10. The supply port 12 is, for example, a nozzle-shaped opening that penetrates the bottom 11a of the container body 11 in its thickness direction. The internal space and the external space of the pressure container 10 are connected via the supply port 12. For example, a pipe (a fluid supply path described later) is connected to the supply port 12.

[0061] The bottom 11a of the container body 11 may further include a discharge port (not shown) for discharging the contents of the pressure container 10 (e.g., fluid remaining in the gap between the pressure container 10 and the processing container 20 after processing an object) to the outside of the pressure container 10. The discharge port is, for example, a nozzle-shaped opening that extends through the bottom 11a of the container body 11 along its thickness. The internal space of the pressure container 10 communicates with the external space via the discharge port. For example, piping is connected to the discharge port.

[0062] The internal capacity of the container body 11 is, for example, 100 mL or more, but may also be 500 mL or more, 2 L or more, 20 L or more, 100 L or more, or even 200 L or more. The upper limit of the internal capacity of the container body 11 is, for example, less than 1000 L, but may also be 500 L or less. A container body 11 with an internal capacity of 1000 L or more is too heavy and difficult to handle.

[0063] The lid 15 has, for example, a discharge port 16 for discharging fluid from the interior of the pressure container 10. The discharge port 16 is, for example, a nozzle-shaped opening that penetrates the lid 15 in its thickness direction. The interior space and the exterior space of the pressure container 10 are connected via the discharge port 16. For example, a pipe (a fluid discharge path described later) is connected to the discharge port 16.

[0064] The lid 15 may further include a supply port (not shown) for supplying an object into the interior of the pressure vessel 10 (more specifically, the processing vessel 20). The supply port is, for example, a nozzle-shaped opening that penetrates the lid 15 along its thickness. The interior and exterior of the pressure vessel 10 are connected via the supply port. For example, a pipe is connected to the supply port. Alternatively, the aforementioned discharge port 16 may be used as the supply port.

[0065] The lid 15 is configured to accommodate, for example, a stirring blade (described later). Specifically, the lid 15 is provided with a bearing that supports the shaft of the stirring blade. The bearing allows the shaft of the stirring blade to be connected to a motor located outside the pressure vessel 10. This configuration allows the stirring blade located inside the pressure vessel 10 to be rotated by the motor while the vessel body 11 is sealed by the lid 15. The bearing is not particularly limited, but for example, a dry-type bearing capable of maintaining performance even under high pressure can be used.

[0066] The container body 11 and the lid 15 are made of a metal material such as stainless steel.

[0067] (Processing container)

[0068] like Figure 1 and 2As shown, the processing container 20 includes, for example, a tubular (particularly cylindrical) main body 21 and a bottom 25. The main body 21 includes, for example, a first end face 21a and a second end face 21b that face each other, and the bottom 25 is configured to cover an opening surrounded by the first end face 21a. Specifically, the bottom 25 covers the first end face 21a and the opening surrounded by the first end face 21a.

[0069] When the processing container 20 is disposed within the pressure vessel 10, the bottom portion 25 and the main body 21 are fixed to each other. For example, the first end face 21a of the main body 21 has a connection portion (not shown) capable of connecting to another component, and the bottom portion 25 has a through-hole 28 extending through the thickness of the bottom portion 25. Typically, the connection portion of the first end face 21a is a threaded portion functioning as an internal thread. The bottom portion 25 and the main body 21 can be fixed to each other by screwing a fastener such as a screw or bolt into the connection portion of the first end face 21a through the through-hole 28 of the bottom portion 25.

[0070] According to the above structure, the bottom portion 25 can be removed from the main body 21 by removing the fasteners. Thus, it is preferable that the bottom portion 25 be detachable from the main body 21. In this case, after processing an object using the processing apparatus 100, the processing container 20 is removed from the pressure vessel 10 and the bottom portion 25 of the processing container 20 is removed from the main body 21, thereby making it easier to remove the processed contents. However, the bottom portion 25 may be integrally formed with the main body 21 so as to be non-detachable from the main body 21.

[0071] The second end surface 21b of the main body 21 has, for example, a connection portion 22 that can be connected to another component. For example, after processing an object using the processing apparatus 100, by connecting the other component to the connection portion 22, the processing container 20 can be easily removed from the pressure vessel 10 by grasping the other component. Typically, the connection portion 22 is a threaded portion that functions as an internal thread, and the other component is a component having a threaded portion that functions as an external thread. Examples of components having a threaded portion include bolts and screws.

[0072] The main body 21 has grooves 23a and 23b formed on its outer wall, for example. Grooves 23a and 23b extend annularly along the circumference of the main body 21, specifically, in a direction perpendicular to the longitudinal direction of the main body 21. Grooves 23a and 23b are formed near the second end face 21b of the main body 21, while grooves 23b are formed near the first end face 21a. Grooves 23a and 23b are suitable for securing a sealing member, described later, when it is installed.

[0073] When the processing container 20 is disposed within the pressure vessel 10, a gap 31 exists between the outer wall of the main body 21 of the processing container 20 and the inner wall of the container body 11 of the pressure vessel 10. From the perspective of processing efficiency, this gap 31 is preferably narrow. As an example, the distance between the outer wall of the main body 21 and the inner wall of the container body 11 is 1 mm or less.

[0074] The bottom portion 25 has, for example, a supply port 26 for supplying fluid into the processing container 20. The supply port 26 is, for example, a nozzle-shaped opening that penetrates the bottom portion 25 along its thickness. The supply port 26 may simply be an opening. The interior and exterior of the processing container 20 are connected via the supply port 26. Alternatively, the bottom portion 25 may not have the supply port 26, but the main body 21 may have the supply port.

[0075] A valve 27 is preferably provided at the supply port 26. Typically, the valve 27 is a check valve that allows fluid to flow from the outside of the processing container 20 to the inside and prevents fluid from flowing from the inside of the processing container 20 to the outside. The valve 27, which serves as a check valve, is adjusted, for example, by a spring, so that it opens only when the pressure outside the processing container 20 is higher than the pressure inside the processing container 20. This prevents objects inside the processing container 20 from moving to the outside. Thus, when the valve 27, which serves as a check valve, is provided, it is possible to prevent objects contained inside the processing container 20 from moving to the outside of the processing container 20 (more specifically, to the gap between the pressure-resistant container 10 and the processing container 20) through the supply port 26.

[0076] The main body 21 and the bottom 25 are made of a metal material such as stainless steel.

[0077] In addition, Figure 2 In the example, the main body 21 does not have a through hole on its wall surface that connects the internal space of the processing container 20 with the external space. In addition to the supply port 26, the bottom 25 also does not have a through hole that connects the internal space of the processing container 20 with the external space. However, depending on the object contained in the processing container 20 and the treatment performed on the object, the main body 21 and the bottom 25 may also have the above-mentioned through holes. As an example, the main body 21 and the bottom 25 may also be a mesh member or a mesh-like object formed with small through holes to the extent that solid objects cannot pass through. The processing container 20 having such a main body 21 and bottom 25 is suitable for, for example, the treatment of extracting components contained in the object.

[0078] (Sealing member)

[0079] The processing apparatus 100 further includes, for example, a sealing member 30. The sealing member 30 is mounted around the main body 21 of the processing container 20, and more specifically, is disposed in the groove 23a of the main body 21. The sealing member 30 can, for example, contact the main body 21 of the processing container 20 and the container body 11 of the pressure container 10 to seal a gap 31 between the main body 21 and the container body 11. This prevents the object from becoming clogged in the gap 31 during processing. Specific examples of the sealing member 30 include an O-ring, putty, or sealing tape.

[0080] Furthermore, the processing apparatus 100 may further include an additional sealing member (not shown) disposed in the groove 23b of the main body 21. Examples of the additional sealing member include those described above with respect to the sealing member 30.

[0081] (Supporting part)

[0082] The processing apparatus 100 further includes, for example, a support portion 35. The support portion 35 is a member disposed within the container body 11 of the pressure-resistant container 10 and supports the processing container 20. Specifically, the support portion 35 is disposed between the bottom 11a of the container body 11 and the bottom 25 of the processing container 20, and is in contact with these members.

[0083] The support portion 35 has, for example, an annular shape in a plan view, and surrounds the valve 27 disposed at the bottom 25 of the processing container 20 in a plan view. This support portion 35 can prevent the valve 27 from interfering with the pressure container 10 when the processing container 20 is disposed inside the pressure container 10, thereby preventing the valve 27 from functioning poorly.

[0084] (Stirring blade)

[0085] The processing apparatus 100 further includes, for example, a stirring blade 40. The stirring blade 40 can stir the object in the processing container 20 while being installed on the lid 15. The stirring blade 40 is connected to, for example, a motor (not shown) disposed outside the pressure container 10.

[0086] exist Figure 1 In the example shown, the stirring blade 40 is a spiral ribbon blade. However, the shape of the stirring blade 40 is not particularly limited and can be appropriately adjusted according to the object contained in the processing container 20 and the processing performed on the object. In addition, depending on the situation, the processing device 100 may not include the stirring blade 40.

[0087] (Handling method)

[0088] In this embodiment, the processing method using the processing apparatus 100 includes, for example, the following steps: processing the object in the processing container 20 while a fluid supplied into the processing container 20 contacts the object.

[0089] As the fluid in contact with the object, gas, liquid, high-pressure gas, subcritical fluid, supercritical fluid etc. can be enumerated, preferably supercritical fluid. As an example, in the processing method of the present embodiment, processing is implemented under the state that the fluid in supercritical state is in contact with the object. As mentioned above, by using supercritical fluid, it is possible to carry out the processing of the chemical reaction (such as polymerization reaction) of the object, the processing of the composition contained in the extraction object, etc., without using an organic solvent.

[0090] The composition of the fluid is not particularly limited and can be appropriately adjusted depending on the object or the treatment being performed on it. Examples of fluid components include carbon dioxide and water. The fluid preferably contains carbon dioxide, and more preferably consists essentially of carbon dioxide. In this specification, "consisting essentially of" means excluding other components that would alter the essential characteristics of the material being referenced, for example, meaning that the material comprises at least 95% by weight, or more preferably at least 99% by weight.

[0091] In a preferred embodiment of the present invention, the object includes a monomer group, and the polymerization reaction of the monomer group is advanced by treating the object, thereby synthesizing a polymer.

[0092] From another aspect, the present invention provides a method for producing a polymer using a processing device 100, wherein:

[0093] This manufacturing method includes the steps of causing a polymerization reaction of a monomer group to proceed in a state where a fluid supplied into the processing container 20 is in contact with the monomer group within the processing container 20 .

[0094] The following describes in detail a treatment method (a method for producing a polymer) in which the object includes a monomer group. Furthermore, in this method, the object including the monomer group is typically a liquid monomer composition. Thus, in this method, the object is sometimes referred to as a monomer composition. Furthermore, in this method, the processing vessel 20 functions as a reaction vessel. The processing apparatus 100 functions as a polymerization apparatus.

[0095] First, the processing container 20 is placed inside the container body 11 of the pressure-resistant container 10. Next, the monomer composition is placed inside the processing container 20. Alternatively, the processing container 20 containing the monomer composition in advance may be placed inside the container body 11.

[0096] The monomer group includes, for example, a (meth)acrylic acid-based monomer. In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid. (Meth)acrylate means acrylic acid ester and / or methacrylate ester.

[0097] Examples of the (meth)acrylic monomer include (meth)acrylic acid, alkyl (meth)acrylates, non-aromatic ring-containing (meth)acrylic monomers, aromatic ring-containing (meth)acrylic monomers, hydroxyl group-containing (meth)acrylic monomers, epoxy group-containing (meth)acrylic monomers, alkoxy group-containing (meth)acrylic monomers, amide group-containing (meth)acrylic monomers, cyano group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, isocyanate group-containing (meth)acrylic monomers, aziridine group-containing (meth)acrylic monomers, halogen atom-containing (meth)acrylic monomers, silicon atom-containing (meth)acrylic monomers, and polyfunctional (meth)acrylic monomers.

[0098] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, and Alkyl (meth)acrylates having an alkyl group with 1 to 20 carbon atoms, such as isononyl, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. [(meth)acrylate C 1-20 Alkyl esters] etc.

[0099] Examples of the non-aromatic ring-containing (meth)acrylic monomer include non-aromatic alicyclic rings (cycloalkane rings such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; cycloolefin rings such as cyclohexene), and non-aromatic bridged rings (for example, bicyclic hydrocarbon rings such as those in pinane, pinene, bornane, norbornane, and norbornene; tricyclic hydrocarbon rings such as those in adamantane; and bridged hydrocarbon rings such as tetracyclic hydrocarbon rings). Examples of the non-aromatic ring-containing (meth)acrylic monomer include cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate; and (meth)acrylates having a non-aromatic bridged ring such as bornyl (meth)acrylate and isobornyl (meth)acrylate.

[0100] Examples of the aromatic ring in the (meth)acrylic monomers containing an aromatic ring include aromatic hydrocarbon rings (e.g., benzene rings, condensed carbon rings in naphthalene, etc.), various aromatic heterocycles, and the like. Specifically, examples of the (meth)acrylic monomers containing an aromatic ring include aryl (meth)acrylates such as phenyl (meth)acrylate and naphthyl (meth)acrylate; aryloxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; and arylalkyl (meth)acrylates such as benzyl (meth)acrylate.

[0101] Examples of the hydroxyl group-containing (meth)acrylic monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and (meth)acrylate monoesters of (mono- or poly-)alkylene glycols such as polyethylene glycol (meth)acrylate monoesters and polypropylene glycol (meth)acrylate monoesters.

[0102] Examples of the epoxy-containing (meth)acrylic monomer include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate. Examples of the alkoxy-containing (meth)acrylic monomer include alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.

[0103] Examples of amide-containing (meth)acrylic monomers include (meth)acrylamide; (N-substituted) (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide, and N-hydroxy (meth)acrylamide; and the like. Examples of cyano-containing (meth)acrylic monomers include (meth)acrylonitrile (acrylonitrile, methacrylonitrile). Examples of amino-containing (meth)acrylic monomers include aminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate; and (N-substituted) aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and tert-butylaminoethyl (meth)acrylate. Examples of isocyanate-containing (meth)acrylic monomers include 2-(meth)acryloyloxyethyl isocyanate. Examples of aziridine-containing (meth)acrylic monomers include (meth)acryloylaziridine.

[0104] Examples of the halogen-containing (meth)acrylic monomer include 2-chloroethyl (meth)acrylate. Examples of the silicon-containing (meth)acrylic monomer include (meth)acryloyloxyalkyltrialkoxysilanes such as γ-(meth)acryloyloxypropyltrimethoxysilane, and (meth)acryloyloxyalkyl (di- or mono-)alkoxysilanes corresponding to the (meth)acryloyloxyalkyltrialkoxysilane.

[0105] Examples of the polyfunctional (meth)acrylic monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, polyurethane acrylate, divinylbenzene, butyl di(meth)acrylate, and hexyl di(meth)acrylate.

[0106] The monomer group may also include monomers (co-monomers) that can be copolymerized with the (meth)acrylic acid monomers. Examples of the co-monomers include carboxyl group-containing vinyl monomers such as itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid, and their anhydrides (maleic anhydride, itaconic anhydride, etc.); vinyl ester monomers such as vinyl acetate and vinyl propionate; styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; olefin monomers such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. Ether monomers; monomers containing an imide group, such as N-cyclohexylmaleimide and N-isopropylmaleimide; monomers containing a sulfonic acid group, such as sodium vinyl sulfonate; monomers containing a phosphate group, such as 2-hydroxyethyl acryloyl phosphate; vinyl monomers containing a heterocyclic ring, such as N-vinyl-2-pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, and N-vinyloxazole.

[0107] The monomer composition may further comprise a polymerization initiator. There are no particular limitations on the polymerization initiator, and the polymerization initiator may be appropriately selected from the polymerization initiators used in conventional free radical polymerization and used. Examples thereof include thermal decomposition polymerization initiators and photoinitiators (photopolymerization initiators) that decompose using light such as ultraviolet rays.

[0108] As the thermal decomposition type polymerization initiator, for example, when the polymerization is carried out at a temperature of 40° C. to 100° C., peroxide-based polymerization initiators such as benzoyl peroxide, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, 2,2 Azo-based polymerization initiators include 1,1'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethylpentane), and dimethyl-2,2'-azobis(2-methyl propionate). Furthermore, when the polymerization is conducted at a temperature of 20°C to 40°C, binary initiators (redox-based initiators) composed of benzoyl peroxide and dimethylaniline can be used.

[0109] As the photoinitiator (photopolymerization initiator), for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. can be used. In addition, the initiator decomposition rate of the photoinitiator is almost unaffected by the polymerization temperature. Therefore, when a photoinitiator is used as the polymerization initiator, the polymerization temperature can be substantially any temperature.

[0110] The amount of the polymerization initiator used may be an amount generally used in the polymerization of a (meth)acrylic monomer, and is, for example, 0.005 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the monomer group.

[0111] The monomer composition may also include a chain transfer agent. The chain transfer agent can easily adjust the weight average molecular weight of the polymer obtained by polymerization of the monomer group to a smaller value of, for example, about 100,000 or less. As chain transfer agents, for example, alkyl mercaptans (dodecyl mercaptan, etc.) having a carbon number of 1 to 15, benzyl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-ethylhexyl mercaptoacetate, 3-mercaptopropionic acid, α-thioglycerol, 2-mercaptoethanol, benzyl alcohol, α-methylbenzyl alcohol, 2,3-dimethylmercapto-1-propanol, α-methylstyrene dimer, etc. In addition, oligomers such as rosin acid, rosin acid esters, and terpene resins can also be used for molecular weight adjustment instead of chain transfer agents.

[0112] The amount of the chain transfer agent used is not particularly limited, and is, for example, 0.005 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the monomer group.

[0113] The monomer composition may contain a small amount of an organic solvent such as toluene, hexane, or ethyl acetate; an emulsifier; a dispersant, etc., but preferably does not contain them.

[0114] Next, the lid 15 is attached to the container body 11 of the pressure container 10 to seal the interior of the container body 11. With the discharge port 16 of the lid 15 open, an inert gas is supplied from the supply port 12 of the container body 11 into the pressure container 10. Examples of the inert gas include carbon dioxide, nitrogen, and argon, with carbon dioxide being preferred.

[0115] The inert gas supplied from the supply port 12 moves toward the inside of the processing container 20 through the supply port 26 at the bottom 25 of the processing container 20. Inside the processing container 20, the inert gas contacts the monomer composition. Thus, the oxygen concentration of the monomer composition can be reduced. In particular, in the processing device 100 of the present embodiment, since the supply port 26 is located at the bottom 25 of the processing container 20, the monomer composition is bubbled by introducing the inert gas into the interior of the processing container 20. Thus, there is a tendency to efficiently reduce the oxygen concentration of the monomer composition. As described above, when the supply port 26 is provided with a check valve as the valve 27, it is possible to prevent the monomer composition from moving to the outside of the processing container 20 (the gap between the pressure-resistant container 10 and the processing container 20) during the bubbling process.

[0116] The inert gas that has moved into the processing container 20 is exhausted to the outside of the processing apparatus 100 through the exhaust port 16 of the cover 15. By this operation, the internal space of the processing apparatus 100 is filled with the inert gas.

[0117] Next, the discharge port 16 of the cover 15 is closed to seal the internal space of the pressure-resistant container 10. Specifically, the internal space of the pressure-resistant container 10 is sealed by closing the valve of the pipe connected to the discharge port 16. In this state, a fluid is supplied to the interior of the pressure-resistant container 10 from the supply port 12 of the container body 11. Typically, the fluid supplied from the supply port 12 is a gas, or it may be the above-mentioned inert gas. The fluid is preferably gaseous carbon dioxide. The content of carbon dioxide in the fluid is not particularly limited, and may be, for example, 95 wt% or more, or 99 wt% or more, or even 99.5 wt% or more.

[0118] The amount of the fluid used is not particularly limited, and is, for example, 5 parts by weight or more, 5 to 2000 parts by weight, or even 20 to 900 parts by weight, relative to 100 parts by weight of the monomer group.

[0119] The fluid supplied from the supply port 12 moves into the interior of the processing container 20 through the supply port 26 at the bottom 25 of the processing container 20. This causes the pressure within the processing container 20 to rise. The pressure within the processing container 20 is adjusted to, for example, 5.0 MPa or higher, 5.73 MPa or higher, 7.3 MPa or higher, or even 10 MPa or higher. The upper limit of the pressure within the processing container 20 is not particularly limited, and may be, for example, 40 MPa or lower, 30 MPa or lower, or even 25 MPa or lower.

[0120] At this time, the temperature within the processing container 20 is adjusted to, for example, 20°C or higher, 30°C or higher, or even 40°C or higher. The upper limit of the temperature within the processing container 20 is not particularly limited, and may be, for example, 100°C or lower, 90°C or lower, or even 70°C or lower. The temperature within the processing container 20 can be adjusted, for example, using an external bath electric heater. Alternatively, the temperature within the processing container 20 can be adjusted by supplying a high-temperature fluid from the supply port 12.

[0121] In this embodiment, the gaseous fluid can be brought into a supercritical state by appropriately adjusting the pressure and temperature within the processing container 20. For example, if the fluid is carbon dioxide, the carbon dioxide can be brought into a supercritical state by adjusting the pressure within the processing container 20 to 7.3 MPa or higher and the temperature to 31°C or higher. Within the processing container 20, the supercritical fluid mixes with the monomer composition and functions as a diluent for the monomer composition.

[0122] For example, by adjusting the pressure and temperature within the processing container 20 to the above-mentioned ranges, a polymerization reaction of the monomer group contained in the monomer composition proceeds. Thus, a polymer can be synthesized. The time required for polymerization (polymerization time) is, for example, 2 to 20 hours, but may also be 3 to 15 hours, or even 5 to 12 hours.

[0123] After the polymerization reaction is completed, the outlet 16 of the lid 15 is opened. Specifically, the outlet 16 is opened by opening the valve of the pipe connected to the outlet 16. As a result, the fluid is discharged from the interior of the processing container 20 to the outside of the processing apparatus 100 through the outlet 16. As an example, when the outlet 16 is opened, the pressure in the processing container 20 decreases, and the supercritical fluid turns into gas, which is then discharged from the outlet 16.

[0124] When the fluid is discharged to the outside of the processing apparatus 100, a solid polymer (e.g., powder) is precipitated inside the processing container 20. The polymer can be easily removed by removing the lid 15 of the pressure container 10 and taking the processing container 20 out of the container body 11.

[0125] In addition, in the above-mentioned method, a polymerization reaction is utilized to obtain a reaction mixture comprising polymers and residual monomers, polymerization initiators, chain transfer agents and other residues. Therefore, in the processing method of the present embodiment, an operation of removing residues from the reaction mixture can also be performed after the polymerization reaction is completed. As an example, after the polymerization reaction is completed, if the discharge port 16 is not opened and the reaction mixture is allowed to stand, the reaction mixture is separated into an upper layer comprising a fluid (supercritical fluid) as the main component and a lower layer comprising a polymer. The above-mentioned residues are usually present in the upper layer. By removing the upper layer and recovering the lower layer, the content of the residues in the reaction mixture can be reduced, and the polymer can be recovered with high purity. This operation can be repeated by transporting a new fluid to the interior of the processing container 20. In this specification, the above-mentioned operation is sometimes referred to as a cleaning operation.

[0126] The above-mentioned treatment method is particularly suitable for the production of polymers with a weight average molecular weight of 100,000 or less. If the molecular weight is as low as this level, the viscosity of the reaction mixture can be suppressed from excessively rising during the polymerization reaction. The weight average molecular weight of the polymer is, for example, 500 to 100,000, or may be 1,000 to 50,000, 2,000 to 30,000, or further 3,000 to 10,000. The weight average molecular weight of the polymer can be controlled by the type of polymerization initiator, chain transfer agent, its usage, the temperature during polymerization, the time, the concentration of the monomer group, etc. In addition, polymers with a weight average molecular weight of 100,000 or less (particularly (meth) acrylic polymers) can be used as modifiers for adhesives, bonding agents, coatings, plastic films, etc.

[0127] The treatment method of the present embodiment can also be used for the production of the (meth)acrylic polymer (B) described in, for example, Japanese Patent Application Laid-Open No. 2014-74179 and International Publication No. 2011 / 118183.

[0128] The weight average molecular weight of the polymer produced by the above-mentioned treatment method may exceed 100,000 in some cases. The weight average molecular weight of the polymer is, for example, 100,000 to 3,000,000, 200,000 to 2,000,000, or 300,000 to 1,500,000.

[0129] Furthermore, the treatment method of this embodiment is not limited to the treatment of an object containing a monomer group. For example, the object may contain a compound other than the aforementioned monomer group, and the treatment of the object may be used to induce a chemical reaction other than polymerization reaction on the compound. Furthermore, the object may be a solid, and the treatment of the object may be used to extract the components contained in the object. A specific example of such a treatment is the extraction of caffeine from coffee beans by contacting them with a supercritical fluid (particularly a supercritical fluid of carbon dioxide).

[0130] Figure 8 1 is a schematic cross-sectional view showing an example of a conventional processing apparatus 200. The processing apparatus 200 has the same Figure 1 The processing apparatus 200 has the same structure as the processing apparatus 100. Specifically, the processing apparatus 200 includes a pressure-resistant container 210 having a container body 211 and a lid 215. The bottom 211a of the container body 211 has a supply port 212, and the lid 215 has a discharge port 216. The pressure-resistant container 210 is typically fixed to the location where the processing apparatus 200 is installed. The processing apparatus 200 also includes a stirring blade 240.

[0131] When an object is treated while in contact with a fluid within the processing apparatus 200 (specifically, within the pressure container 210), the processed contents remain within the pressure container 210, particularly near the bottom 211a of the container body 211. As described above, the pressure container 210 is typically fixed to the location where the processing apparatus 200 is installed, making it difficult to fully remove the contents remaining near the bottom 211a from above the container body 211.

[0132] If the outlet for discharging the contents is located at the bottom 211a, the inner diameter of the outlet is often adjusted to be small, for example, less than 1 mm, to ensure sufficient durability of the pressure-resistant container 210 under high pressure. An outlet with such a small inner diameter is prone to clogging during the discharge of the contents. This problem is particularly prominent when the target object is a solid such as a powder, or when a solid object is obtained from the target object through processing. Furthermore, in the processing device 200, the supply port 212 at the bottom 211a may become clogged with the contents.

[0133] In contrast, the processing apparatus 100 of this embodiment includes a processing container 20 detachably disposed within a pressure-resistant container 10. In the processing apparatus 100, the object is processed within the processing container 20. Therefore, after processing the object, the processed contents can be easily removed by removing the processing container 20 from the pressure-resistant container 10. Furthermore, in the processing apparatus 100 of this embodiment, the ports provided in the pressure-resistant container 10 are less likely to become clogged by the contents.

[0134] <Modification of the Processing Device>

[0135] Figure 3 1 is a schematic diagram showing a modified example of the processing device 110. Figure 3As shown, in processing apparatus 110, the supply port 12 of pressure-resistant container 10 is provided on lid 15 rather than on bottom 11a of container body 11. Bottom 25 of processing container 20 does not have supply port 26. Except for the above, the structure of processing apparatus 110 of this embodiment is identical to that of processing apparatus 100. Therefore, elements common to processing apparatus 100 and processing apparatus 110 of this embodiment are denoted by the same reference numerals, and their description may be omitted. That is, the descriptions of each embodiment are applicable to each other unless there is a technical conflict.

[0136] In the processing apparatus 110, the fluid supplied into the pressure vessel 10 from the supply port 12 of the cover 15 moves into the processing vessel 20 through the opening surrounded by the second end surface 21b of the main body 21 of the processing vessel 20. Thus, the object can come into contact with the fluid inside the processing vessel 20.

[0137] In the processing apparatus 110 , the cover 15 may not include the discharge port 16 , and the supply port 12 may also function as the discharge port.

[0138] <Implementation Method of Processing System>

[0139] like Figure 4 As shown, the processing system 150 of this embodiment includes a processing device 100. The processing system 150 further includes a fluid supply path 50 and a tank 55. The tank 55 stores fluid and functions as a fluid supply source. The tank 55 is, for example, a gas cylinder for storing gas. The fluid supply path 50 is a path that connects the tank 55 and the supply port 12 of the pressure-resistant container 10 of the processing device 100 and is used to supply fluid from the tank 55 to the processing device 100.

[0140] Fluid supply path 50 is provided with valves 51 and 52, a pressurizing device 53, and a heat exchanger 54. Valves 51 and 52 are each an on-off valve or a flow control valve. Valve 51 can, for example, adjust the flow rate of fluid delivered from tank 55 to fluid supply path 50. Valve 52 can, for example, adjust the flow rate of fluid delivered from fluid supply path 50 to processing device 100.

[0141] The pressurizing device 53 is located between valves 51 and 52 and is capable of increasing the pressure of the fluid delivered from the tank 55. Examples of the pressurizing device 53 include a booster pump, a blower, and a back-pressure valve. The heat exchanger 54 is located between the pressurizing device 53 and the valve 52 and is, for example, a preheating coil that increases the temperature of the fluid.

[0142] The processing system 150 further includes a fluid discharge path 60. The fluid discharge path 60 is connected to the discharge port 16 of the pressure vessel 10 of the processing device 100 and is used to discharge fluid from the processing device 100. A valve 61 is disposed in the fluid discharge path 60. The valve 61 is an on-off valve or a flow control valve. For example, the valve 61 can adjust the flow rate of the fluid discharged from the processing device 100.

[0143] Unless otherwise specified, each path of the processing system 150 is formed of, for example, a metal or resin pipe.

[0144] The processing system 150 further includes a motor 70. The motor 70 is connected to the stirring blade 40 included in the processing device 100. By operating the motor 70, the stirring blade 40 can be rotated.

[0145] <Modification of the Processing System>

[0146] Figure 5 1 is a schematic diagram showing a modified example of a processing system 160. Figure 5 As shown, the processing system 160 has a reference Figure 3 The processing apparatus 110 described above. Except for the above, the configuration of the processing system 160 of this embodiment is the same as that of the processing system 100.

[0147] In the processing system 160, the fluid supply path 50 is connected to the supply port 12 provided in the upper portion of the processing device 110 (specifically, the lid 15 of the pressure-resistant container 10). The fluid supplied from the tank 55 to the processing device 110 moves into the processing container 20 through the opening surrounded by the second end surface 21b of the main body 21 of the processing container 20, and can come into contact with the object inside the processing container 20.

[0148] Example

[0149] The present invention will be described in further detail below using examples. However, the present invention is not limited to the examples shown below.

[0150] (Example 1)

[0151] In Example 1, using Figure 1The monomer composition was processed using the processing apparatus 100 shown to produce a polymer. Specifically, a processing vessel 20 was first placed inside the container body 11 of the pressure-resistant container 10, and a monomer composition was placed inside the processing vessel 20. The monomer composition contained 50 parts by weight of dicyclopentanyl methacrylate (trade name "FANCRYL FA-513M", manufactured by Riseno Corporation), 50 parts by weight of methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2 parts by weight of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a chain transfer agent, and 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an initiator.

[0152] Next, a lid 15 is installed above the container body 11 of the pressure-resistant container 10 to seal the interior of the container body 11. With the discharge port 16 of the lid 15 open, gaseous carbon dioxide is supplied from the supply port 12 of the container body 11 into the interior of the pressure-resistant container 10. The carbon dioxide moves into the interior of the processing container 20 through the supply port 26 at the bottom 25 of the processing container 20. Thus, a bubbling treatment of the monomer composition is performed. At this time, the motor connected to the stirring blade 40 is operated to rotate the stirring blade 40.

[0153] Next, the discharge port 16 of the lid 15 was closed to hermetically seal the interior of the pressure vessel 10. In this state, gaseous carbon dioxide was supplied from the supply port 12 of the container body 11 into the pressure vessel 10. The carbon dioxide moved into the processing vessel 20 through the supply port 26 in the bottom 25 of the processing vessel 20. This operation raised the pressure within the processing vessel 20 to 7 MPa.

[0154] Next, the processing apparatus 100 was heated using an external bath electric heater, raising the temperature within the processing vessel 20 to 70°C. Carbon dioxide was continuously supplied while the processing apparatus 100 was heated. By the time the temperature within the processing vessel 20 reached 80°C, the pressure within the processing vessel 20 was 25 MPa. Consequently, the carbon dioxide within the processing vessel 20 reached a supercritical state.

[0155] The above-mentioned temperature and pressure were maintained for 10 hours to allow the polymerization reaction of the monomer group to proceed. Thus, a polymer (weight average molecular weight: 5000) was obtained. After the polymerization reaction was completed, the discharge port 16 of the cover 15 was opened to discharge carbon dioxide from the inside of the processing container 20 to the outside of the processing device 100. The cover 15 of the pressure-resistant container 10 was disassembled, and the processing container 20 was taken out from the container body 11 to recover the powdered polymer. After taking out the processing container 20, the inside of the container body 11 was visually observed. As a result, almost no residues such as polymer were confirmed inside the container body 11 ( Figure 6 ).

[0156] (Comparative Example 1)

[0157] In Comparative Example 1, in addition to using Figure 8 The polymer was produced by treating the monomer composition in the same manner as in Example 1 except for the treatment apparatus 200 shown in FIG. 2 . After the polymer was taken out from the upper portion of the container body 211 of the pressure-resistant container 210, the interior of the container body 211 was visually observed. As a result, a large amount of polymer residue ( Figure 7 ).

[0158] Industrial applicability

[0159] The processing apparatus of the present invention can be used to process various objects. In particular, the processing apparatus is suitable for processing that causes a polymerization reaction of a monomer group.

Claims

1. A processing device, wherein: The processing device has: pressure vessels; and A processing container for storing objects to be processed. The processing container is detachably disposed inside the pressure container.

2. The processing device according to claim 1, wherein The processing container includes a cylindrical main body having a first end surface and a second end surface facing each other, and a bottom portion covering an opening surrounded by the first end surface.

3. The processing device according to claim 2, wherein The bottom portion has a supply port for supplying a fluid into the processing container.

4. The processing device according to claim 3, wherein A check valve is disposed at the supply port. The check valve allows the fluid to flow from outside to inside the processing container and prevents the fluid from flowing from inside to outside the processing container.

5. The processing device according to claim 2, wherein The bottom portion is detachable from the main body portion.

6. The processing device according to claim 2, wherein: The second end surface of the main body has a connection portion that can be connected to another member.

7. The processing device according to claim 2, wherein: The processing device further includes a sealing member attached to the periphery of the main body.

8. The processing device according to claim 1, wherein The pressure-resistant container includes a container body and a lid.

9. The processing device according to claim 8, wherein The bottom of the container body has a supply port for supplying a fluid into the interior of the pressure-resistant container.

10. The processing device according to claim 8, wherein The cover portion has a discharge port for discharging fluid from the interior of the pressure-resistant container.

11. The processing device according to claim 1, wherein The object comprises a monomer group, The treatment allows the polymerization reaction of the monomer group to proceed.

12. The processing device according to claim 1, wherein The object is processed in the processing container while the fluid supplied into the processing container is in contact with the object.

13. The processing device according to claim 12, wherein: The treatment is performed while the fluid in a supercritical state is in contact with the object.

14. A processing method using the processing apparatus according to any one of claims 1 to 13, wherein: The processing method includes the step of processing the object in the processing container while a fluid supplied into the processing container is in contact with the object.

15. The processing method according to claim 14, wherein: The treatment is performed while the fluid in a supercritical state is in contact with the object.

16. The processing method according to claim 14, wherein: The fluid comprises carbon dioxide.

17. The processing method according to claim 14, wherein: The object comprises a monomer group, The treatment allows the polymerization reaction of the monomer group to proceed.

18. A method for producing a polymer, using the processing apparatus according to any one of claims 1 to 13, wherein: The manufacturing method includes the step of causing a polymerization reaction of the monomer group to proceed in the processing container while a fluid supplied into the processing container is in contact with the monomer group.

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