Method for producing polymer

Abstract

A method for producing a polymer according to the present invention comprises: a polymerization step including a polymerization treatment in which a polymerization initiator and two or more types of monomers are subjected to a polymerization reaction in a liquid to obtain a polymerization reactant; and performing at least one additional polymerization step in which an additive component is added and a further polymerization reaction is performed. Wherein the additive component includes at least one of the two or more monomers, and the addition of the additive component in each of the additional polymerization steps is performed while controlling the composition ratio of the monomer units contained in the polymer obtained in each of the additional polymerization steps.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing polymers. Background Technology

[0002] Generally, the production of polymers that are copolymers obtained by polymerization of two or more monomers is carried out by a method, such as using a batch process, which involves continuously adding a solution containing multiple monomers and a polymerization initiator, or continuously adding a solution containing a first monomer and a solution containing a second monomer and a polymerization initiator.

[0003] For example, Patent Document 1 discloses a method for preparing a first solution containing a monomer having a specific structure, and preparing a second solution containing other monomers and a polymerization initiator, heating the first solution, and adding the second solution dropwise to the heated first solution, thereby producing a copolymer useful for a resist composition.

[0004] In recent years, methods for manufacturing copolymers other than the dropwise addition method described above have also been developed. For example, Patent Document 2 discloses a method for introducing a first monomer, a second monomer, and a polymerization initiator from other introduction paths and mixing them.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-28904

[0008] Patent Document 2: Japanese Patent Application Publication No. 2020-29518 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In the batch process method disclosed in Patent Document 1, due to the different reaction rates of each monomer, there is a problem that copolymers with discrepancies in monomer composition are synthesized in the first and second halves of the reaction. This is believed to be due to the difficulty in controlling the distribution of raw material concentration and temperature in the reaction tank during the batch process, resulting in a deviation in the tank environment over time from a microscopic perspective.

[0011] On the other hand, the inventors have found that in a flow-based method as disclosed in Patent Document 2, the deviation of the tank environment over time can be easily suppressed because the amount of each component introduced can be controlled. However, compared with the batch method, research on the flow-based method is not sufficient, and there is still room for exploration from the viewpoint of controlling the structure of the obtained copolymer. Specifically, for example, in the flow-based method, attempts have not yet been made to control not only the final product but also the monomer composition ratio of the copolymer throughout the entire reaction.

[0012] The subject of this disclosure is to provide a method for manufacturing polymers that can stably obtain copolymers with desired monomer composition ratios throughout the entire reaction.

[0013] Problem Solving Methods

[0014] The inventors conducted in-depth research and found that, in a method of polymerizing two or more monomers while adding an additive containing monomers, the above-mentioned problem can be solved by controlling the amount of additive added in such a way that the composition ratio of monomer units in the polymer reactants obtained in each additional polymerization step reaches a given ratio, thereby completing the invention disclosed herein.

[0015] That is, the main point of this disclosure is as follows.

[0016] <Method 1>

[0017] This disclosure relates to a method for manufacturing a polymer, the method comprising:

[0018] Polymerization processes include polymerization treatments that involve carrying out a polymerization reaction between a polymerization initiator and two or more monomers in a liquid to obtain a polymerized product; and

[0019] An additional polymerization step is performed, in which additives are added to carry out a further polymerization reaction, and this additional polymerization step is performed at least once.

[0020] The above-mentioned additives contain at least one of the two or more monomers mentioned above.

[0021] In each additional polymerization step, the amount of the above-mentioned additives is controlled so that the composition ratio of monomer units in the polymer reactants obtained in each additional polymerization step reaches a given ratio.

[0022] <Method 2>

[0023] In Method 1, the amount of the added ingredients can be based on a molar basis.

[0024] <Method 3>

[0025] In method 1 or 2, it can be that, in the case of performing the above-mentioned additional polymerization steps n times (n≥1), the k-th (1≤k≤n) additional polymerization step processes the liquid containing the polymerization reactants obtained in the above-mentioned polymerization steps (in the case of k=1), or the liquid containing the polymerization reactants obtained in the (k-1)-th additional polymerization step (in the case of k≥2).

[0026] The addition of the additives in the k-th additional copolymerization process is controlled under the following M ki M ka and M kf Simultaneously

[0027] M ki The molar amount of each monomer unit in the reactive polymer contained in the liquid at the start of the k-th additional polymerization step.

[0028] M ka The molar amount of each monomer added in the k-th additional polymerization step.

[0029] M kf The molar amount of each monomer unit in the reactive polymer contained in the liquid at the end of the k-th additional polymerization step.

[0030] <Method 4>

[0031] In any of methods 1 to 3, if the above-mentioned added components include two or more monomers, the amount of each monomer added in at least one of the above-mentioned additional polymerization steps is determined based on the polymerizability of each monomer as evaluated by the following evaluation method.

[0032] (Evaluation Method)

[0033] When a polymer is produced by polymerizing each monomer using a solution containing the same molar amount of each monomer, and the molar amounts of each monomer unit in the polymer are compared, the monomer constituting the monomer unit with the larger molar amount is considered the monomer with high polymerizability, and the monomer constituting the monomer unit with the smaller molar amount is considered the monomer with low polymerizability.

[0034] <Method 5>

[0035] In method 4, the addition of the additive component in the above-mentioned additional polymerization step may be carried out in a manner that at least satisfies the following condition (1).

[0036] Condition (1): If a / b is less than A / B, then let α > β.

[0037] α: The molar amount of monomer A added

[0038] β: The molar amount of monomer B added

[0039] A: The molar amount of monomer A units in the target polymer

[0040] B: The molar amount of monomer B units in the target polymer.

[0041] a: The molar amount of monomer A when the above evaluation method was performed using monomer A and monomer B.

[0042] b: The molar amount of monomer B when the above evaluation method was performed using monomer A and monomer B.

[0043] <Method 6>

[0044] In any of the methods 1 to 5, it may be that in at least one of the above-mentioned additional polymerization steps, at least one monomer X contained in the above-mentioned added components that is repeated with the above-mentioned two or more monomers satisfies the following condition (2).

[0045] Condition (2): x1 and x2 are different.

[0046] x1: Parts by weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer.

[0047] x2: The weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0048] <Method 7>

[0049] In method 6, the monomer X can satisfy the following condition (3) respectively.

[0050] Condition (3): The value x3, represented by (x1 / x2-1)×100, is less than -5 and greater than 5.

[0051] x1: Parts by weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer.

[0052] x2: The weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0053] <Method 8>

[0054] In any of methods 1 to 7, as the monomer used in the above-described polymerization step, at least one monomer selected from the group consisting of: a polymerizable monomer containing (meth)acryloyl groups, a polymerizable monomer containing isocyanate groups, a polymerizable monomer containing carboxyl groups, a polymerizable monomer containing hydroxyl groups, a polymerizable monomer containing epoxy groups, or a polymerizable monomer containing... Polymerizable monomers with azoline group, polymerizable monomers containing maleimide group, polymerizable monomers containing amino group, styrene monomers, fluorinated vinyl monomers, silicone vinyl monomers, vinyl ester monomers, diene monomers, vinyl chloride, vinylidene chloride, allyl chloride, and vinyl ethyl ether.

[0055] <Method 9>

[0056] In any of the methods 1 to 8, the polymerization initiator can be a free radical polymerization initiator.

[0057] <Method 10>

[0058] In any of the methods 1 to 9, at least one step selected from the above-described polymerization step and the above-described additional polymerization step performed at least once can be carried out using an apparatus having a reaction flow path for the polymerization reaction of monomers.

[0059] <Method 11>

[0060] In method 10, the above-mentioned apparatus may be a microfluidic reactor, and the above-mentioned reaction flow path may be a microflow path.

[0061] <Method 12>

[0062] Embodiment 12 of this disclosure relates to a method for manufacturing a composition, the method comprising:

[0063] The composition is obtained by using a polymer manufactured by any of the polymer manufacturing methods of methods 1 to 11.

[0064] <Method 13>

[0065] This disclosure relates to a method for manufacturing a molded article, the method comprising:

[0066] The process of molding a polymer manufactured by a method of manufacturing a polymer according to any of the methods 1 to 11, or a composition manufactured by a method of manufacturing a composition according to method 12.

[0067] The effects of the invention

[0068] According to the technology disclosed herein, at least the following effects can be achieved: a method for manufacturing polymers that can stably produce copolymers with desired monomer composition ratios throughout the entire reaction can be achieved. Attached Figure Description

[0069] Figure 1 It is a diagram used to illustrate the process of polymerization and additional polymerization.

[0070] Figure 2 This is a structural diagram of one implementation of a polymer manufacturing system.

[0071] Figure 3 This is a top view of one embodiment of the reactor.

[0072] Figure 4 This is a graph showing the relationship between the monomer MMA consumption rate and the ratio of MMA units in the polymer in Example 1 and Comparative Example 1.

[0073] Figure 5 This is a graph showing the relationship between the monomer MMA consumption rate and the ratio of MMA units in the polymer in Example 2 and Comparative Example 1.

[0074] Symbol Explanation

[0075] 2b Reaction Flow Path

[0076] 10 Reactors

[0077] 20. Heater (an example of a reaction accelerator)

[0078] 100 Polymer Manufacturing System Detailed Implementation

[0079] The following describes in detail the embodiments of the invention disclosed herein, but these descriptions are only examples (representative examples) of the embodiments of the invention disclosed herein. The invention disclosed herein is not limited to these contents as long as it does not deviate from its spirit.

[0080] In this disclosure, the numerical range represented by "~" refers to the range of values ​​included before and after "~" as the lower and upper limits, and "A~B" means above A and below B.

[0081] In addition, in this specification, the expression "A or B" can be replaced with "selected from at least one of A and B".

[0082] Furthermore, multiple embodiments have been described in this disclosure, and various conditions in each embodiment can be applied to each other to the extent applicable.

[0083] In this disclosure, the unit of the monomer that constitutes the polymer is also referred to as a "monomer unit", and the compound (monomer) that corresponds to the monomer unit contained in the polymer is also referred to as a "compound (monomer) derived from the monomer unit".

[0084] In addition, some embodiments are described based on the accompanying drawings, but the dimensions, materials, shapes and relative arrangements of the constituent elements shown in the drawings are just one example.

[0085] <Methods for manufacturing polymers>

[0086] One embodiment of the present disclosure of a method for manufacturing a polymer (also referred to simply as a "polymer manufacturing method") includes:

[0087] Polymerization processes, including polymerization treatments that involve polymerizing an initiator and two or more monomers in a liquid to obtain a polymeric product; and

[0088] Further polymerization reactions are carried out by adding additives, and at least one additional polymerization step is performed.

[0089] The aforementioned added ingredients contain at least one of the two or more monomers mentioned above.

[0090] In each additional polymerization step, the amount of the above-mentioned additive is controlled in such a way that the composition ratio of monomer units in the polymer reactants obtained in each additional polymerization step reaches a given ratio.

[0091] Hereinafter, polymers will also be referred to as "copolymers".

[0092] Furthermore, in this disclosure, "the composition ratio of monomer units" (hereinafter also simply referred to as "composition ratio" or "monomer composition ratio") refers to the ratio of the amounts of two or more monomer units contained in the copolymer. From the viewpoint of easily obtaining a copolymer with a desired monomer composition ratio, this amount (the amount of added component) is preferably molar.

[0093] It should be noted that, within the scope of the technical effects of this disclosure, the above-described method for manufacturing polymers may also include any steps other than the polymerization step and the additional polymerization step.

[0094] The types of monomers constituting the copolymer can be selected according to the intended use. From the viewpoint of obtaining the desired properties, it is preferable that the monomer units of the multiple copolymers in the final product have the same composition ratio. In the existing production of copolymers using a batch process (intermittent), due to the different reaction rates of the monomers, copolymers with discrepancies in monomer composition ratios are synthesized in the first and second halves of the reaction. As a result, the final product contains copolymers with composition ratios that are significantly different from the desired monomer composition ratios, making it difficult to obtain the desired properties.

[0095] The inventors conducted in-depth research on the polymerization reaction of monomers and found that, compared with batch polymerization, a process flow in which raw materials are added during the reaction can control the amount of each component introduced, thus easily suppressing the deviation of the tank environment over time. Furthermore, it was found that by controlling the monomer composition ratio in the polymer reactants, and specifically by controlling the amount of monomer added in accordance with the reactivity and consumption rate of the monomers, copolymers with the desired monomer composition ratio can be stably obtained throughout the entire reaction.

[0096] Furthermore, in existing batch polymerization processes, there is a problem that the polymerization of highly reactive monomers proceeds first in the first half of the reaction, while the polymerization of less reactive monomers tends to deviate in the latter half. In this case, the arrangement of monomers in the final polymer is not optimal, making it difficult to obtain copolymers with the desired properties. For example, copolymers formed by a continuous arrangement of poorly soluble monomers exhibit poor solubility. However, with the method of this embodiment, for example, by varying the amount of added monomer while taking into account the reactivity of the monomers, it is possible to suppress the arrangement deviation and obtain copolymers with the desired properties.

[0097] It should be noted that, in this disclosure, "being able to stably obtain the desired monomer composition ratio throughout the entire reaction" does not mean that a copolymer with the desired monomer composition ratio can be obtained at any point in the reaction process, but rather that a copolymer with the desired monomer composition ratio can be obtained in each additional polymerization step of the reaction process. Furthermore, "obtaining a copolymer with the desired monomer composition ratio" does not mean merely obtaining a copolymer with the target monomer composition ratio, but rather obtaining a copolymer with the target monomer composition ratio, or a monomer composition ratio close to that target.

[0098] [Polymerization Process]

[0099] A method for manufacturing a polymer includes a polymerization step, which comprises a polymerization treatment in which a polymerization initiator and two or more monomers undergo a polymerization reaction in a liquid to obtain a polymeric product. To the extent that the technical effects of this disclosure are achieved, the polymerization step may include treatments other than polymerization treatment.

[0100] It should be noted that during the polymerization process, all or part of the monomers in the liquid may be polymerized. From the viewpoint of ensuring the fluidity of the liquid in subsequent additional polymerization processes and from the viewpoint of consistently obtaining copolymers with the desired monomer composition ratio, it is preferable not to polymerize all the monomers. If not all monomers are polymerized, the remaining monomers can be polymerized together with monomers that can be added additionally in subsequent additional polymerization processes.

[0101] (Aggregation Processing)

[0102] There are no particular restrictions on the types of polymerization in a polymerization reaction. The types of polymerization can be appropriately set according to the types of monomers. From the perspective of reaction sites, examples include chain polymerization, step polymerization, or living polymerization. From the perspective of reaction mechanisms, examples include addition polymerization, ring-opening polymerization, condensation polymerization, addition polymerization, or addition condensation. From the perspective of chemical reaction species, examples include free radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization.

[0103] Furthermore, in the polymer manufacturing method of this embodiment, within the scope of obtaining the technical effects of this disclosure, multiple polymerization reactions can be carried out simultaneously. For example, in the case of free radical polymerization, polymerization with a different chemical reaction species than free radical polymerization can be carried out together with free radical polymerization, such as anionic polymerization, cationic polymerization, or coordination polymerization.

[0104] It should be noted that polymerization can be carried out while the materials contained in the liquid are being mixed (stirred).

[0105] (1) Monomer

[0106] There are no particular restrictions on the number of monomer types, as long as there are two or more. It should be noted that there are also no particular restrictions on the arrangement of copolymers, for example: random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization, etc.

[0107] Furthermore, there are no particular restrictions on the structure of the obtained polymer; it can be linear, branched, or cyclic.

[0108] The monomer can be any monomer that undergoes polymerization (hereinafter also referred to as "polymerizable monomer"), and there are no particular restrictions on its type. For example, polymerizable monomers disclosed in Japanese Patent Application Publication No. 2018-149791 and Japanese Patent Application Publication No. 2010-194983 are examples. Specifically, polymerizable monomers are selected from those containing (meth)acryloyl groups, polymerizable monomers containing isocyanate groups, polymerizable monomers containing carboxyl groups, polymerizable monomers containing hydroxyl groups, polymerizable monomers containing epoxy groups, and polymerizable monomers containing... The monomers include at least one monomer selected from the following: azoline-containing polymerizable monomers, maleimide-containing polymerizable monomers, amino-containing polymerizable monomers, styrene monomers, fluorinated vinyl monomers, silicone vinyl monomers, vinyl ester monomers, conjugated diene monomers (diene monomers), aromatic vinyl monomers, vinyl carboxylate esters, olefin monomers, halogenated vinyl groups, vinylidene halide, allyl halides, and vinyl ethyl ethers. Specifically, the monomers may be selected from polymerizable monomers containing (meth)acryloyl groups, isocyanate groups, carboxyl groups, hydroxyl groups, epoxy groups, and other groups. The monomers include at least one monomer selected from the following groups: azoline-based polymerizable monomers, maleimide-containing polymerizable monomers, amino-containing polymerizable monomers, styrene monomers, fluorinated vinyl monomers, silicone vinyl monomers, vinyl ester monomers, diene monomers, vinyl chloride, vinylidene chloride, allyl chloride, and vinyl ethyl ether. Additionally, the monomers listed below can also be their derivatives.

[0109] In addition, either synthetic monomers or commercially available monomers can be used.

[0110] It should be noted that in this disclosure, the terms "(meth)acrylic acid" and "(meth)acrylate" refer to "methacrylic acid or acrylic acid" and "methacrylate and / or acrylate", respectively.

[0111] There are no particular restrictions on the combination of two or more monomers used; the combination can be set appropriately according to the intended use.

[0112] Examples of polymerizable monomers containing (meth)acryloyl groups include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluene methacrylate, benzyl methacrylate, and propylene methacrylate. 2-Methoxyethyl ester, 3-Methoxybutyl acrylate, stearyl acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, trifluoromethyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl methacrylate, 2-perfluoroethyl methacrylate, perfluorobutyl methacrylate, perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methacrylate, 2-perfluoromethyl 2-perfluoroethyl methacrylate, 2-perfluorohexyl methacrylate, 2-perfluorodecyl methacrylate, or 2-perfluorohexadecyl methacrylate, etc.

[0113] Examples of aromatic vinyl monomers include: styrene; alkylstyrene such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-ethylstyrene, p-isopropylstyrene, p-n-butylstyrene, p-tert-butylstyrene, α-methylstyrene, or α-methylp-methylstyrene; alkoxystyrene such as o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, or p-tert-butoxystyrene; halostyrene such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, or p-bromostyrene; hydroxystyrene such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, or 3,5-dihydroxystyrene; or styrene sulfonic acid or its alkali metal salt; and so on.

[0114] If examples of vinyl carboxylic acids are given, specific examples include vinyl formate, vinyl acetate, vinyl propionate, or vinyl neopentanoate, which are vinyl carboxylic acids with 3 or more but less than 10 carbon atoms.

[0115] Examples of conjugated diene monomers include butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, isoprene, 3-butyl-1,3-octadiene, or 1-phenyl-1,3-butadiene, which are conjugated dienes with 4 or more carbon atoms and 16 or fewer carbon atoms.

[0116] If we give examples of olefin monomers, we can specifically mention olefins with 2 or more carbon atoms but less than 10, such as ethylene, propylene, 1-butene, 2-butene, or isobutene.

[0117] If we were to give examples of halogenated ethylene, we could specifically mention: vinyl fluoride, vinyl chloride, or vinyl bromide, etc.

[0118] If we were to give examples of vinylidene halide, we could specifically mention vinylidene fluoride, vinylidene chloride, or vinylidene bromide, etc.

[0119] If we give examples of allyl halides, specific examples include allyl fluorine, allyl chloride, or allyl bromide, etc.

[0120] The polymer used for manufacturing is preferably a polymer for photoresist. In the case of a polymer for photoresist, a monomer having a chemical structure exhibiting photosensitivity is used instead of the aforementioned monomer, or used together with the aforementioned monomer. For example, in the case of manufacturing a polymer for a chemically amplified photoresist using a photoacid generator, the monomer preferably contains a group having a portion of which detaches under the action of acid to generate a polar group (sometimes called an "acid-degrading group"). The polarity of the polymer for photoresist increases due to the action of acid, thereby increasing its solubility in alkaline developing solutions, enabling the formation of patterns.

[0121] Examples of polar groups include acidic groups or hydroxyl groups. Examples of acidic groups include: phenolic hydroxyl groups; carboxyl groups; fluoroalcohol groups such as hexafluoro-2-hydroxyisopropyl; 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; tri(alkylcarbonyl)methylene groups, or tri(alkylsulfonyl)methylene groups, etc. Among these, the preferred polar groups are carboxyl groups, fluoroalcohol groups, or sulfonic acid groups.

[0122] As an acid-degrading group, it is preferable to have a group obtained by replacing the hydrogen atom of the above-mentioned polar group with a group that is degraded by acid. Examples of acid-degrading groups include: -C(R I (R) II (R) III The group represented by ) or -C(R IV (R) V (OR) VI Groups, etc., represented by ) in the above formula. I ~R III and R VI Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R IV and R V Each can independently represent a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. I ~R III At least two groups in it can also bond with each other to form a ring. Additionally, R IV With R V They can also bond together to form a ring.

[0123] The lower limit of the number of carbon atoms in the acid-degrading group is not particularly limited, but it is preferably 4 or more, more preferably 5 or more. The upper limit of the number of carbon atoms in the acid-degrading group is not particularly limited, but it is preferably 20 or less.

[0124] R I ~R VI The alkyl group represented is preferably an alkyl group having 1 or more and 8 or fewer carbon atoms. Examples of alkyl groups having 1 or more and 8 or fewer carbon atoms include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, or octyl.

[0125] R I ~R VI The cycloalkyl group can be either a monocyclic or a polycyclic (bridged) cycloalkyl group. Examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cyclooctyl, which have 3 or more but less than 8 carbon atoms. Examples of polycyclic cycloalkyl groups preferably include adamantyl, norbornyl, isobornyl, camphoryl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, or androstyl, which have 6 or more but less than 20 carbon atoms. In the above-mentioned cycloalkyl groups, the carbon atoms other than position 1 of the carbon atom constituting the cycloalkane ring may optionally be replaced by heteroatoms such as oxygen atoms. In this case, the number of carbon atoms replaced by heteroatoms is not particularly limited.

[0126] As R I ~R VI The aryl group represented is preferably phenyl, naphthyl, or anthracene, which have 6 or more but less than 14 carbon atoms.

[0127] As R I ~R VI Aryl groups, for example, preferably include aryl groups with 7 or more and 12 or fewer carbon atoms, such as benzyl, phenethyl, or naphthylmethyl.

[0128] As R I ~R VI The alkenyl group represented is preferably, for example, vinyl, allyl, butenyl, or cyclohexenyl, which have 2 or more but less than 8 carbon atoms.

[0129] R I ~R III The ring formed by the bonding of at least two groups in the ring, and R IV With R V The ring formed by bonding is preferably a cycloalkane ring. Examples of such cycloalkane rings include monocyclic cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane; and polycyclic cycloalkane rings such as norbornene, tricyclic decane, tetracyclic dodecane, or adamantane.

[0130] It should be noted that R I ~R VI The alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups, or the aforementioned cycloalkane rings, may each have substituents to a extent that does not impede the polymerization reaction.

[0131] As an acid-degrading group, tert-butyl, tert-pentyl, or groups represented by formulas (I) to (IV) below are preferred.

[0132] [Chemical Formula 1]

[0133]

[0134] R in equations (I) to (IV) 2 ~R 7 R a , n, p or ring Z 1 R in equations (a1) to (a4) described later are respectively 2 ~R 7 R a , n, p or ring Z 1 The meanings are the same.

[0135] Acid-degrading groups can bond to polymerizable functional groups through spacer groups. Examples of such spacer groups include the linking group represented by A in formula (1) described later.

[0136] As a monomer having an acid-degradable group, examples include monomers represented by the following formula (1).

[0137] [Chemical Formula 2]

[0138]

[0139] In equation (1), R 1 This indicates an acid-degrading group. Furthermore, in formula (1), R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 or more but less than 6 carbon atoms optionally containing a halogen atom. Examples of halogen atoms that are optional alkyl groups having 1 or more but less than 6 carbon atoms include chlorine atoms, bromine atoms, or iodine atoms. Examples of alkyl groups having 1 or more but less than 6 carbon atoms optionally containing a halogen atom include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, or hexyl. Examples of alkyl groups having 1 or more but less than 6 carbon atoms optionally containing a halogen atom include trifluoromethyl and 2,2,2-trifluoroethyl.

[0140] In formula (1), A represents a single bond or a linking group. Examples of such linking groups include: carbonyl (-C(=O)-), ether (-O-), ester (-C(=O)-O-), amide (-C(=O)-NH-), carbonate (-OC(=O)-O-), groups formed by multiple links of these, or groups formed by alkylene groups bonded to them. Examples of alkylene groups include: linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, or trimethylene; or divalent alicyclic hydrocarbon groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, or cyclohexylene (especially divalent cycloalkylene groups); etc.

[0141] As the monomer represented by formula (1), one or more monomers selected from the monomers represented by formulas (a1) to (a4) below are preferred.

[0142] [Chemical Formula 3]

[0143]

[0144] In formulas (a1) to (a4), R is the same as R in formula (1), representing a hydrogen atom, a halogen atom, or an alkyl group having 1 or more but less than 6 carbon atoms, and A represents a single bond or a linking group. A in formulas (a1) to (a4) is preferably a single bond or a group formed by the bonding of an alkylene group and a carbonyl group (alkylene-carbonyl group). 2 ~R 4 Each of the following independently represents an alkyl group having 1 or more but less than 6 carbon atoms and optionally a substituent. R 2 and R3 They can be arbitrarily bonded together to form a ring. R 5 and R 6 Each of the following can independently represent a hydrogen atom or an alkyl group having 1 or more but less than 6 carbon atoms and optionally a substituent: R 7 Indicates -COOR c Base. R c This indicates an optional tertiary hydrocarbon group, tetrahydrofuranyl, tetrahydropyranyl, or oxehexylheptanyl group with substituents. n represents an integer greater than or equal to 1 and less than or equal to 3. When n is 2 or 3, it represents 2 or 3 R groups. 7 They can be the same or different. R a It is related to ring Z 1 The bonded substituents independently represent an oxo group, an alkyl group, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a carboxyl group optionally protected by a protecting group. p represents an integer greater than or equal to 0 and less than 3. Z 1 This refers to alicyclic hydrocarbon rings with 3 or more but less than 20 carbon atoms. When p is 2 or 3, it consists of 2 or 3 R atoms. a They can be the same or different.

[0145] As R a Alkyl groups, for example, include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, or n-hexyl, which have 1 or more but less than 6 carbon atoms.

[0146] As R a Examples of hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, or 6-hydroxyhexyl, which have 1 or more but less than 6 carbon atoms.

[0147] As R a The hydroxyl or hydroxyalkyl group may optionally have a protecting group, for example, alkyl groups having 1 or more but less than 4 carbon atoms, such as methyl, ethyl, and tert-butyl; groups that form an acetal bond together with the oxygen atom constituting the hydroxyl group (e.g., methoxymethyl, etc.). 1-4 Alkyl-OC 1-4 Alkyl groups; or groups that form ester bonds with the oxygen atoms that constitute the hydroxyl group (e.g., acetyl, benzoyl, etc.).

[0148] As R a Protecting groups representing carboxyl groups include, for example, alkyl groups with 1 or more but less than 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, or hexyl; 2-tetrahydrofuranyl; 2-tetrahydropyranyl; or 2-oxacycloheptyl, etc.

[0149] As R 2 ~R 6 The alkyl group represents an alkyl group with 1 or more but less than 6 carbon atoms. Examples of such alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, or hexyl, which are straight-chain or branched alkyl groups. 2 ~R 6 The alkyl group having 1 or more and 6 or less carbon atoms preferably has 1 or more and 4 or less carbon atoms, more preferably 1 or more and 3 or less carbon atoms, and even more preferably 1 or more and 2 or less carbon atoms.

[0150] As R 2 ~R 6 The alkyl group represented by the substituent optionally having 1 or more and 6 or less carbon atoms may include, for example, a halogen atom, a hydroxyl group, a substituted hydroxyl group (e.g., an alkoxy group having 1 or more and 4 or less carbon atoms, such as methoxy, ethoxy, or propoxy), or a cyano group. Examples of alkyl groups having substituents that are 1 or more and 6 or less carbon atoms include, for example, a haloalkyl group having 1 or more and 6 or less carbon atoms, such as trifluoromethyl or 2,2,2-trifluoroethyl; a hydroxyalkyl group having 1 or more and 6 or less carbon atoms, such as hydroxymethyl or 2-hydroxyethyl; an alkoxyalkyl group having 1 or more and 6 or less carbon atoms, such as methoxymethyl, 2-methoxyethyl, ethoxymethyl, or 2-ethoxyethyl; or a cyanoalkyl group having 1 or more and 6 or less carbon atoms, such as cyanomethyl or 2-cyanoethyl; and so on.

[0151] In R 2 and R 3 When the rings are formed by mutual bonding, examples of such rings include: alicyclic hydrocarbon rings with 3 or more and 12 or fewer carbon atoms having substituents.

[0152] As R c The tertiary hydrocarbon group can be represented by, for example, tert-butyl or tert-pentyl.

[0153] As R c The tertiary hydrocarbon group may optionally have the following substituents, for example: halogen atom, hydroxyl group, substituted hydroxyl group (e.g., alkoxy group with 1 or more carbon atoms and less than 4 carbon atoms, such as methoxy, ethoxy, or propoxy), or cyano group.

[0154] As Z 1Examples of alicyclic hydrocarbon rings with 3 or more but less than 20 carbon atoms include: monocyclic alicyclic hydrocarbon rings, rings containing norbornene or norbornene rings, adamantane rings, rings formed by hydrogenation of polycyclic aromatic fused rings (preferably rings formed by complete hydrogenation), or bridged rings of 2 to 6 rings. Examples of monocyclic alicyclic hydrocarbon rings include: cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, or cyclooctane rings, which are 3 to 20 quintone (preferably 3 to 15 quintone, particularly preferably 5 to 12 quintone) cycloalkanes; or cyclopropylene rings, cyclobutene rings, cyclopentene rings, or cyclohexene rings, which are 3 to 20 quintone (preferably 3 to 15 quintone, particularly preferably 5 to 10 quintone) cycloalkenes. Examples of rings containing a norbornene ring include: norbornene ring, norbornene ring, bornene ring, isobornene ring, tricyclic ring [5.2.1.0] 2,6 ] Decane ring, or tetracyclic [4.4.0.1 2,5 .1 7,10 Dodecane ring, etc. Examples of polycyclic aromatic fused rings formed by hydrogenation include: perhydroindene ring, decahydronaphthalene ring, tricyclic [7.4.0.0] 3,8 Tridecane rings, or perhydroanthracene rings, etc. Examples of bridged cyclic hydrocarbon rings of the 2-6 ring class include: tricyclic rings [4.2.2.1] 2,5 Undecane ring, etc. For 2-6 ring bridged ring hydrocarbons, the number of carbon atoms is preferably 6 or more and 20 or less.

[0155] Furthermore, the monomer preferably comprises an alicyclic monomer having [-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-OC(=O)-]. Using an alicyclic monomer imparts higher substrate adhesion and etch resistance to the polymer used for photoresist. Hereinafter, an alicyclic monomer having "[-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-OC(=O)-]" will sometimes be referred to as "monomer b".

[0156] Wherein, monomer b is preferably one or more monomers selected from the monomers represented by formulas (b1) to (b5) below. In formulas (b1) to (b5) below, R represents a hydrogen atom, a halogen atom, or optionally an alkyl group having 1 or more but less than 6 carbon atoms, and A represents a single bond or a linking group. X represents a single bond, methylene, ethylene, oxygen atom, or sulfur atom. Y represents a methylene or carbonyl group. Z represents a divalent organic group (for example, alkylene groups exemplified and described as optional alkylene groups included in formulas (a1) to (a4) (especially straight-chain alkylene groups having 1 or more but less than 3 carbon atoms) etc.). V 1 ~V 3 Each can be independently represented as -CH2-, [-C(=O)-], or [-C(=O)-O-]. Where V1 ~V 3 At least one of them is [-C(=O)-O-]. R 8 ~R 14 Each of the following can independently represent a hydrogen atom, a fluorine atom, or an alkyl group optionally containing a fluorine atom, an alkyl group optionally protected by a protecting group, a hydroxyl group optionally protected by a protecting group, a carboxyl group optionally protected by a protecting group, or a cyano group.

[0157] [Chemical Formula 4]

[0158]

[0159] As R and A in equations (b1) to (b5), they can have the same meaning as R and A in equations (a1) to (a4).

[0160] R in equations (b1) to (b5) 8 ~R 14 R represents an alkyl group, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a carboxyl group optionally protected by a protecting group. 8 ~R 14 The alkyl group, optionally protected hydroxyl group, optionally protected hydroxyalkyl group, or optionally protected carboxyl group can be exemplified as R in formulas (a1) to (a4). a The alkyl group, optionally a hydroxyl group protected by a protecting group, optionally a hydroxyalkyl group protected by a protecting group, or optionally a carboxyl group protected by a protecting group are all represented. Furthermore, as R... 8 ~R 14 Alkyl groups, for example, include trifluoromethyl or 2,2,2-trifluoroethyl alkyl halogenated groups having 1 or more but less than 6 carbon atoms.

[0161] The monomers represented by equations (b1) to (b4) may be selected to have one or more R atoms. 8 ~R 11 Preferably, it has 1 to 3 R 8 ~R 11 Furthermore, the monomers represented by equations (b1) to (b4) have more than two R atoms. 8 ~R 11 In the case of 2 or more R 8 ~R 11 They can be the same or different.

[0162] Wherein, monomer b is preferably represented by formula (b1) and R 8 It is a cyano group, or a group having an amide group, a group having an imide group, or fluorine (C 1-6Monomers containing electron-withdrawing groups such as alkyl groups; monomers represented by formula (b2); monomers represented by formula (b3) where Y is a carbonyl group; monomers represented by formula (b4); or monomers represented by formula (b5). The photoresist polymers obtained by polymerizing these monomers exhibit excellent substrate adhesion and etching resistance, and excellent solubility in alkaline developing solutions, thus enabling the formation of fine patterns with high precision.

[0163] In equation (b1), in R 8 When the group is an electron-withdrawing group such as a cyano group, an amide group, an imide group, or a fluoroalkyl group having 1 or more but less than 6 carbon atoms, R is particularly preferred. 8 It is bonded to at least the carbon atom marked * in formula (b1).

[0164] The monomer may further comprise monomer c. Monomer c is a monomer represented by the following formula (c1). The photoresist polymer obtained by polymerization of a monomer comprising monomer c has high transparency and excellent etching resistance. In the formula, R represents a hydrogen atom, a halogen atom, or optionally an alkyl group having 1 or more but less than 6 carbon atoms. A represents a single bond or a linking group. R b This indicates a hydroxyl group, a hydroxyalkyl group, a carboxyl group, or a cyano group that are optionally protected by a protecting group, preferably a hydroxyl or cyano group. q represents an integer from 1 to 5. Z 2 This refers to alicyclic hydrocarbon rings with 6 or more but less than 20 carbon atoms. When q is an integer from 2 to 5, it represents 2 to 5 R atoms. b They can be the same or different.

[0165] [Chemical Formula 5]

[0166]

[0167] The meanings of R and A in equation (c1) are the same as those of R and A in equations (a1) to (a4).

[0168] R in equation (c1) b This indicates a hydroxyl group, a hydroxyalkyl group, or a carboxyl group that is optionally protected by a protecting group. R b The hydroxyl group, hydroxyalkyl group, and carboxyl group optionally protected by the protected group are respectively associated with R in formulas (a1) to (a4). a The terms "optionally protected hydroxyl group", "optionally protected hydroxyalkyl group", and "optionally protected carboxyl group" have the same meaning.

[0169] Z in equation (c1) 2This refers to alicyclic hydrocarbon rings with 6 or more but less than 20 carbon atoms. Examples of alicyclic hydrocarbon rings with 6 or more but less than 20 carbon atoms include: monocyclic alicyclic hydrocarbon rings, rings containing norbornene or norbornene rings, adamantane rings, rings formed by hydrogenation of polycyclic aromatic fused rings (preferably rings formed by complete hydrogenation), or bridged rings of 2 to 6 rings. Examples of monocyclic alicyclic hydrocarbon rings include: 6 to 20 quintone (preferably 6 to 15 quintone, particularly preferably 6 to 12 quintone) cycloalkanes such as cyclohexane or cyclooctane rings; or 6 to 20 quintone (preferably 6 to 15 quintone, particularly preferably 6 to 10 quintone) cycloalkenes such as cyclohexene rings. Examples of rings containing norbornene or norbornene rings include norbornene rings, ... 2,6 ] Decane ring, or tetracyclic [4.4.0.1 2,5 .1 7,10 Dodecane ring, etc. Examples of polycyclic aromatic fused rings formed by hydrogenation include perhydroindene ring, decahydronaphthalene ring, and tricyclic ring [7.4.0.0]. 3,8 Tridecane rings, or perhydroanthracene rings, etc. Examples of bridged ring hydrocarbons of the 2-6 ring class include: tricyclic rings [4.2.2.1] 2,5 Undecane ring, etc. For 2-6 ring bridged hydrocarbon rings, the number of carbon atoms is preferably 6 or more and 20 or less. Among them, Z... 2 Preferably, it contains a norbornene ring or a norbornene ring, or an adamantane ring.

[0170] (2) Polymerization initiator

[0171] A polymerization initiator is a compound that promotes the polymerization reaction of a curable compound through treatment such as heating or light exposure. Polymerization initiators can be thermal polymerization initiators that initiate polymerization by heat, photopolymerization initiators that initiate polymerization by light, or polymerization initiators that initiate polymerization by other means. From the viewpoint of polymer functional performance and processing safety, thermal polymerization initiators are preferred. Furthermore, there are no particular limitations on the type of polymerization initiator; examples include free radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators. A single polymerization initiator can be used, or two or more can be used in combination.

[0172] In addition, the polymerization initiator can be a manufactured polymerization initiator or a commercially available one.

[0173] It should be noted that the polymerization initiator is included in the liquid used in the polymerization process, but it can also be added as an additive in additional polymerization processes.

[0174] Examples of thermal polymerization initiators that initiate free radical polymerization via heat include: peroxides, peroxycarboxylic acids, peroxyesters, ketone peroxides, peroxyketals, diacyl peroxides, or peroxycarbonates containing peroxy or hydrogen peroxide groups; bibenzyl compounds such as diphenylbutane; azo compounds; oxime esters; benzoin compounds; or acetophenone derivatives. From a processing safety perspective, azo compounds are preferred.

[0175] If we take azo compounds as an example, specific examples include: 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2-methylbutanonitrile), 2,2'-azobisisobutanonitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropanediamine) dihydrochloride, 2 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropamidinium] dihydrochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropamidinium] dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propamidinium] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propamidinium] dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropamidinium] dihydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolinium)propane] dihydrochloride [2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazazo-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride [2,2'-Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis(2-methylpropionamide), 2,2'-Azobis(2,4,4-trimethylpentane), 2,2'-Azobis(2-methylpropane), 4,4'-Azobis(4-cyanopentanoic acid), or 2,2'-Azobis[2-(hydroxymethyl)propionitrile], etc.

[0176] Examples of photopolymerization initiators that initiate free radical polymerization by light include: 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0177] Examples of cationic polymerization initiators include protic acids such as hydrochloric acid, sulfuric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, or fluorosulfonic acid; or Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, tin chloride, or ferric chloride.

[0178] Examples of anionic polymerization initiators include: organoalkali metals such as methyllithium, n-butyllithium, sec-butyllithium, or tert-butyllithium; organoalkaline earth metals such as methylmagnesium chloride or methylmagnesium fluoride; or alkali metals such as lithium, sodium, or potassium.

[0179] When using a free radical polymerization initiator, all polymerization initiators used in the reaction system can be free radical polymerization initiators, or only a portion of them can be free radical polymerization initiators. For example, in any additional polymerization step up to the nth time, if a polymerization initiator is added as the above-mentioned additive, the polymerization initiator and the polymerization initiator used in the above-mentioned polymerization step can be free radical polymerization initiators.

[0180] There are no particular restrictions on the content of polymerization initiators and monomers in the liquid containing polymerization initiators and monomers used in the polymerization process. The content can be set to the desired range according to the manufacturing conditions and their types.

[0181] In the polymerization process, the ratio of (total moles of monomers consumed in the polymerization process) / (moles of initiator consumed in the polymerization process) in the liquid containing polymerization initiator and monomers (hereinafter also referred to as "liquid in the polymerization process") is not particularly limited. From the point of view of controlling Mw / Mn, it is usually 0 or more and less than 100, it can be 0 or more and less than 80, it can be 0 or more and less than 60, or it can be 0 or more and more than 30.

[0182] (3) Other ingredients

[0183] Within the scope of the technical effects of this disclosure, the liquid in the polymerization process may contain components other than polymerization initiators and monomers (hereinafter referred to as "other components"), such as solvents, dispersion media, chain transfer agents, modifiers, deprotecting agents, or stabilizers.

[0184] The solvent can be any solvent that dissolves the monomers and polymerization initiators contained in the liquid during the polymerization process; there are no special restrictions, and it can be appropriately selected according to the types of these components.

[0185] If an example of a solvent is given, examples include: water; or organic solvents such as glycol solvents (diol compounds), ester solvents, ketone solvents, ether solvents, amide solvents, sulfoxide solvents, or hydrocarbon solvents. Among these, glycol solvents are preferred from the viewpoint of exhibiting the function of the polymer product. A single solvent may be used, or two or more may be used in combination as a mixed solvent.

[0186] Alternatively, either manufactured solvents or commercially available solvents can be used.

[0187] Examples of glycol solvents include propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, or ethylene glycol monobutyl ether acetate.

[0188] Examples of ester solvents include: lactate solvents such as ethyl lactate; propionate solvents such as methyl 3-methoxypropionate; or acetate solvents such as methyl acetate, ethyl acetate, propyl acetate, or butyl acetate.

[0189] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, or cyclohexanone.

[0190] Examples of ether solvents include: diethyl ether, diisopropyl ether, dibutyl ether, or dimethoxyethane, etc.; or tetrahydrofuran or diethyl ether. Alkane and other cyclic ethers, etc.

[0191] Examples of amide solvents include N,N-dimethylformamide.

[0192] Examples of sulfoxide solvents include dimethyl sulfoxide (DMSO).

[0193] Examples of hydrocarbon solvents include: aliphatic hydrocarbons such as pentane, hexane, heptane, or octane; alicyclic hydrocarbons such as cyclohexane or methylcyclohexane; or aromatic hydrocarbons such as benzene, toluene, or xylene.

[0194] Among these, preferred solvents include glycol solvents such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclopentanone, or cyclohexanone; or mixtures thereof.

[0195] To optimize the efficiency of the polymerization reaction, the liquid in the polymerization process can contain a chain transfer agent.

[0196] There are no particular restrictions on the type of chain transfer agent. Well-known or conventional chain transfer agents used in polymerization reactions can be used, such as chain transfer agents containing mercapto groups, chain transfer agents containing thiocarbonyl thio groups (chain transfer agents containing cyano and thiocarbonyl thio groups, and chain transfer agents containing thiocarbonyl thio groups but without cyano groups), etc. A single chain transfer agent can be used, or two or more can be used in combination.

[0197] In addition, chain transfer agents can be manufactured or commercially available products can be used.

[0198] Examples of chain transfer agents containing a thiol group include: 1-butanethiol, 2-butanethiol, tert-butanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol, 1-octylthiol, 1-decathiol, 1-dodecathiol, 1-tetradecathiol, laurylthiol, cyclohexylthiol, 1-mercaptoethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-1,2-propanediol, triethylene glycol dithiol, p-mercaptophenylmethanol, 2-(p-mercaptophenyl)ethanol, p-(mercaptomethyl)phenylmethanol, 2-(p-(mercaptomethyl)phenyl)ethanol, p-mercaptophenol, p-(mercaptomethyl)phenol, p-(1-mercaptoethyl)phenol, or p-(2-mercaptophenyl)ethanol. Thiols such as thioethyl phenol (preferably thiols having an aliphatic hydrocarbon group having 1 to 20 carbon atoms optionally having a substituent, more preferably thiols having an aliphatic hydrocarbon group having 6 to 12 carbon atoms optionally having a substituent); thiopropionic acid, thiobenzoic acid, mercaptoacetic acid, or thiomalic acid; or thioglycolic acid methyl ester, ethyl mercaptoacetate, n-butyl mercaptoacetate, methyl 2-mercaptopropionate, ethyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, methyl p-mercaptobenzoate, ethyl p-mercaptobenzoate, methyl p-(mercaptomethyl)benzoate, or ethyl p-(mercaptomethyl)benzoate, etc. (preferably alkyl thioglycolic acid esters). One or more of the above-mentioned thiol-containing chain transfer agents may be used.

[0199] Examples of chain transfer agents containing cyano and thiocarbonyl thio groups include: 2-cyano-2-propyl 4-cyanobenzodithioate, 4-cyano-4-(phenylthiocarboxylthio)pentanoic acid, 2-cyano-2-propyl benzodithioate, or 4-cyano-4-(phenylthiocarboxylthio)pentanoic acid N-succinimide and other dithiobenzoic acid esters containing cyano groups; 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]pentanoic acid, 2-cyano-2-propyl dodecyl trithiocarbonate, 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]pentanol, poly(ethylene glycol) methyl ether 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]pentanoic acid, poly(ethylene glycol) methyl ether (4-cyano-4-pentanoic acid dodecyl trithiocarbonate) Chain transfer agents containing cyano groups, such as cyanomethyl methyl (phenyl) dithiocarbamate, cyanomethyl diphenyl dithiocarbamate, 1-succinimide-4-cyano-4-[N-methyl-N-(4-pyridyl)thiocarbamate-thio]valerate, 2-cyanopropane-2-ylN-methyl-N(pyridyl-4-yl)dithiocarbamate, or cyanomethyl methyl (4-pyridyl)dithiocarbamate; or chain transfer agents containing cyano groups, such as xanthate esters. Preferably, 4-cyano-4-(phenylthiocarbamoylthio)valerate, or 2-cyano-2-propylbenzodithioate, 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valerate, or 2-cyano-2-propyldodecyltrithiocarbonate.

[0200] Examples of chain transfer agents containing thiocarbonyl thio groups but without cyano groups include: 2-phenyl-2-propylbenzodithioate, 1-(methoxycarbonyl)ethylbenzodithioate, benzylbenzodithioate, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, methyl 2-phenyl-2-(phenylthioformylthio)acetate, ethyl 2-(phenylthioformylthio)propionate, or bis(thiobenzoyl)disulfide, etc., which are cyano-free dithiobenzoate chain transfer agents; 2- (dodecylthiocarbonylthio)propionic acid, 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, methyl 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, N-hydroxysuccinimide ester of 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, poly(ethylene glycol) methyl ether (dodecyl trithiocarbonate of 2-methyl-2-propionic acid), poly(ethylene glycol) bis[2-(dodecylthiocarbonylthio)-2-methylpropionic acid], 2-(dodecylthio)-[dodecylthiocarbonylthio]-2-methylpropionic acid Alkylthiothiocarbonylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid pentafluorophenyl ester, poly(ethylene glycol) methyl ether 2-(dodecylthiothiocarbonylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether 2-(dodecylthiothiocarbonylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether 2-(dodecylthiothiocarbonylthio)-2-methylpropionate, poly(ethylene glycol) bis[2 Chain transfer agents such as 2-methyl-2-(phenylthiocarbonylthio)-2-methylpropionate, or bis(dodecylthiocarbonyl) disulfide, which are cyano-free trithiocarbonates; chain transfer agents such as 1H-pyrrole-1-dithiocarboxylic acid benzyl ester, methyl (4-pyridyl)dithiocarbamate, or N,N'-dimethylN,N'-di(4-pyridyl)thiuram disulfide, which are cyano-free dithiocarbamates; or chain transfer agents such as xanthate esters, which are cyano-free. Ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate is preferred.

[0201] The liquid in the polymerization process may contain a modifying agent for modifying (substituting) a portion of the monomer or polymer using other groups. There are no particular restrictions on the type of modifying agent; it can be appropriately selected depending on the purpose, and well-known modifying agents can be used.

[0202] The liquid in the polymerization process may contain stabilizers that inhibit the decomposition of monomers and polymers.

[0203] There are no particular restrictions on the type of stabilizer; it can be selected appropriately according to the purpose. Well-known stabilizers such as tertiary amines can be used.

[0204] The reaction conditions for polymerization in the polymerization process are not particularly limited and can be appropriately set according to the type of monomer and polymerization initiator. For example, the reaction temperature can be above 0°C and below 200°C, or above 20°C and below 150°C. In addition, the reaction time can be above 1 millisecond and below 12 hours, or above 30 seconds and below 2 hours.

[0205] In the polymerization process, there is no particular limit to the number of polymerization treatments; it can be done only once or more than twice.

[0206] There are no particular limitations on the apparatus used for polymerization; any known container capable of performing polymerization reactions can be used. From the viewpoint of easily controlling the molecular weight distribution, it is preferable to use an apparatus having a reaction flow path for the polymerization reaction of the monomers described later. It is particularly preferable to use an apparatus having a reaction flow path for the polymerization reaction of the monomers described later for at least one step selected from the above-described polymerization steps and at least one of the above-described additional polymerization steps.

[0207] (Liquid preparation and processing)

[0208] The polymerization process may further include a liquid preparation process, which involves preparing a liquid containing a polymerization initiator and two or more monomers, prior to the polymerization treatment described above.

[0209] There are no particular limitations on the method for preparing a liquid containing a polymerization initiator and a monomer; known methods can be used, such as adding the polymerization initiator and monomer into a container. In this case, a method can be used to pre-dissolve at least one of the polymerization initiator and monomer in a solvent. In such a method, it is preferable to obtain a liquid containing the polymerization initiator and monomer by circulating them. In particular, for liquid preparation processing, it is preferable to use an apparatus, described later, having an inlet for introducing at least one of the plurality of liquids into the given processing flow path for mixing multiple liquids within a given processing flow path.

[0210] [Additional polymerization process]

[0211] The method for manufacturing the polymer includes adding an additive component to carry out a further polymerization reaction and performing at least one additional polymerization step. The additional polymerization step may include processes other than treatments related to the addition of the additive component (addition treatment) and treatments related to the polymerization reaction (polymerization reaction treatment).

[0212] Additional polymerization steps are steps performed after the polymerization step or other additional polymerization steps. Therefore, regarding the object to which the additional polymerization step is performed, for example, in the case of n (n≥1) additional polymerization steps, the k-th (1≤k≤n) additional polymerization step can be described as a method of processing the liquid containing the polymerization reactants obtained in the above-mentioned polymerization step (in the case of k=1), or the liquid containing the polymerization reactants obtained in the (k-1)-th additional polymerization step (in the case of k≥2), specifically, a method of adding additives to these liquids.

[0213] An example of the polymerization step and additional polymerization step in the polymer manufacturing method of this embodiment is shown below. Figure 1 . Figure 1 The process flow illustrates a method of performing three additional polymerization steps. Specifically, it shows the following: After a polymerization process in which monomers are polymerized to obtain a liquid containing polymer reactants, in the first additional polymerization step, an additional addition process 1 for adding additives and an additional polymerization process 1 for further polymerization of monomers are performed. Then, in the second additional polymerization step, an additional addition process 2 for adding additives and an additional polymerization process 2 for further polymerization of monomers are performed. Finally, in the third additional polymerization step, an additional addition process 3 for adding additives and an additional polymerization process 3 for further polymerization of monomers are performed.

[0214] It should be noted that, as shown in the specific example above, when k is 1, the liquid added in the kth additional polymerization step is the liquid containing the polymerization reactants obtained in the polymerization step; when k is 2 or above, the liquid added in the kth additional polymerization step becomes the liquid containing the polymerization reactants obtained in the (k-1)th additional polymerization step.

[0215] Here, we consider cases where other processes are included between the polymerization step and the additional polymerization step, or between the additional polymerization steps. For example, if a ripening step is included between the polymerization step and the first additional polymerization step, the liquid containing the polymerization reactants obtained in the polymerization step becomes the liquid obtained after the polymerization step and the ripening step. The polymerization reactants obtained in the polymerization step are included not only in the liquid obtained after the polymerization step but also in the liquid obtained after the ripening step. Similarly, if a purification step is included between the first additional polymerization step and the second additional polymerization step, the liquid containing the polymerization reactants obtained in the first additional polymerization step becomes the liquid obtained after the first additional polymerization step and the purification step. The polymerization reactants obtained in the first additional polymerization step are included not only in the liquid obtained after the first additional polymerization step but also in the liquid obtained after the purification step.

[0216] The number of additional polymerization steps, n, can be 1 or more without particular restriction. However, from the viewpoint of easily controlling the molecular weight distribution of the polymer, a larger n is preferred. Specifically, it can be 2 or more, 3 or more, 5 or more, 10 or more, 20 or more, 50 or more, 100 or more, or even larger. Furthermore, from the viewpoint of manufacturing efficiency, it is preferable that n is not too large; for example, it can be less than 10,000, less than 5,000, less than 1,000, less than 500, less than 100, less than 50, or less than 10.

[0217] (Add processing)

[0218] There are no particular limitations on the method of adding the additive component (addition process), and it can be carried out by known methods or by a combination of known methods. The additive component must include at least one of the two or more monomers used in the polymerization step, and may also include other components such as polymerization initiators, to the extent that the technical effects of this disclosure are obtained. Examples of such other components include those mentioned in the above-described polymerization steps. Furthermore, in the case of multiple additional polymerization steps, the additive component added in each additional polymerization step may be the same or different. It should be noted that an additional polymerization step only needs to include at least one step of adding an additive component that includes at least one of the two or more monomers used in the polymerization step; to the extent that the effects of this disclosure are obtained, it may also include an additional polymerization step that only adds a monomer not used in the polymerization step.

[0219] The type of monomer used in the polymerization process or in other additional polymerization processes can be the same as or different from the type of monomer used in the polymerization process itself. For example, in any additional polymerization process up to the nth time, the type of monomer (monomer type A) can be at least partially the same as the type of monomer (monomer type B) used in the above-mentioned polymerization process (or the polymerization process and other additional polymerization processes). Furthermore, monomer type A and monomer type B can be exactly the same or completely different. Additionally, there can be one type of monomer or two or more types.

[0220] It should be noted that other ingredients can also be added.

[0221] The monomers, polymerization initiators and other components that can be used in the additional polymerization step can also be the same monomers, polymerization initiators and other components described in the polymerization step.

[0222] There are no particular limitations on the monomer composition ratio in the copolymer to be obtained in each additional polymerization step, and it can be appropriately set according to the intended use of the copolymer. For example, if it is a binary system, the molar ratio can be 5~95:95~5, 10~90:90~10, 20~80:80~20, 30~70:70~30, 40~60:60~40, or 50:50.

[0223] In the additive process, the amount of the above-mentioned additive is controlled in such a way that the composition ratio of monomer units in the polymer reactants obtained in each additional polymerization step reaches a given ratio.

[0224] There are no particular limitations on the means of performing the above-mentioned control, but it is preferable to do so in a manner that yields a copolymer with the desired monomer composition ratio. Specifically, for example, from the viewpoint of easily obtaining a copolymer with the desired monomer composition ratio throughout the reaction, when the added component contains two or more monomers, it is preferable that the amount of each monomer added in at least one additional polymerization step, preferably in at least two or more additional polymerization steps, more preferably in at least half of the additional polymerization steps in total, and even more preferably in all additional polymerization steps, is determined based on the polymerizability of each monomer as evaluated by the following evaluation method.

[0225] (Evaluation Method)

[0226] When a polymer is produced by polymerizing each monomer using a solution containing the same molar amount of each monomer, and the molar amounts of each monomer unit in the polymer are compared, the monomer constituting the monomer unit with the larger molar amount is considered the monomer with high polymerizability, and the monomer constituting the monomer unit with the smaller molar amount is considered the monomer with low polymerizability.

[0227] The addition of the additive can be performed manually or automatically. Specifically, it is preferable to use an apparatus (device) with an information providing unit that provides information on the amount of monomer to be added. More preferably, it is preferable to use an apparatus (device) with a control unit that can control the addition of the additive in a manner that ensures the amount of monomer added is within a desired range.

[0228] Furthermore, from the viewpoint that it is easy to obtain copolymers with the desired monomer composition ratio throughout the reaction, it is more preferable that the addition of the additives in at least one additional polymerization step is carried out in a manner that at least satisfies the following condition (1).

[0229] Condition (1): If a / b is less than A / B, then let α > β.

[0230] α: The molar amount of monomer A added

[0231] β: The molar amount of monomer B added

[0232] A: The molar amount of monomer units from monomer A in the target polymer.

[0233] B: The molar amount of monomer units from monomer B in the target polymer.

[0234] a: The molar amount of monomer A in the reactive polymer when evaluated using monomers A and B based on the above evaluation method.

[0235] b: The molar amount of monomer B in the reactive polymer when evaluated using monomers A and B according to the above evaluation method.

[0236] Condition (1) is preferably satisfied in the first half of the reaction, specifically, preferably in at least the first additional polymerization step in all additional polymerization steps, and more preferably in at least the first half of the additional polymerization steps in all additional polymerization steps.

[0237] Furthermore, from the viewpoint of easily obtaining copolymers with the desired monomer composition ratio throughout the entire reaction, in the case of n (n≥1) additional polymerization steps, the k-th (1≤k≤n) additional polymerization step processes the liquid containing the polymer reactants obtained in the above polymerization steps (in the case of k=1), or the liquid containing the polymer reactants obtained in the (k-1)-th additional polymerization step (in the case of k≥2).

[0238] Preferably, in controlling the following M ki M ka and M kf Simultaneously, the additives for the kth additional polymerization step are added.

[0239] M ki The molar amount of each monomer unit in the reactive polymer contained in the liquid at the start of the k-th additional polymerization step.

[0240] M ka The molar amount of each monomer added in the k-th additional polymerization step.

[0241] M kf The molar amount of each monomer unit in the reactive polymer contained in the liquid at the end of the k-th additional polymerization step.

[0242] The first addition process in the polymerization step (hereinafter, sometimes referred to as the "first addition process") is the process of adding an additive to the liquid containing the polymerization reactants obtained in the polymerization step. The kth (k≥2)th addition process in the polymerization step (hereinafter, sometimes referred to as the "kth addition process") is the process of adding an additive to the liquid containing the polymerization reactants obtained in the (k-1)th addition process. This means that the first addition process is different from the monomer supply process in the polymerization step, and the kth (k≥2)th addition process is different from the monomer addition process in the (k-1)th addition process. In other words, while the additive supply in the polymerization step is continuous, the addition of additives in subsequent addition processes is not continuous; rather, the overall operation corresponds to the monomer supply process in the polymerization step. Similarly, in the case of continuously adding monomers in the (k-1)th (k≥2)th additional polymerization step, it is not the case that the subsequent kth monomer addition process is continuously performed, but rather that the continuous supply as a whole operation corresponds to the addition of monomers in the (k-1)th additional polymerization step.

[0243] In addition, from the viewpoint of easily obtaining copolymers with the desired monomer composition ratio, it is preferable that in at least one additional polymerization step, at least one monomer X (which may be one or more monomers) contained in the added component that is repeated with the two or more monomers mentioned above, respectively, satisfies the following condition (2).

[0244] Condition (2): x1 and x2 are different.

[0245] x1: The weight ratio of monomer X in the liquid relative to 100 parts by weight of the total monomer in the polymerization process.

[0246] x2: The weight ratio of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0247] From the viewpoint of easily obtaining copolymers with the desired monomer composition ratio, if there are two or more monomers X in the added components that are repeated with the two or more monomers mentioned above, all monomers X can satisfy the above condition (2) respectively.

[0248] Furthermore, from the viewpoint that it is easy to obtain copolymers with the desired monomer composition ratio throughout the entire reaction, it is preferable to satisfy the above condition (2) in all additional polymerization steps.

[0249] Furthermore, from the viewpoint of easily obtaining copolymers with the desired monomer composition ratio, it is more preferable that, in at least one additional polymerization step, at least one monomer X (which may be one or more monomers) contained in the added component that is repeated with the two or more monomers mentioned above, satisfies the following condition (3).

[0250] Condition (3): The value x3 represented by (x1 / x2-1)×100 is less than -5 or greater than 5.

[0251] x1: Parts by weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer.

[0252] x2: Parts by weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0253] x1 and x2 have the same meaning as x1 and x2 in the above formula (2).

[0254] From the viewpoint of easily obtaining copolymers with the desired monomer composition ratio, when there are two or more monomers X in the added components that are repeated with the two or more monomers mentioned above, it is more preferable that all monomers X satisfy the above condition (3) respectively.

[0255] Furthermore, from the viewpoint that it is easy to obtain copolymers with the desired monomer composition ratio throughout the entire reaction, it is preferable to satisfy the above condition (3) in all additional polymerization steps.

[0256] In addition, x3 is not particularly limited, but is preferably less than -5, more preferably less than -10, more preferably less than -14, and even more preferably less than -20. Furthermore, it is preferably more than 5, more preferably more than 10, more preferably more than 14, and even more preferably more than 20.

[0257] The preferred method is to perform the addition process while allowing the added ingredient to flow, and it is particularly preferred to use an apparatus described later that has an inlet portion for introducing at least one of the plurality of liquids to be mixed into the given processing flow path in order to mix the plurality of liquids to be mixed in a given processing flow path.

[0258] (Additional aggregation processing)

[0259] Additional polymerization treatment is a process that polymerizes monomers contained in a liquid, and / or monomers that may be contained in an additive.

[0260] There are no particular restrictions on the polymerization method; the same method used in the polymerization process described above can be applied.

[0261] It should be noted that in the additional polymerization process, all or part of the monomers in the liquid may be polymerized. If not all monomers are polymerized, the remaining monomers may be polymerized together with monomers added in subsequent additional polymerization steps. Furthermore, it is preferable that the amount of remaining monomers at the end of each additional polymerization step decreases as the number of additional polymerization steps increases, and preferably that all monomers in the liquid and the added monomers have polymerized at the end of the final additional polymerization step.

[0262] It should be noted that the additional polymerization treatment can be carried out simultaneously with mixing (stirring) the materials contained in the liquid.

[0263] There is no particular limit to the number of additional polymerization processes in each additional polymerization step; it can be done once or more than twice.

[0264] [Other processes]

[0265] Within the scope of the technical effects of this disclosure, the polymer manufacturing method may include steps other than the polymerization step and additional polymerization step described above (hereinafter also referred to as "other steps"). Preferably, these other steps are not steps that initiate a polymerization reaction, such as steps that heat the liquid obtained through the various steps or steps that irradiate the liquid with light that initiates polymerization.

[0266] Other steps include, for example, preparing the components contained in a liquid including a polymerization initiator and monomers before the polymerization step, and preparing additional monomers before an additional polymerization step. These prepared components can be obtained through synthesis or as commercially available products.

[0267] The following is an example of a process other than the preparation process.

[0268] (Cooking process)

[0269] The manufacturing method of polymers may include a maturation process (aging process) after the polymerization process to allow the polymerization reaction of the monomers that have been initiated in the polymerization process to proceed.

[0270] There are no particular limitations on the method for carrying out the polymerization reaction of the monomer. Examples include: maintaining the liquid containing the polymerization reactants obtained from the polymerization process in a static state, or maintaining the liquid while it flows through a flow path in a vessel with a flow path. Furthermore, there are no particular limitations on maintaining the temperature of the monomer during the curing process; it can be room temperature, but a cooling mechanism can also be used to achieve a temperature below room temperature.

[0271] In addition, the polymer manufacturing method may include the same process as the curing process described above after the additional polymerization.

[0272] (Purification process)

[0273] The method of manufacturing the polymer may include a purification step, which purifies the additional polymerization reactants from a liquid containing additional polymerization reactants obtained by an additional polymerization step (in the case of multiple additional polymerization steps, not limited to the last additional polymerization step, but also including intermediate additional polymerization steps).

[0274] There are no particular limitations on the methods used to purify the additional polymerization reactants. Examples include methods using filtration, distillation / concentration, extraction, crystallization, adsorption, membrane separation, solid-liquid separation, or drying. These purification methods can be carried out using well-known techniques, and one or more methods may be used.

[0275] (Product filling process)

[0276] The polymer manufacturing method may include a product filling step, which involves filling the obtained polymer into any container, after the above-described steps, preferably after the purification step.

[0277] There is no particular limitation on the molecular weight of the polymer manufactured by the above manufacturing method. It can be set according to the intended use of the polymer. For example, the weight-average molecular weight (Mw) can be above 1,000 and below 1,000,000, above 2,000 and below 100,000, or above 3,000 and below 20,000.

[0278] In addition, there is no particular limitation on the molecular weight of the polymer manufactured by the above manufacturing method. It can be set according to the intended use of the polymer. For example, the number average molecular weight (Mn) can be 500 or more and 500,000 or less, 1,000 or more and 50,000 or less, or 1,500 or more and 10,000 or less.

[0279] There are no particular limitations on the polydispersity index (Mw / Mn) of the polymer manufactured by the above-described manufacturing method. However, from the viewpoint of easily obtaining polymers with small molecular weight deviations and desired properties, a small polydispersity index (Mw / Mn) is preferred. Specifically, it is preferred to be 3.0 or less, more preferably 2.0 or less, further preferably 1.8 or less, and particularly preferably 1.7 or less.

[0280] The polydispersity index can be determined, for example, by gel permeation chromatography (GPC) of the polymer's weight-average molecular weight (Mw) and number-average molecular weight (Mn), and calculated by dividing the former by the latter. The following conditions can be used as the determination conditions for GPC.

[0281] Device: GPC system (manufactured by Shimadzu Corporation)

[0282] System controller: SIL-20A (manufactured by Shimadzu Corporation)

[0283] Pump: LC-20AD (manufactured by Shimadzu Corporation)

[0284] Degassing device: DGU-20A3R (manufactured by Shimadzu Corporation)

[0285] Column oven: CTO-20AC (manufactured by Shimadzu Corporation)

[0286] RI detector: RID-20A (manufactured by Shimadzu Corporation)

[0287] Chromatographic column: GPC KF-806L (column size: 8.0mm (ID) × 300mm (L), manufactured by Resonac Co., Ltd.) × 3 columns

[0288] Protective post: KF-G 4A (Post size: 4.6mm (ID) × 10mm (L), manufactured by Resonac Co., Ltd.)

[0289] Column temperature: 40℃

[0290] Pool temperature: 40℃

[0291] Eluent: Tetrahydrofuran

[0292] Elution buffer flow rate: 0.8 mL / min

[0293] Injection volume: 35μL

[0294] Analysis time: 60 minutes

[0295] Sample: 5% tetrahydrofuran solution

[0296] Sample used for calibration curve preparation: Polystyrene calibration kit SM-10 (manufactured by Agilent Technologies)

[0297] Polymers manufactured by the above-described manufacturing method can be circulated in the market in the form of polymers, or in the form of mixtures with other components, or in the form of molded parts after molding.

[0298] <Appliances>

[0299] There are no particular limitations on the specific apparatus used to implement the above-described polymer manufacturing method, and it can be an apparatus composed of combinations of known apparatuses. For example, as apparatuses that can manufacture polymers in a flow-through manner, multi-tube heat exchangers, stacked multi-flow reactors, tubular reactors, or double-tube reactors can be cited. However, the inventors have learned through in-depth research that, from the viewpoint of easily obtaining copolymers with the desired monomer composition ratio throughout the reaction, it is preferable to use, in the polymerization step and the additional polymerization step, an apparatus having an inlet section that introduces at least one of the multiple liquids to be mixed into the given processing flow path for mixing multiple liquids in a given processing flow path, or an apparatus having a reaction flow path that allows the polymerization reaction of monomers contained in the mixture of multiple liquids to be mixed to take place. It is particularly preferred to use a reactor having such an inlet section and such a reaction flow path.

[0300] Furthermore, since the specific surface area can be increased, temperature unevenness can be reduced. In addition, since the components are easy to mix, the concentration unevenness of each component can be reduced. Therefore, from the viewpoint of reducing the deviation of monomer composition ratio and molecular weight distribution of copolymer, a microfluidic reactor (also called a "microfluidic reactor") is preferred as an apparatus. As a microfluidic reactor, for example, a microfluidic reactor with a microflow path in a reactor having the above-described flow path is preferred.

[0301] The following describes an example of a microfluidic reactor, but the apparatus used to carry out the above-described method for manufacturing polymers is not limited thereto.

[0302] A microfluidic reactor is a reactor that forms micro-flow paths (micro-flow channels) with flow path widths on the order of μm. There are no particular limitations on microfluidic reactors; they can be chip-type microfluidic reactors with micro-flow paths formed inside or on the surface of a substrate, or tubular-type microfluidic reactors with micro-flow paths formed inside a tube. Chip-type microfluidic reactors can also be called microfluidic chip reactors, and tubular-type microfluidic reactors can also be called microfluidic tube reactors.

[0303] Microchannels can be formed inside or on the surface of a substrate. The cross-sectional shape of the microchannels is not particularly limited and can be appropriately selected according to the purpose; examples include circular, rectangular, semi-circular, and triangular shapes. Furthermore, the width (inner diameter) and cross-sectional area of ​​the microchannels are not particularly limited as long as they do not impair the technical effects of this disclosure and can be appropriately selected according to the purpose. For example, the width of the reaction flow path is preferably 15 mm or less, more preferably 20 μm or more and 1000 μm or less, and even more preferably 100 μm or more and 500 μm or less. If the flow path width exceeds 15 mm, the surface area per unit volume becomes smaller, which can sometimes lead to difficulties in rapid mixing and heat dissipation. If the flow path width is greater than 1000 μm, the diffusion distance of molecules becomes longer, thus reducing mixing efficiency and sometimes resulting in a decrease in the function of the microfluidic reactor. Additionally, if the flow path width is less than 20 μm, the pressure loss of the liquid flowing in the flow path increases, requiring a high-pressure pump for liquid delivery, which can sometimes lead to higher manufacturing costs. Furthermore, the cross-sectional area of ​​the reaction flow path is preferably set to 0.0001 mm. 2 Above and 225mm 2 Hereinafter, more preferably, is set to 0.0003mm 2 Above and 1mm 2 The following is a further preferred setting: 0.01mm 2 Above and 0.25mm 2The following applies. Furthermore, the length of the flow path formed in the microfluidic reactor (flow path length) is not particularly limited and can be appropriately set according to the mixing time and reaction time. Preferably, the flow path length is 10 mm or more and 500 mm or less, more preferably 20 mm or more and 1000 mm or less, and even more preferably 50 mm or more and 500 mm or less. The volume of the flow path formed in the microfluidic reactor is not particularly limited and can be appropriately set according to the mixing time and reaction time. Preferably, the volume of the reaction flow path is 0.001 μL or more and 112500 μL or less, more preferably 0.0006 μL or more and 1000 μL or less, and even more preferably 0.5 μL or more and 1000 μL or less. It can also be 1 μL or more and 1000 μL or less, 5 μL or more and 500 μL or less, or 10 μL or more and 100 μL or less. Furthermore, the flow rate of the liquid flowing in the microflow path of the microfluidic reactor is not particularly limited and can be appropriately selected according to the purpose. For example, in polymer manufacturing, it is preferably set to 0.000001 mL / min or more and 10 mL / min or less, more preferably 0.00001 mL / min or more and 0.1 mL / min or less, and even more preferably 0.0001 mL / min or more and 0.05 mL / min or less. If the flow rate is within the above range, there is a tendency to achieve rapid mixing of monomer components and polymerization initiators, and thus a tendency to suppress pressure loss. It should be noted that the above refers to the flow rate of the fluid immediately after being introduced into the microflow path.

[0304] Microfluidic reactors can have reaction-promoting mechanisms to facilitate reactions. The reaction-promoting mechanism is not particularly limited and can be appropriately selected according to the desired chemical reaction. Examples of reaction-promoting mechanisms include: heating mechanisms, illumination mechanisms, vibration energy imparting mechanisms, and voltage application mechanisms. Examples of heating mechanisms include heaters and microwave irradiation devices; examples of illumination mechanisms include LEDs, organic light-emitting devices (OLEDs), lasers, or arc lamps; examples of vibration energy imparting mechanisms include ultrasonic generators and piezoelectric transducers; and examples of voltage application mechanisms include electrodes. A reaction-promoting mechanism can include at least one of the above-mentioned mechanisms, or a combination of several. For example, a reaction-promoting mechanism can heat the fluid in the reaction flow path using a microwave irradiation device as a heating mechanism, or it can irradiate the fluid in the reaction flow path with light using an illumination device that is an illumination mechanism employing various light sources.

[0305] There are no particular limitations on the type of microfluidic reactor. From the viewpoint of being able to easily control the molecular weight distribution of the polymer, a reactor having an inlet and a reaction flow path is preferred. The inlet introduces at least one of the plurality of liquids to be mixed into the given processing flow path for mixing the liquids. The reaction flow path is disposed downstream of the inlet and is formed in the microfluidic reactor as a micro-flow path constituting part of the given processing flow path. The reaction flow path allows the chemical reaction of the reactants contained in the plurality of liquids to take place.

[0306] <Polymer Manufacturing Systems>

[0307] The inventors conducted further in-depth research and found that, from the viewpoint of easily obtaining copolymers with the desired monomer composition ratio throughout the entire reaction, the system shown below as an example is preferred in the above-described polymer manufacturing method.

[0308] The polymer manufacturing system used to implement the above-described polymer manufacturing method is a microfluidic system comprising multiple microfluidic reactors with microflow paths.

[0309] The polymer manufacturing system includes an inlet and a reaction flow path. The inlet introduces at least one of the plurality of liquids to be mixed into the given processing flow path for mixing. The reaction flow path is disposed downstream of the inlet and is formed in the microfluidic reactor as a micro-flow path constituting part of the given processing flow path. The reaction flow path enables the chemical reaction of the reactants contained in the mixture of the plurality of liquids to take place.

[0310] The aforementioned reaction mechanisms are arranged in series in a manner that connects them to each other via the aforementioned reaction flow paths.

[0311] The volume of the reaction flow path in at least one of the above-mentioned reaction mechanisms may be different from the volume of the reaction flow path in the other above-mentioned reaction mechanisms.

[0312] The microfluidic system will be described in detail below, but the system used to implement the above-described method for manufacturing polymers is not limited thereto.

[0313] [Overall Composition]

[0314] First, the overall structure of the polymer manufacturing system 100 will be described. The polymer manufacturing system 100 comprises multiple microfluidic reactors with microflow paths formed on a substrate. More specifically, as... Figure 2As shown, the polymer manufacturing system 100 includes: multiple reactors 10 serving as microfluidic reactors, a heater 20, raw material tanks 30a and 30b, delivery pumps 40a and 40b, a product tank 50, and conduits 60a, 60b, 60c, and 60d. It should be noted that in this embodiment, "upstream side" refers to the raw material tank 30a side of the generation flow path F1 (an example of a "given processing flow path") from the raw material tank 30a to the product tank 50, and "downstream side" refers to the product tank 50 side of the generation flow path F1. It should be noted that the generation flow path F1 is a continuous flow path from the raw material tank 30a, which serves as the fluid supply source, to the product tank 50, which serves as the fluid discharge end.

[0315] The raw material tank 30a contains a solution containing polymerization initiator A (polymerization initiator A solution). The polymerization reaction is initiated by treating polymerization initiator A (hereinafter, sometimes simply referred to as "polymerization initiator A") with heat or light, thereby promoting the polymerization of the monomers. The raw material tank 30b contains a solution containing monomers B and C as reactants (monomer BC solution). Monomers B and C are monomers that polymerize with each other in the presence of polymerization initiator A. Polymer initiator A solution and monomer BC solution are examples of the "multiple mixed liquids" disclosed herein.

[0316] like Figure 2 As shown, in the polymer manufacturing system 100, multiple reactors 10, which are multiple microfluidic reactors, are arranged in a flow direction. Reactors 10 adjacent to each other in the flow direction are connected via conduits 60c in a manner that allows them to communicate with each other. Therefore, in the polymer manufacturing system 100, multiple reactors 10 are arranged in series. Furthermore, a heater 20, described later, is provided together with each reactor 10.

[0317] Hereinafter, the number of reactors 10 in this embodiment will be referred to as N (N is an integer of 2 or more). The number N of reactors 10 is not particularly limited, but is preferably set to 5 or more. In addition, the kth reactor (k is an integer of 1 or more and less than N) from the upstream side among the plurality of reactors 10 included in the polymer manufacturing system 100 will be referred to as reactor 10k. That is, in the polymer manufacturing system 100, reactors 101, 102, ..., and reactor 10N are arranged sequentially from the upstream side.

[0318] The polymer manufacturing system 100 continuously supplies polymerization initiator A solution and monomer BC solution to the generation flow path F1 via the upstream reactor 101, and continuously supplies (adds) monomer BC solution to the generation flow path F1 via the downstream reactor 10, thereby gradually generating polymer D. The polymer D generated by the polymer manufacturing system 100 is discharged from the downstream reactor 10N among the multiple reactors 10.

[0319] Conduits 60a, 60b, 60c, and 60d are pipes that allow fluid to flow. Conduit 60a connects feed tank 30a and reactor 101 in a communicable manner, and conduit 60b connects feed tank 30b and reactor 10 in a communicable manner. Additionally, conduit 60c connects reactors 10 adjacent to each other in the flow direction in a communicable manner. Conduit 60d connects reactor 10N and product tank 50 in a communicable manner.

[0320] As described above, raw material tanks 30a and 30b are containers for holding polymerization initiator A solution and monomer BC solution, respectively. The polymerization initiator A solution and monomer BC solution are supplied to reactor 10 via conduits 60a and 60b, respectively. Product tank 50 is a container for storing polymer D generated by polymer manufacturing system 100. Polymer D is discharged from reactor 10N to product tank 50 via conduit 60d.

[0321] Liquid delivery pumps 40a and 40b are respectively installed in conduits 60a and 60b. Liquid delivery pumps 40a and 40b are liquid delivery mechanisms used to transport the fluids in raw material tanks 30a and 30b to reactor 10. The polymerization initiator A solution in raw material tank 30a is pressurized within conduit 60a and supplied to reactor 10 by the drive of liquid delivery pump 40a. The monomer BC solution in raw material tank 30b is pressurized within conduit 60b and supplied to reactor 10 by the drive of liquid delivery pump 40b. It should be noted that, for example, liquid delivery pumps include syringe pumps, diaphragm pumps, and pressure-controlled pumps. In this embodiment, for example, instead of using raw material tanks 30a and 30b, syringe pumps containing polymerization initiator A solution and monomer BC solution can be used to supply the solutions to reactor 10.

[0322] [Reactor]

[0323] Next, the structure of reactor 10 will be described. Figure 3 This is a top view of the reactor 10 of this embodiment. The reactor 10 of this embodiment is configured as a microfluidic reactor in which microflow paths (also called microchannels) are formed inside a substrate. The reactor 10 is an example of the "reaction mechanism" disclosed herein. Figure 3 As shown, reactor 10 has a substrate 1, a first flow path 2 and a first inlet flow path 3.

[0324] Substrate 1 is a rectangular plate-shaped component viewed from above. The material of substrate 1 is not particularly limited; for example, silicon, silicon dioxide, quartz, glass, resin, silicon carbide, etc., can be used. From the viewpoint of manufacturing resist polymers, glass chips can be appropriately used as a non-metallic material with solvent resistance.

[0325] The first flow path 2 and the first inlet flow path 3 are formed in the form of grooves on the surface of the substrate 1. The first flow path 2 and the first inlet flow path 3 can be formed, for example, by etching the substrate 1.

[0326] The first flow path 2 is formed in the form of a tiny flow path that constitutes part of the generating flow path F1. For example... Figure 3 As shown, the first flow path 2 has a serpentine shape when viewed from above. A supply port 21 for supplying fluid into the first flow path 2 is formed at one end, and a discharge port 22 for discharging the solution from the first flow path 2 is formed at the other end. That is, the first flow path 2 extends serpentinely and continuously from the supply port 21 to the discharge port 22. Fluid supplied to the supply port 21 flows through the first flow path 2 and is discharged from the discharge port 22. The first flow path 2 includes: a plurality of straight flow paths 23 formed in a straight line and arranged side-by-side in 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 through these straight flow paths 23 and curved flow paths 24.

[0327] Furthermore, in the middle section of the first flow path 2 in the flow direction, more specifically, in the middle section of the upstream straight flow path 23 in the first flow path 2, an inlet section 25 is formed for introducing fluid from the first inlet flow path 3 into the first flow path 2. The inlet section 25 introduces the monomer BC solution into the first flow path 2 to mix the polymerization initiator A solution and the monomer BC solution, which are multiple liquids to be mixed, within the generation flow path F1 (the first flow path 2 in this example). The inlet section 25 is formed as a confluence section with the first inlet flow path 3. That is, the first flow path 2 merges with the first inlet flow path 3 at the inlet section 25. Figure 3 As shown in the enlarged view A1, the inlet portion 25 has a first inlet port 25a that opens into the first inlet flow path 3.

[0328] In this disclosure, the micro-flow path in the reaction mechanism that allows the chemical reaction of reactants contained in a mixture of multiple mixed liquids is referred to as a "reaction flow path". That is, the reaction flow path is the region where the chemical reaction of reactants introduced through the inlet proceeds. In the polymer manufacturing system 100, the region in the first flow path 2 located downstream of the inlet 25 corresponds to the "reaction flow path". The region in the first flow path 2 located upstream of the inlet 25 is designated as the transport flow path 2a, and the region located downstream of the inlet 25 is designated as the reaction flow path 2b. That is, the transport flow path 2a is the region from the supply port 21 to the inlet 25, and the reaction flow path 2b is the region from the inlet 25 to the outlet 22. As detailed later, in the transport flow path 2a of the upstream reactor 101 among the multiple reactors 10, a polymerization initiator A solution is transported. In the transport flow path 2a of the reactor 10 located further downstream than reactor 101, a generating liquid (reaction mixture) containing the polymerization initiator A solution and polymer D is transported. The fluid transported from the first flow path 2a and the monomer BC solution transported from the first inlet flow path 3 merge at the inlet 25 of the first flow path 2 and mix while flowing in the reaction flow path 2b. Furthermore, as detailed later, by heating the mixture flowing in the reaction flow path 2b with the heater 20 to raise it above the reaction temperature, the polymerization reaction of monomer B and monomer C in the presence of polymerization initiator A can be promoted. That is, the reaction flow path 2b is a micro-flow path for mixing the polymerization initiator A solution and monomer BC solution as multiple mixed liquids, and for carrying out the chemical reaction of the mixture of polymerization initiator A solution and monomer BC solution. It should be noted that the reaction mechanism of this disclosure may have multiple inlet sections depending on the type, amount, and timing of the introduction of the liquid being mixed. In this case, the reaction flow path can be defined as a miniature flow path disposed in the reaction mechanism further downstream than the inlet section located at the most downstream side.

[0329] Furthermore, the flow path length (length in the flow direction) of reaction flow path 2b is set as L1. That is, L1 is the flow path length of the first flow path 2 located downstream of the inlet 25, and can be defined as the flow path length from the inlet 25 to the outlet 22. In other words, the flow path length L1 can be defined as the flow path length of the first flow path 2 located downstream of the starting point of mixing of the monomer BC solution and the polymerization initiator A solution introduced from the inlet 25.

[0330] Here, the flow path length L1 of the reaction flow path 2b in the k-th reactor 10k from the upstream side among the multiple reactors 10 included in the polymer manufacturing system 100 is recorded as L1k. That is, the flow path length L1 of the reaction flow path 2b in the reactors 101, 102, ..., and 10N from the upstream side is called L11, L12, ..., and L1N. At this time, in the polymer manufacturing system 100, the cross-sectional area of ​​the flow path 2b of the multiple reactors 101 to 10N is set to be equal (constant), and the flow path length L1 of the reaction flow path 2b in each reactor 10 is set such that L1k < L1(k+1). That is, the flow path length L1 of the reaction flow path 2b in each reactor 10 is set such that the reactor 10 located further downstream has a longer flow path length L1. Therefore, in the polymer manufacturing system 100 of this embodiment, the volume of the reaction flow path 2b is larger the downstream reactor 10. However, the technology disclosed herein is not limited to this, and the volume can be set appropriately.

[0331] 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. A supply port 31 for supplying fluid (in this example, the monomer BC solution) into the first inlet flow path 3 is formed at one end of the first inlet flow path 3, and the other end of the first inlet flow path 3 is connected to the inlet portion 25 of the first flow path 2. Thus, the first inlet flow path 3 and the first flow path 2 are connected via the first inlet port 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 generally Y-shaped structure. 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 port 25a of the inlet portion 25.

[0332] It should be noted that in the technology disclosed herein, the inlet flow path (the first inlet flow path 3 in this example) for introducing fluid into the reaction flow path is not a necessary configuration. For example, the reactor 10 may be configured to directly introduce the monomer BC solution from the inlet section 25 of the first flow path 2 without having the first inlet flow path 3. However, from the viewpoint of efficient mixing, the reaction mechanism preferably has an inlet flow path that guides the fluid to the inlet section. In addition, the reaction mechanism of the present disclosure may have multiple inlet paths.

[0333] like Figure 2As shown, the supply port 21 of the first flow path 2 in the upstream reactor 101 of the plurality of reactors 10 is connected to a conduit 60a for supplying the polymerization initiator A solution from the raw material tank 30a to the first flow path 2. Furthermore, the discharge port 22 of the first flow path 2 in the downstream reactor 10N of the plurality of reactors 10 is connected to a conduit 60d for discharging the product liquid from the first flow path 2 to the product tank 50. Moreover, in reactors 10 adjacent to each other in the flow direction, the discharge port 22 of the first flow path 2 in the upstream reactor 10 and the supply port 21 of the first flow path 2 in the downstream reactor 10 are connected via a conduit 60c. Thus, the first flow path 2 constitutes part of the product flow path F1. Furthermore, the plurality of reactors 10 are arranged in series such that their reaction flow paths 2b are connected. Additionally, a conduit 60b is connected to the supply port 31 of the first inlet flow path 3 in the reactor 10 for supplying monomer BC solution from the raw material tank 30b to the first inlet flow path 3.

[0334] [Heater]

[0335] Heater 20 is an apparatus for promoting a chemical reaction (polymerization reaction) by heating the mixture flowing in the reaction flow path 2b of reactor 10. Heater 20 is an example of the "reaction promotion mechanism" of this disclosure. The heating temperature of heater 20 is not particularly limited and can be appropriately set according to the reaction temperature. Heater 20 heats the mixture in reaction flow path 2b to a temperature above the reaction temperature of the polymerization reaction in order to promote the polymerization reaction of monomers B and C in the presence of polymerization initiator A. It should be noted that the reaction temperature here refers, for example, the decomposition temperature of polymerization initiator A. There is no particular limitation on heater 20, and known heaters such as electric heaters can be used. Here, in this embodiment, heater 20 is provided in reactor 10 in order to promote the chemical reaction of reactants in reaction flow path 2b.

[0336] [Methods for manufacturing polymers using polymer manufacturing systems]

[0337] The following describes a method for manufacturing a polymer using the polymer manufacturing system 100. The polymer in this embodiment is manufactured by continuously supplying a polymerization initiator A solution and a monomer BC solution to a generation flow path F1 comprising multiple first flow paths 2. Specifically, the polymerization initiator A solution is continuously supplied to the first flow path 2 of reactor 101 via a delivery pump 40a, and the monomer BC solution is continuously supplied to the first flow path 2 of each reactor 10 via a delivery pump 40b. The flow rate and velocity of each solution supplied to the first flow path 2 are not particularly limited and can be appropriately set according to the purpose. In the polymer manufacturing system 100, a polymer is generated in each reactor 10. Hereinafter, the generation liquid supplied from the kth reactor 10 (k+1) from the upstream side, i.e., reactor 10k, is referred to as the k-th generation liquid.

[0338] First, the generation of the polymer in the upstream reactor 101 will be described. A polymerization initiator A solution, supplied to reactor 101 via feed pump 40a from feed tank 30a through conduit 60a, is introduced into the first flow path 2 via supply port 21. Conversely, a monomer BC solution, supplied to reactor 101 via feed pump 40b from feed tank 30b through conduit 60b, is introduced into the first inlet flow path 3 via supply port 31. Furthermore, the monomer BC solution transported from the first inlet flow path 3 is introduced into the first flow path 2 via inlet section 25, merging with the polymerization initiator A solution transported in transport flow path 2a. Thus, mixing of the polymerization initiator A solution and the monomer BC solution begins at inlet section 25. The polymerization initiator A solution and the monomer BC solution flow in reaction flow path 2b under pressure from feed pumps 40a and 40b, and are mixed by diffusion mixing with reaction flow path 2b as a mixing field, which serves as a micro-flow path. At this point, the mixture of polymerization initiator A solution and monomer BC solution flows in reaction flow path 2b while being heated by heater 20 to a temperature above the reaction temperature. Thus, the polymerization reaction of monomers B and C in the presence of polymerization initiator A is promoted, generating polymer D. At this point, a portion of polymerization initiator A, at least a portion of monomer B, and at least a portion of monomer C contained in the mixture are consumed through the polymerization reaction. Monomers B and C may polymerize completely or partially.

[0339] Next, the generation of polymer in reactor 10p (p is an integer of 2 or more and less than N), which is located downstream of reactor 101, will be described. The secondary generated liquid (p-1) flowing from reactor 10 (p-1) located directly upstream of reactor 10p through conduit 60c and supplied to reactor 10p is introduced into the first flow path 2 via supply port 21. This secondary generated liquid (p-1) contains polymerization initiator A and polymer D. Additionally, monomers B and C, which have not reacted in the reactors 10 located upstream of reactor 10p, may remain in the secondary generated liquid (p-1). On the other hand, similar to reactor 101, monomer BC solution is supplied to reactor 10p via delivery pump 40b. Then, the monomer BC solution transported from the first inlet flow path 3 is introduced into the first flow path 2 via inlet 25, merging with the secondary generated liquid (p-1) transported in transport flow path 2a. Therefore, monomer BC solution is added to the generating flow path F1 for additional monomer injection. Then, the secondary generating liquid (p-1) containing polymerization initiator A and polymer D is mixed with the added monomer BC solution at the inlet 25 while flowing and mixing in the reaction flow path 2b. Furthermore, the mixture flowing in the reaction flow path 2b is heated by heater 20 to above the reaction temperature, thereby promoting the polymerization reaction of monomer B and monomer C in the presence of polymerization initiator A, and generating new polymer D. At this time, monomers B and C may all polymerize, or some may polymerize residually. In addition, if unreacted monomers B and C remain in the mixture in the reactors 10 upstream of reactor 10p, they can also be polymerized. The p-secondary generating liquid containing polymerization initiator A and polymer D is discharged from outlet 22, flows through conduit 60c and is supplied to reactor 10 (p+1) located directly downstream.

[0340] In the manufacture of polymers using the polymer manufacturing system 100, from the viewpoint of obtaining polymers with a smaller polydispersity index Mw / Mn, it is preferable to adjust the molar ratio of monomers to polymerization initiators (hereinafter sometimes referred to as the "M / I ratio") throughout the reaction time. When using two or more monomers, the amount of the monomer targeted in this M / I ratio is set as the total amount of the two or more monomers. The adjustment of the M / I ratio can be performed by continuously supplying (adding injection) monomer BC solution to the reaction flow path 2b of the reactor 10N, which is located downstream of the upstream reactor 101. In the manufacturing of polymers using the polymer manufacturing system 100, from the above viewpoint, it is preferable that in at least two of the plurality of reactors 10, the reactor 10 located further downstream has a larger M / I ratio in the inlet 25; more preferably, in at least three of the plurality of reactors 10, the reactor 10 located further downstream has a larger M / I ratio in the inlet 25; even more preferably, in at least four of the plurality of reactors 10, the reactor 10 located further downstream has a larger M / I ratio in the inlet 25; and particularly preferably, in the reactor 10 located further downstream has a larger M / I ratio in the inlet 25.

[0341] From the viewpoint of obtaining a polymer with a smaller polydispersity index Mw / Mn, the largest M / I ratio among the M / I ratios in the inlet sections 25 of the plurality of reactors 10p (where p is an integer of 2 or more and less than N) is preferably 1.0 times or more and 5.0 times or less, more preferably 1.0 times or more and 4.0 times or less, and even more preferably 1.5 times or more and 3.0 times or less.

[0342] Furthermore, from the viewpoint of obtaining a polymer with a smaller polydispersity index Mw / Mn, the M / I ratio in the inlet section 25 of the upstream reactor 10 is preferably 1.0 or more and 30.0 or less, more preferably 1.0 or more and 25.0 or less, even more preferably 1.5 or more and 20.0 or less, even more preferably 5.0 or more and 20.0 or less, even more preferably 5.0 or more and 15.0 or less, even more preferably 10.0 or more and 15.0 or less, and particularly preferably 11.0 or more and 15.0 or less.

[0343] From the viewpoint of obtaining polymers with a smaller polydispersity index (Mw / Mn), when the residence time in the overall reaction flow path of the reactor is set to 100, the M / I ratio at residence time 0 relative to the M / I ratio at residence time 80 ((M / I ratio at residence time 0) / (M / I ratio at residence time 80)) is preferably 1.00 or more and 4.00 or less, more preferably 1.30 or more and 4.00 or less, even more preferably 1.50 or more and 4.00 or less, even more preferably 2.00 or more and 4.00 or less, even more preferably 2.50 or more and 4.00 or less, and particularly preferably 3.00 or more and 4.00 or less.

[0344] From the viewpoint of obtaining polymers with a smaller polydispersity index (Mw / Mn), when the residence time in the overall reaction flow path of the reactor is set to 100, the M / I ratio at residence time 0 relative to the M / I ratio at residence time 100 ((M / I ratio at residence time 0) / (M / I ratio at residence time 100)) is preferably 1.00 or more and 20.00 or less, more preferably 1.00 or more and 15.00 or less, even more preferably 1.30 or more and 10.00 or less, even more preferably 1.50 or more and 8.00 or less, even more preferably 2.00 or more and 5.00 or less, even more preferably 2.50 or more and 5.00 or less, and particularly preferably 3.00 or more and 5.00 or less.

[0345] Next, the formation of the polymer in the downstream reactor 10N will be described. The reaction process in reactor 10N is the same as in reactor 10p, therefore detailed descriptions are omitted. Similar to reactor 10p, in reaction flow path 2b of reactor 10N, the (N-1)th secondary product containing polymerization initiator A and polymer D is mixed with an additional monomer BC solution. This mixture is heated by heater 20 to above the reaction temperature, thereby promoting the polymerization reaction and generating new polymer D. At this time, in reaction flow path 2b of reactor 10N, all of the polymerization initiator A contained in the mixture can be consumed through the polymerization reaction of monomer B and monomer C. Furthermore, all of monomer B and all of monomer C contained in the mixture can also be consumed through polymerization reactions.

[0346] The N-stage product liquid containing polymer D is discharged from outlet 22, flows through conduit 60d, and is discharged into product tank 50. Thus, polymer D generated in reactors 101, 102, ..., 10N is recovered. As described above, in the polymer manufacturing method using the polymer manufacturing system 100 of the embodiment, (N-1) additional injections are performed, thereby enabling the mass production of polymer D.

[0347] [The role / effect of polymer manufacturing systems]

[0348] In the polymer manufacturing system 100 of this embodiment, where monomer polymerization is carried out, multiple polymerization processes are performed in the generation flow path F1 by adding monomers to the reactor 10. Therefore, the number of polymer D molecules flowing in the generation flow path F1 increases each time they pass through each reaction flow path 2b from upstream to downstream. That is, the higher the reactor 10 is located, the lower the concentration of polymer D in the reaction flow path 2b, and the relatively higher the concentration of monomers as reactants. Therefore, in the reaction flow path 2b of the reactor 10 located further upstream, especially the most upstream, the monomer concentration is high, resulting in more reaction opportunities and easier polymerization compared to the reaction flow path 2b of the downstream reactor 10. As a result, sometimes the amount of polymer D as a reaction product increases rapidly within the reaction system, causing a deviation in the molecular weight of polymer D. Therefore, from the viewpoint of reducing the polydispersity index Mw / Mn of polymer D, it is preferable to shorten the residence time in the reaction flow path 2b of the reactor 10 located further upstream, thereby suppressing deviations in the molecular weight of the generated polymer D.

[0349] Furthermore, in the polymer manufacturing system 100 of this embodiment, the volume of the reaction flow path 2b can be larger the reactor 10 located further downstream. That is, the volume of the reaction flow path 2b can be smaller the reactor 10 located further upstream. In this case, the residence time in the reaction flow path 2b is shorter in the reactor 10 located further upstream, which can ensure a sufficient reaction rate in the reaction flow path 2b while suppressing deviations in the molecular weight of the generated polymer D. As a result, the polydispersity index Mw / Mn of polymer D can be reduced according to the polymer manufacturing system 100 of this embodiment.

[0350] It should be noted that, from the above-mentioned viewpoint of uniformly mixing multiple liquids and ensuring uniform reaction, the polymer manufacturing system 100 may be equipped with a different type of microfluidic device than the reactor 10. For example, a device may be sandwiched between reactor 10k and reactor 10(k+1) to perform extraction or other chemical / physical processes as unit operations on the fluid flowing in the microfluidic path.

[0351] Furthermore, from the above perspective, the inlet section 25 only needs to introduce at least one of the polymerization initiator A solution and monomer BC solution, which are multiple liquids to be mixed, into the reaction flow path 2b in a manner that includes the reactive substances in the mixture. For example, only the monomer BC solution, or only the polymerization initiator A solution, or both the monomer BC solution and the polymerization initiator A solution can be introduced into the reaction flow path 2b. Additionally, the inlet section 25 can also introduce a fluid different from the polymerization initiator A solution and the monomer BC solution.

[0352] The technology disclosed herein does not limit the volume of reaction flow path 2b to be larger for reactors located further downstream, without setting the volumes of multiple reaction flow paths to be completely equal. It allows the volume of the reaction flow path in at least one reaction unit to differ from the volumes of the reaction flow paths in other reaction units. Therefore, the residence time in the reaction flow path can be set according to the type of reaction, reaction time, etc., occurring in the reaction flow path. Furthermore, the reaction rate can be improved by adjusting the residence time for each of the multiple reaction flow paths. For example, in a reaction unit located further downstream, the volume of the mixed liquid is larger than that in a reaction unit located upstream, which may sometimes reduce the reaction opportunity due to a decrease in the frequency of collisions between reactants. In this case, the reaction rate decreases in the reaction unit located further downstream. By adjusting the reaction flow path of the reaction unit located further downstream, sufficient residence time can be ensured, resulting in an improved reaction rate. Furthermore, the technology disclosed herein can be configured such that the volume of the reaction flow path is smaller the downstream reaction mechanism, depending on various conditions such as the type of reaction and the characteristics of the reactants.

[0353] In the case of using multiple reaction mechanisms, the reaction flow paths of at least two of them can have equal volumes. For example, if the chemical reaction in the downstream reaction mechanism has a higher reaction rate than that in the upstream reaction mechanism, the reaction can proceed sufficiently even if the residence time in the reaction flow path of the downstream reaction mechanism is shorter. Therefore, in such cases, good reaction rates can be achieved in both reaction mechanisms even if the volumes of the two reaction flow paths are equal ("equal" includes identical).

[0354] Furthermore, the polymer manufacturing system 100 of this embodiment is equipped with a heater 20 as a reaction promotion mechanism, thereby promoting the polymerization reaction of monomer B and monomer C in the reaction flow path 2b.

[0355] It should be noted that in the above embodiment, the polymerization initiator A solution and the monomer BC solution were mixed as multiple mixed liquids. However, the multiple mixed liquids may also contain only a fluid containing a polymerization initiator and a fluid containing one monomer. The fluid containing one monomer can be introduced into the reaction flow path 2b of the reactor 10 from the inlet 25. In the reaction flow path 2b of the reactor 10, the monomer is polymerized in the presence of the polymerization initiator.

[0356] In addition, the above method is for the polymerization reaction of monomer B and monomer C introduced into reactor 10, but it is not limited to the reaction between the reactants contained in the mixed liquid (polymerization of monomers, etc.). For example, the fluid containing the reactants and the fluid containing the decomposition catalyst can be mixed as multiple mixed liquids and the decomposition reaction of the reactants can be carried out in the reactor.

[0357] Furthermore, in the above embodiments, a chip-type microfluidic reactor was used as the microfluidic device, but a tubular microfluidic reactor (microfluidic tube reactor) or other types of microfluidic reactors can also be used. For example, reactor 10 can be configured as a microfluidic tube reactor. Also, in the above embodiments, the reaction mechanism is constituted by a single microfluidic reactor (reactor 10), but this approach is not limited to this. The reaction mechanism can be configured to include multiple microfluidic reactors. For example, the inlet and the reaction flow path can be provided in different microfluidic reactors. Alternatively, the inlet may not be formed in the microfluidic reactor.

[0358] <Module>

[0359] As a specific reactor for implementing the polymer manufacturing method described above, an example of multiple reactors 10 arranged in series has been described, but multiple reactors 10 can also be arranged in parallel. In particular, when multiple reactors 10 arranged in series are considered as a single series unit, it is preferable to arrange this series unit in parallel with each other. In the following description, the structure formed by arranging multiple series units of reactors 10 in series in parallel is referred to as a module. This can be treated as a reactor 10. Therefore, the polymer manufacturing system described above can also be configured to use a module as the reactor 10. For example, a module can be used as the reactor 10. Figure 2 The reactors 10 arranged in series as shown are used as series units for processing, and the structure formed by arranging them in parallel is called a module. In addition, the system can use one or more modules.

[0360] There are no particular limitations on the type of module. From the viewpoint of easily controlling the molecular weight distribution of the polymer, a reactor comprising a module is preferably a reactor equipped with a microfluidic reactor 10. In this disclosure, a module equipped with a microfluidic reactor 10 as a reactor 10 included in a module is referred to as a microfluidic module.

[0361] The following describes an example of a microfluidic module, but the apparatus used to implement the above-described method for manufacturing polymers is not limited thereto.

[0362] One embodiment of the microfluidic module for implementing the above-described polymer manufacturing method relates to a microfluidic module having microflow paths formed on a substrate and having a plurality of microfluidic reactors 10 relative to the fluid flowing in the microflow paths, wherein the microfluidic module has a plurality of series units comprising at least a plurality of the aforementioned microfluidic reactors 10 connected in series with each other, and the plurality of series units are arranged in parallel with each other.

[0363] The aforementioned microfluidic reactor is preferably chip-type. In this case, a microfluidic module can be fabricated, which has microflow paths formed on a substrate and includes multiple chip-type microfluidic reactors 10 that perform unit operations on the fluid flowing in the microflow paths. This microfluidic module includes multiple series units comprising at least multiple chip-type microfluidic reactors 10 connected in series with each other, and these multiple series units are connected in parallel with each other. Hereinafter, this preferred microfluidic module will be described.

[0364] There are no particular restrictions on the configuration of the series units in the microfluidic module. It can have a base plate configuration in which multiple chip-type microfluidic reactors 10 contained in the series units connected in parallel are mounted on a base plate.

[0365] The number and configuration of the microfluidic reactors 10 mounted on the base plate of the microfluidic module can be varied, for example, they can be mounted on the base plate in a configuration of 4 longitudinal segments and 10 transverse columns.

[0366] In the case of a polymer manufacturing system with microfluidic modules, the system can be a system with multiple microfluidic modules having a base plate shape.

[0367] In addition, when a polymer manufacturing system includes a microfluidic module, the system may be a microfluidic system having a microflow path formed on a substrate and having multiple microfluidic chips that perform unit operations on the fluid flowing in the microflow path. The microfluidic system has a substrate-shaped microfluidic module in which multiple microfluidic chips connected in parallel to each other are mounted on a substrate.

[0368] Furthermore, these systems can be systems configured with multiple microflow path modules having the aforementioned base plate shape.

[0369] The chip-type microfluidic reactor 10 may include, for example, a substrate and microflow paths formed within the substrate. The cross-sectional shape of the microflow paths is not particularly limited and can be appropriately selected according to the purpose; for example, circular, rectangular, semi-circular, or triangular shapes may be used. The shape of the substrate is not particularly limited; for example, it may be a plate-like component with a rectangular shape when viewed from above. Furthermore, the material of the substrate is not particularly limited; for example, glass, silicon, silicon dioxide, quartz, resin, or silicon carbide may be used.

[0370] Next, one method of forming microflow paths on the substrate of the microfluidic reactor 10 will be described. Here, an example of using the microfluidic reactor 10 as a microchip reactor for mixing and reacting multiple liquids will be described. The number of microflow paths in the microfluidic reactor 10 is not particularly limited; for example, a configuration including a first flow path, a first inlet flow path, and a mixing / reaction flow path can be described. This mixing / reaction flow path can be a microflow path for mixing and reacting multiple liquids.

[0371] Micro-flow paths formed on a substrate can be formed, for example, by etching the substrate, but the method of forming micro-flow paths is not particularly limited. For example, when the substrate is configured as a two-layer structure, after a groove for forming micro-flow paths is formed in the first layer substrate, the second layer cover substrate is bonded to the substrate in such a way that the groove in the substrate is blocked from above, thereby forming micro-flow paths inside the substrate.

[0372] It should be noted that a reaction-promoting mechanism, such as a heater, can be provided on the lower surface of the substrate in the microfluidic reactor 10. The heater heats the fluid flowing in the microflow path (mixing / reaction path 15) within the microfluidic reactor 10. Additionally, a temperature sensor can be disposed on the lower surface of the substrate. The type of heater is not particularly limited; for example, a known heater such as an electric heater can be used. For instance, by heating the fluid flowing in the microflow path (mixing / reaction path) to a reaction temperature range, the chemical reaction of the fluid flowing in the microflow path (mixing / reaction path) can be promoted. Furthermore, the temperature sensor can be, for example, a thermocouple-based sensor.

[0373] The chip-type series unit may include a microfluidic reactor 10 having a mixing / reaction flow path that mixes multiple liquids and causes the reactive components contained in the mixture of the multiple liquids to react. In addition, multiple microfluidic reactors 10 may be included. Furthermore, the volume of the mixing / reaction flow path in at least one of the multiple microfluidic reactors 10 may be different from the volume of the mixing / reaction flow path in the other microfluidic reactors 10.

[0374] Furthermore, there are no particular restrictions on the shape of the mixing / reaction flow path; it can be like... Figure 2 The reaction flow path shown has a serpentine shape. Furthermore, there is no particular limitation on the number of liquid inlets in the microflow path; the number of inlets can be increased or decreased depending on the type of liquid.

[0375] The microfluidic module comprises multiple chip-type series units, each containing at least a plurality of microfluidic reactors 10 connected in series with each other. These series units are connected in parallel with each other; the term "connection" here refers to a fluid connection (hereinafter also referred to as "fluid connection"). That is, each series unit of the microfluidic module contains at least a portion in which multiple microfluidic reactors 10 are connected in series in a fluid manner. For the meaning of "at least," it is sufficient to include a portion in which multiple microfluidic reactors 10 are connected in series with each other; alternatively, a portion (section) in which microfluidic reactors 10 are connected in parallel with each other may be included within a part of the series unit. It should be noted that the number of series units is not particularly limited. For example, the number of chip-type series units provided in the microfluidic module can be a multiple of 2 or 3. For example, the number (parallel number) of chip-type series units provided in the microfluidic module can be 2 or more, 4 or more, 6 or more, or 8 or more. Furthermore, the number (parallel number) of chip-type series units provided in the microfluidic module can be 2. m ×3 n (m and n are integers greater than or equal to 0). In this case, when m + n ≥ 2 and n = 0, m ≥ 3 can be set. The number of parallel units in the series connection of the microfluidic module can be appropriately set according to the type and amount of raw material supplied to the microfluidic reactor 10 by the supply device.

[0376] There are no particular limitations on the number of microfluidic reactors 10 included in the series unit (e.g., the number of microfluidic reactors 10 in series) or the arrangement pattern on the base plate.

[0377] Next, the series connection method of the microfluidic reactors 10 in each series unit will be described. There are no particular restrictions on the way the series units are connected. For example, the outlet at the downstream end of the microflow path in the first microfluidic reactor and the supply port at the upstream end of the microflow path in the second microfluidic reactor can be connected via a connecting conduit. In addition, the connecting conduit can have an internal flow path for fluid circulation.

[0378] The supply port of the k-th segment (k≥2) microfluidic reactor 10 and the discharge port of the (k-1)-th segment microfluidic reactor 10 can be connected via a connector. Through this connector, the internal flow path of the connecting conduit, and various conduits described later, can be liquid-tightly and airtightly connected to the microflow path. The type of conduit is not particularly limited and can be a flexible tube. The conduit can be, for example, formed of a resin such as polyetheretherketone (PEEK). Such connectors and connecting conduits can be used not only for connecting the microfluidic reactors 10 to each other, but also for fluid connections between units connected in series.

[0379] Furthermore, the connecting conduits that link the microfluidic reactors 10 installed on the microfluidic module can be constructed from pipe components different from those of the microfluidic device, but are not limited thereto. For example, multiple microflow paths (microchannels) of the microfluidic reactors 10 and flow paths (channels) connecting the microflow paths of each microfluidic reactor 10 can be formed within the base plate (substrate) of the microfluidic module. That is, the microfluidic module can be constructed entirely from a single substrate. In this case, a portion of the supply conduit for supplying liquid and a portion of the recovery conduit for recovering liquid can be formed by the flow paths (channels) of the microfluidic module formed on the substrate. In this case, the substrate can have a multi-layer structure for the microfluidic module, and the layer forming the microflow paths of each microfluidic reactor 10 and the layer forming the flow paths corresponding to the supply conduit and the recovery conduit can be formed as separate layers.

[0380] Furthermore, the microfluidic module may have a base plate configuration where multiple microfluidic reactors 10 contained within the microfluidic module are mounted on a base plate, but it is not limited to this. That is, the microfluidic module only needs to contain multiple series-connected units connected in parallel, and its configuration is not particularly limited. For example, the microfluidic module may also not have a base plate. In this case, the microflow paths of the series-connected microfluidic reactors 10 can be fluidly connected to each other simply through connecting conduits.

[0381] For example, a block-shaped microfluidic module can be constructed by centrally forming the microflow paths of multiple microfluidic reactors 10 constituting each series unit in a microfluidic module on a substrate, and then stacking such chip-shaped series units. It should be noted that in the chip-shaped series units, the microflow paths corresponding to each microfluidic reactor 10 can be connected in series. Furthermore, multiple microfluidic reactors 10 can be fluidly connected to each other via connecting conduits; for example, the connecting conduits can be connected to the supply and discharge ports of each microfluidic reactor 10.

[0382] Furthermore, the block-shaped microfluidic module can be a stack of multiple chip-shaped series units, or it can be held in a state where the series units are clamped by a pair of retaining plates (upper retaining plate and lower retaining plate). Of course, the number of chip series units held between the upper and lower retaining plates can be multiple. For example, the upper and lower retaining plates can be rectangular flat plates with bolt insertion holes formed at appropriate positions (e.g., the four corners of the plane), and fastened by appropriate fasteners composed of bolts, nuts, etc.

[0383] In a block-shaped microfluidic module, the openings (supply ports, discharge ports, etc.) in the microflow paths of the microfluidic reactors included in each chip-connected unit can be connected vertically between the stacked chip-connected units. For example, in the first (uppermost) microfluidic device 10A, its supply ports are arranged in overlapping positions between each series unit, and the supply ports of the microfluidic reactors 10 in each series unit are connected in parallel. Furthermore, in the upper retaining plate, supply ports can be formed at positions coinciding with the supply ports in each series unit, and discharge ports can be formed at positions coinciding with the discharge ports in each series unit. With this configuration, fluid as raw material can be supplied from each supply port in the upper retaining plate to each supply port in each series unit, and products from each discharge port in each series unit can be recovered from the discharge ports. In addition, with this configuration, the supply ports and discharge ports in each series unit can be directly connected to each other without pipes or the like.

[0384] Furthermore, in the above embodiments, the reaction-promoting mechanism that facilitates the reaction process of the reactive components contained in the mixed liquid flowing in the micro-flow path (mixing / reaction flow path) is not particularly limited. Not only the heater exemplified above can be used, but other heating mechanisms such as microwave irradiation devices can also be employed. In addition to heating mechanisms, reaction-promoting mechanisms such as light-emitting mechanisms, vibration energy-imposing mechanisms, and voltage-applying mechanisms can be used. Examples of light-emitting mechanisms include LEDs, organic light-emitting devices (OLEDs), lasers, and arc lamps. Examples of vibration energy-imposing mechanisms include ultrasonic generators and piezoelectric transducers. Examples of voltage-applying mechanisms include electrodes. Furthermore, the reaction-promoting mechanism can be a combination of the various mechanisms described above.

[0385] When a microfluidic module is used as part of a polymer manufacturing system, the polymer manufacturing system may include a liquid supply device. The relationship between this supply device and the microfluidic module is not particularly limited; for example, when multiple microfluidic modules are used, a supply device corresponding to each microfluidic module may be provided, supplying each microfluidic module with a liquid containing materials such as monomers or polymerization initiators. The type of liquid supplied to each microfluidic module may be the same or different.

[0386] The supply device can be configured with multiple supply units, each including a raw material tank for storing raw materials, a supply conduit, and a pump. In this supply unit, a supply conduit is connected to the pump. When the pump operates, the raw material stored in the raw material tank is pressurized (e.g., liquid is supplied) to the supply conduit, where it flows from upstream to downstream. While liquid can be supplied from one supply unit to multiple units in series, it is also possible to supply liquid from one supply unit to multiple units in series. However, when using multiple supply units, liquid can be supplied from each supply unit to different units in series.

[0387] There is no particular limitation on the type of pump; examples include syringe pumps and diaphragm pumps. The supply conduit may have branch conduits that branch off midway. In this case, the branch conduits are preferably provided only in the number corresponding to the series units contained in each microfluidic module. By configuring it in this way, raw materials can be supplied to each series unit in parallel.

[0388] When using microfluidic modules as part of a polymer manufacturing system, the polymer manufacturing system may include a recovery device for recovering the polymer (or a liquid containing the polymer). This recovery device may be a device for recovering the final polymer, or a device for recovering each microfluidic module, each series unit, or each microfluidic reactor 10. The polymer (or liquid containing the polymer) recovered by the recovery device may be stored in a recovery tank.

[0389] When using a microfluidic module as part of a polymer manufacturing system, the polymer manufacturing system can include a control device. This control device can communicate with, for example, the on / off valves, flow regulating valves, flow sensors, pressure sensors, pumps, heaters, and temperature sensors of the aforementioned supply units via wired or wireless means. The control device, for example, receives status signals output from flow sensors, pressure sensors, temperature sensors, etc., and outputs control signals for controlling the on / off valves, flow regulating valves, pumps, heaters, etc., based on the received status signals.

[0390] When using multiple microfluidic modules with a base plate shape, the multiple microfluidic modules can be configured in multiple segments. For example, a rack can be used to configure the microfluidic modules in each segment of the rack.

[0391] It should be noted that when using a support or similar device to configure multiple microfluidic modules in multiple segments, it is preferable that the microfluidic modules stacked vertically have appropriate gaps between them. In other words, multiple microfluidic modules are arranged in multiple segments with intervals in the vertical direction. Of course, this arrangement of microfluidic modules is just one example, and various other arrangements can be used.

[0392] By using the microfluidic module of this method, the reaction process of the reactive components contained in the mixed liquid can be carried out in the microflow path (mixing / reaction flow path) of the interconnected microfluidic reactors 10 constituting each series unit, thereby obtaining the desired reaction product. Since the microfluidic reactors 10 in each series unit are connected in series, the reaction process in the mixing / reaction flow path can be controlled stepwise and with good precision for each microfluidic reactor 10. For example, by individually setting the heating temperature of the fluid using a heater for each microfluidic reactor 10, the reaction process in the mixing / reaction flow path can be controlled with good precision.

[0393] The microfluidic module has a series unit consisting of reactors 10 arranged in series. However, within this series unit, not only can they be arranged in series, but some reactors 10 can also be arranged in parallel. In addition, series units can be arranged in parallel, but units arranged in parallel can also be arranged in series.

[0394] When using microfluidic modules as part of a polymer manufacturing system, the system can be structured as a block CB if the control device, multiple microfluidic modules, a supply device for supplying raw materials to the multiple microfluidic modules, and a recovery device for recovering products from the multiple microfluidic modules are collectively categorized into these blocks. In this case, the various machines (pumps, on / off valves, flow control valves, etc.) belonging to a single block CB are controlled by their respective control devices, and the status signals from the various sensors contained within that single block CB are input to the corresponding control devices. The number of microfluidic modules belonging to a single block CB can be determined based on the amount of information processed, such as the control signals output to the control devices and the status signals input from the various sensors.

[0395] Next, the volume of the mixing / reaction flow path in the microfluidic reactor 10 will be explained. As described above, in the microfluidic module, multiple microfluidic reactors 10 constituting a series unit are connected in series, and in the microfluidic reactors after the second stage, the additional supply of reactants is carried out continuously in multiple stages. Therefore, in the processing flow path section of the series unit, the downstream microfluidic reactor 10 tends to have a higher flow rate of the mixed liquid flowing in the mixing / reaction flow path. Based on this, from the viewpoint of ensuring that the reaction process in the mixing / reaction flow path proceeds sufficiently and thus effectively obtains the reaction products, it is preferable to ensure a longer residence time of the mixed liquid in the downstream microfluidic reactor 10 in the chip series unit.

[0396] Furthermore, considering the molecular weight of the mixed liquid containing reaction products flowing in the processing flow path of the chip series unit, the more downstream the microfluidic chip 10 (microchip reactor) is in the chip series unit, the greater the tendency for the molecular weight of the reaction products contained in the mixed liquid flowing in the mixing / reaction flow path to increase and the viscosity to rise. Therefore, in the mixing / reaction flow path 15, from the viewpoint of facilitating more uniform mixing of the mixed liquids (raw materials), it is also preferable to ensure a longer fluid residence time in the microfluidic chip 10 (microchip reactor) located more downstream in the chip series unit.

[0397] Therefore, for a series unit, when comparing the volumes of the mixing / reaction flow paths of at least two microfluidic reactors 10 connected in series, the volume of the mixing / reaction flow path can be increased for the microfluidic reactor 10 located further downstream. For example, in a series unit, it is set such that, among a plurality of microfluidic reactors 10 connected in series, the volume of the mixing / reaction flow path is larger for the microfluidic reactor 10 located further downstream.

[0398] In other words, the relationship V1k < V1(k+1) holds when the volume V1 of the mixing / reaction flow path 15 in the kth segment of the microfluidic chip 10k from the upstream side in the multiple microfluidic reactors 10 connected in series in the series unit is denoted as V1k.

[0399] According to the aforementioned microfluidic module, by having multiple microfluidic reactors 10 connected in series in each series unit, complex multi-stage unit operations can be achieved. Furthermore, when using the microfluidic module as part of a polymer manufacturing system, due to the presence of multiple series units connected in parallel, numbering up is possible, and the yield of polymer after unit operations in each series unit can be easily increased. That is, by connecting multiple series units in parallel, the production volume (industrial production volume) of the final product after unit operation processing can be ensured. A large-scale polymer manufacturing system composed of such series and parallel combinations of microfluidic reactors 10 can be called a desktop chemistry plant.

[0400] As described above, the aforementioned technique can be defined as a scaling-up method. That is, a scaling-up method is a scaling-up method that increases the number of series units (parallel units) in a microfluidic module to achieve scaling. Alternatively, the aforementioned technique can also be defined as a microfluidic module design method. That is, a microfluidic module design method is a method for determining the number of parallel units in a series unit based on the target production quantity (target output quantity) of the final product obtained in the microfluidic module after unit operation processing. The final product after unit operation processing refers to the final product generated by performing unit operations on the fluid through each series unit configured in the microfluidic module (the base plate). The target production quantity refers to the target production quantity (target output quantity) of the final product in each microfluidic module. By determining the number of parallel units in the series unit configured in the microfluidic module (the base plate) based on this target production quantity (target output quantity), a final product conforming to the target production quantity (target output quantity) can be obtained in each microfluidic module.

[0401] Furthermore, since the aforementioned microfluidic modules have a base plate shape, even if the number of microfluidic modules included in the system is increased, the overall system compactness can be achieved. For example, even when multiple microfluidic modules are set on the support shown in the example above, by setting the microfluidic modules in a base plate shape, the installation space will not occupy a large volume, and more microfluidic modules can be set in a limited space. That is, by stacking multiple microfluidic modules with a base plate shape and arranging them in multiple segments (hierarchical), the number of modules is easily increased, and the product yield can be easily improved. That is, by increasing the number of multiple microfluidic modules with a base plate shape in multiple segments, it is possible to balance the high-precision chemical / physical process based on tandem units with the mass production of products at a high level. In other words, the technology of this method can also be defined as a number-scale method that increases the number of microfluidic modules in the system. In addition, the technology of this method can also be defined as a system design method that determines the number of microfluidic modules in the system based on the target production volume of the final product obtained from the unit operation processing in multiple microfluidic modules. Regarding the final product obtained from the unit operation processing, as described above. The target production quantity of the final product mentioned here refers to the total amount of the final product obtained in multiple microfluidic modules; it is the sum of the final products obtained in each individual microfluidic module. In other words, the total amount of the final product can be determined on a system-wide basis. Thus, by determining the number of microfluidic modules included in the system based on the target production quantity (target output quantity) of the final product when observed in the system as a whole, it is possible to obtain a final product that meets the target production quantity (target output quantity) in the system as a whole.

[0402] Furthermore, considering the relationship between the series units, in the microfluidic module, the microfluidic reactors 10 in each series unit can be connected in parallel through branch conduits in each supply unit. In this case, even if the number of series units installed on the base plate of the microfluidic module increases, the number of various machines (pumps, switching valves, flow regulating valves, etc.) used to supply raw materials from the supply device to each series unit can be reduced, thereby reducing the construction cost of the system.

[0403] Alternatively, in this system, intermediate tanks for storing raw materials can be installed in each supply unit of the supply device without being located midway through the supply conduit or in the connecting conduit that connects the microfluidic reactors 10 in the series units. In this case, undesirable situations such as unnecessary reactions (changes) occurring in the intermediate tank, increased system start-up time, and increased number of tanks (machine components) can be avoided. Furthermore, by suppressing the increase in the number of tanks, the amount of solvent used when cleaning the tanks periodically or irregularly can be reduced.

[0404] Furthermore, in this system, the microfluidic module is designed as a base plate, allowing for easy replacement at the microfluidic module (base plate) level, resulting in excellent maintainability. Specifically, this system allows for the installation of a switching valve in each supply conduit of each supply unit of the supply device. With this configuration, if an anomaly is detected in any microfluidic module during system operation, the supply of raw materials to the detected microfluidic module can be stopped by activating the switching valve and closing the flow path of the main flow conduit. This facilitates easy inspection of the detected microfluidic module or replacement with a spare (new) microfluidic module.

[0405] As described above, this technique can also be established as a system maintenance method. That is, the system maintenance method involves stopping the supply of fluid (as raw material) to any microfluidic module among the multiple microfluidic modules included in the system when an anomaly is detected, and replacing the anomaly-detecting microfluidic module with a new (other) microfluidic module. In this way, when some microfluidic modules malfunction (blockage, leakage, flow fluctuation, etc.), the performance of other normal microfluidic modules is not affected, and the malfunctioning microfluidic modules can be easily replaced with new ones without stopping the overall system operation. Based on this characteristic, an uninterrupted continuous operation system can be achieved. Furthermore, by operating the microfluidic modules independently, the reliability, monitoring, and conservatism of scaling up the number of microfluidic modules can be improved.

[0406] The larger the volume of the mixing / reaction flow path in the microfluidic reactor 10, the longer the residence time of the mixed liquid flowing in the mixing / reaction flow path can be ensured. Therefore, by specifying the volume of the mixing / reaction flow path as described above, even in the microfluidic reactor 10 located further downstream in the series unit, the residence time of the mixed liquid flowing in the mixing / reaction flow path can be ensured, thus enabling efficient acquisition of reaction products. Furthermore, even if the viscosity of the mixed liquid flowing in the mixing / reaction flow path of the microfluidic reactor 10 located further downstream increases, uniform mixing can be obtained by ensuring the residence time.

[0407] Furthermore, according to the above method, in the series unit, the more upstream the microfluidic reactor 10 is located, the smaller the volume of the mixing / reaction flow path, and the shorter the residence time of the fluid. As a result, it is possible to suppress the excessive increase in molecular weight of the reaction products generated in the upstream microfluidic reactor 10 in the series unit, and consequently, it is also possible to narrow the molecular weight distribution of the products ultimately recovered in the recovery device.

[0408] <Method for manufacturing the composition>

[0409] Another embodiment of this disclosure relates to a method for manufacturing a composition, specifically a method for obtaining a composition using a polymer manufactured by the above-described polymer manufacturing method, the method comprising: a mixing step of mixing the polymer manufactured by the above-described polymer manufacturing method with other substances. The method for manufacturing the composition may also include other steps besides the mixing step.

[0410] The composition is not particularly limited in form; it can be either solid or liquid.

[0411] In the mixing process, there are no particular restrictions on the method of mixing the polymer with other substances, and well-known methods can be used.

[0412] There are no particular restrictions on other substances that can be mixed with the polymer, and they can be selected appropriately depending on the application. Examples include polymers other than those obtained by the polymer manufacturing methods described above, various additives, solvents, etc.

[0413] <Method for manufacturing molded parts>

[0414] Another embodiment of this disclosure relates to a method for manufacturing a molded article, specifically a method for manufacturing a molded article (hereinafter also simply referred to as "the method for manufacturing a molded article") comprising the following steps: molding a polymer manufactured by the above-described polymer manufacturing method, or a composition manufactured by the above-described composition manufacturing method. According to this manufacturing method, a molded article of a copolymer having a desired monomer composition ratio can be obtained.

[0415] There are no particular limitations on the method of molding polymers. Examples include: a method of molding by removing the solvent or dispersion medium after dissolving the polymer in a solvent or dispersing it in a dispersion medium in a desired mold; a method of molding by mixing the polymer with a curing agent and then allowing the curing reaction to occur in a desired mold; a method of molding by introducing the polymer into a desired mold in a state where it has been softened by heating or the like, and then cooling it; and a method of molding by allowing the curing reaction to occur in a desired mold when the polymer has functional groups that react with heat or light, or when functional groups that react with heat or light are introduced into the polymer.

[0416] These methods can be carried out using well-known methods, or by combining well-known methods.

[0417] Example

[0418] The invention disclosed herein will be described in more detail below with reference to embodiments. However, the interpretation of the invention disclosed herein is not limited to the following embodiments.

[0419] <Experiment 1>

[0420] [Polymer Manufacturing]

[0421] (Example 1)

[0422] The polymer manufacturing system used in this embodiment for manufacturing the polymer is Figure 2 The polymer manufacturing system shown includes an unused portion of the raw material tank and delivery pump. Specifically, this polymer manufacturing system is a microfluidic system comprising multiple devices (hereinafter also referred to as "reactors") forming microflow paths.

[0423] The aforementioned microfluidic system includes multiple reaction mechanisms with an inlet and a reaction flow path. The inlet introduces at least one of the multiple liquids to be mixed into the given processing flow path for mixing. The reaction flow path is disposed downstream of the inlet and is formed in the reactor as a microflow path constituting part of the given processing flow path. This reaction flow path enables the chemical reaction of the reactants contained in the mixture of the multiple liquids to take place.

[0424] The aforementioned reaction mechanisms are arranged in series to connect the aforementioned reaction flow paths of each other.

[0425] In this Experiment 1, for both Example 1 and Comparative Example 1, the experimental conditions were set with the aim of obtaining a copolymer with a molar ratio of two monomer units of 1:1.

[0426] For reactor 101, the flow path width of the first flow path 2 and the first inlet flow path 3 is set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 is set to 1600 mm (flow path volume: 33.0 μL). The liquid delivery pumps 40a and 40b use injection pumps YSP-301 (manufactured by YMC Corporation). To raw material tank 30a, a liquid (liquid 1a, solvent concentration: 85.8% by mass) is obtained by dissolving dimethyl 2,2-azobis(2-methylpropionic acid) (V-601; manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.; polymerization initiator) in propylene glycol monomethyl ether acetate (MMPGAC; manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.; boiling point 145°C, melting point below -10°C, specific gravity 0.97; solvent). To raw material tank 30b, methyl methacrylate (MMA; manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.; boiling point 145°C, melting point below -10°C, specific gravity 0.97) is dissolved in propylene glycol monomethyl ether acetate (MMPGAC; manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.; boiling point 145°C, melting point below -10°C, specific gravity 0.97; solvent). A liquid (liquid 1b, solvent concentration: 79.1 wt%) was obtained by dissolving phenyl methacrylate (PhMA; manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.; boiling point 198°C, melting point -17°C, specific gravity 0.94) in propylene glycol monomethyl ether acetate (MMPGAC as described above) to achieve a phenyl methacrylate concentration of 11.4 wt%. Liquid 1a and liquid 1b were introduced into the inlet section 25 at flow rates of 0.40 μL / min and 1.98 μL / min, respectively. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 75 ± 2°C, and the monomer polymerization reaction was carried out.

[0427] The process using the reactor 101 described above is the polymerization process involved in the polymer manufacturing method of the above embodiment.

[0428] For reactor 102, the flow path width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2197 mm (flow path volume: 45.5 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 1c, solvent concentration: 85.0 wt%) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 7.9 wt% and PhMA (same as the above-mentioned PhMA) to achieve a concentration of 12.1 wt% was introduced into the raw material tank 30b. Liquid 1c was introduced into the inlet 25 at a flow rate of 0.28 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 75 ± 2 °C, and the monomer polymerization reaction was carried out.

[0429] The process using the reactor 102 described above is the (first) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0430] For reactor 103, the flow path width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2604 mm (flow path volume: 54.0 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 1d, solvent concentration: 85.0 wt%) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 7.9 wt% and PhMA (same as the above-mentioned PhMA) to achieve a concentration of 12.1 wt% was introduced into the raw material tank 30b. Liquid 1d was introduced into the inlet 25 at a flow rate of 0.18 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 75 ± 2 °C, and the monomer polymerization reaction was carried out.

[0431] The process using the reactor 103 described above is the (second) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0432] For reactor 104 ( Figure 2 In the reactor 10N (N=4), the width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the length of the flow path from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2895 mm (flow path volume: 60.0 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 1e, solvent concentration: 85.0 wt%) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 7.9 wt% and PhMA (same as the above-mentioned PhMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 12.1 wt% was introduced into the raw material tank 30b. Liquid 1e was introduced into the inlet 25 at a flow rate of 0.11 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 75 ± 2 °C, and the monomer polymerization reaction was carried out.

[0433] The process using the reactor 104 described above is the (3rd) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0434] The flow path width of each conduit, such as the conduit 60c connecting each reactor, is set to 0.26 mm.

[0435] Using the polymer manufacturing system described above, a copolymer (random copolymer) of methyl methacrylate and phenyl methacrylate was manufactured.

[0436] The injection amounts of monomers, polymerization initiators, and solvents in Example 1 above are summarized in Table 1.

[0437] It should be noted that the "mmol ratio" item is set in the total amount column of Table 1, which represents the value obtained by dividing the mass % of each monomer by the molecular weight and multiplying by 1000.

[0438] In Example 1, x3, represented by the following formula, was calculated. The result is that x3 in the first, second, and third additional polymerization steps is -16.8 (≈(7.9 / 9.5-1)×100) for MMA and 6.14 (≈(12.1 / 11.4-1)×100) for PhMA.

[0439] x3=(x1 / x2-1)×100

[0440] x1: Parts by weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer.

[0441] x2: Parts by weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0442] Empty columns in Table 1 indicate that no columns have been added.

[0443]

[0444] (Comparative Example 1)

[0445] Solution 1 was obtained by dissolving each monomer in propylene glycol monomethyl ether acetate (MMPGAC) to a concentration of 17.0% by mass of methyl methacrylate (same as MMA above) and 26.9% by mass of phenyl methacrylate (same as PhMA above). Solution 2 was obtained by dissolving the polymerization initiator in propylene glycol monomethyl ether acetate (MMPGAC above) to a concentration of 20.0% by mass of dimethyl 2,2-azobis(2-methylpropionic acid) (same as V-601 above).

[0446] Next, 197.4 kg of MMPGAC was added to a stirred tank connected to a thermometer, reflux pipe, and nitrogen inlet pipe. The tank was heated to 80°C, and solution 1 was added dropwise at a rate of 1.0 kg / min and solution 2 at a rate of 0.3 kg / min over a period of 6 hours to obtain a reaction solution. After the addition was completed, the reaction solution was heated and stirred for 2 hours, and then cooled to room temperature to obtain a copolymer (random copolymer) of methyl methacrylate and phenyl methacrylate.

[0447] [Determination of the content of MMA units in polymers]

[0448] pass 1 The content of MMA units in the polymer was determined by 1H-NMR.

[0449] A graph created by setting the horizontal axis as the MMA consumption rate and the vertical axis as the MMA unit content in the polymer, as shown below. Figure 4 As shown. It should be noted that the content of MMA units in the polymer is obtained by performing the above-described measurement method on the liquid in the reaction process. In addition, the MMA consumption rate refers to the consumption rate of MMA as a monomer raw material, which represents the mass ratio of monomer supplied for polymerization when the amount of MMA used in the total reaction is set to 100% by mass.

[0450] according to Figure 4 It can be seen that in Comparative Example 1, the MMA ratio in the polymer changed along with the change in the monomer MMA consumption rate. In contrast, in Example 1, the MMA ratio in the polymer remained constant at approximately 50% at any given point. It should be noted that in Example 1 and Example 2 described below, measurements were only performed up to approximately 60% monomer consumption. Figure 4 The results of subsequent consumption rate measurements are not shown.

[0451] [Determination of polydispersity index Mw / Mn]

[0452] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained polymer were determined by gel permeation chromatography (GPC), and the polydispersity index (Mw / Mn) was calculated. The GPC determination conditions are as follows.

[0453] Device: GPC system (manufactured by Shimadzu Corporation)

[0454] System controller: SIL-20A (manufactured by Shimadzu Corporation)

[0455] Pump: LC-20AD (manufactured by Shimadzu Corporation)

[0456] Degassing device: DGU-20A3R (manufactured by Shimadzu Corporation)

[0457] Column oven: CTO-20AC (manufactured by Shimadzu Corporation)

[0458] RI detector: RID-20A (manufactured by Shimadzu Corporation)

[0459] Chromatographic column: GPC KF-806L (column size: 8.0mm (ID) × 300mm (L), manufactured by Resonac Co., Ltd.) × 3 columns

[0460] Protective post: KF-G 4A (Post size: 4.6mm (ID) × 10mm (L), manufactured by Resonac Co., Ltd.)

[0461] Column temperature: 40℃

[0462] Pool temperature: 40℃

[0463] Eluent: Tetrahydrofuran

[0464] Elution buffer flow rate: 0.8 mL / min

[0465] Injection volume: 35μL

[0466] Analysis time: 60 minutes

[0467] Sample: 5% tetrahydrofuran solution

[0468] Sample used for calibration curve preparation: Polystyrene calibration kit SM-10 (manufactured by Agilent Technologies)

[0469] The polydispersity index was determined, and the results showed that the polydispersity index of the polymer obtained in Example 1 was 1.70, and the polydispersity index of the polymer obtained in Comparative Example 1 was 1.80.

[0470] [Comparison of the polymerizability of monomers]

[0471] The polymerizability of the monomers described above was evaluated using MMA and PhMA, and it was confirmed that PhMA has higher polymerizability than MMA. Therefore, it can be concluded that in this experiment, the MMA:PhMA ratio of the target polymer was 1:1, thus satisfying condition (1) above.

[0472] <Experiment 2>

[0473] [Polymer Manufacturing]

[0474] (Example 2)

[0475] The polymer manufacturing system used in this embodiment for manufacturing the polymer is the same as that used in Experiment 1 described above. Figure 2 The polymer manufacturing system shown is partially unused, including some of the raw material tanks and delivery pumps.

[0476] In Experiment 2, for both Example 1 and Comparative Example 1, the experimental conditions were set with the aim of obtaining a copolymer with a molar ratio of two monomer units of 1:1.

[0477] For reactor 101, the flow path width of the first flow path 2 and the first inlet flow path 3 is set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 is set to 1600 mm (flow path volume: 33.0 μL). The liquid delivery pumps 40a and 40b use injection pumps YSP-301 (manufactured by YMC Corporation). To feed tank 30a, a liquid (liquid 2a, solvent concentration: 70.0 wt%) obtained by dissolving dimethyl 2,2-azobis(2-methylpropionic acid) (V-601; polymerization initiator) in propylene glycol monomethyl ether acetate (same as MMPGAC above; solvent) to achieve a free radical polymerization initiator concentration of 30.0 wt% is introduced. To feed tank 30b, methyl methacrylate (same as MMA above) is introduced in a manner that achieves a free radical polymerization initiator concentration of 17.0 wt%, and... Furthermore, phenyl methacrylate (same as PhMA mentioned above) was dissolved in propylene glycol monomethyl ether acetate (same as MMPGAC mentioned above) to achieve a phenyl methacrylate concentration of 17.0% by mass, resulting in a liquid (liquid 2b, solvent concentration: 66.0% by mass). Liquid 2a and liquid 2b were introduced into the inlet section 25 at flow rates of 0.40 μL / min and 1.98 μL / min, respectively. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 86°C, and the monomer polymerization reaction was carried out.

[0478] The process using the reactor 101 described above is the polymerization process involved in the polymer manufacturing method of the above embodiment.

[0479] For reactor 102, the flow path width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2197 mm (flow path volume: 45.5 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 2c, solvent concentration: 68.5% by mass) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 14.5% by mass and PhMA (same as the above-mentioned PhMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 17.0% by mass was introduced into the raw material tank 30b. Liquid 2c was introduced into the inlet 25 at a flow rate of 0.28 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 89°C, and the monomer polymerization reaction was carried out.

[0480] The process using the reactor 102 described above is the (first) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0481] For reactor 103, the flow path width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the flow path length from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2604 mm (flow path volume: 54.0 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 2d, solvent concentration: 72.5% by mass) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 10.5% by mass and PhMA (same as the above-mentioned PhMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 17.0% by mass was introduced into the raw material tank 30b. Liquid 2d was introduced into the inlet 25 at a flow rate of 0.18 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 88°C, and the monomer polymerization reaction was carried out.

[0482] The process using the reactor 103 described above is the (second) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0483] For reactor 104 ( Figure 2 In the reactor 10N (N=4), the width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the length of the flow path from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2895 mm (flow path volume: 60.0 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 2e, solvent concentration: 74.0 mass%) obtained by dissolving MMA (same as the above MMA) in propylene glycol monomethyl ether acetate (same as the above PhMA) to achieve a concentration of 9.0 wt% and PhMA (same as the above PhMA) in propylene glycol monomethyl ether acetate (same as the above MMPGA) to achieve a concentration of 17.0 wt% was introduced into the raw material tank 30b. Liquid 2e was introduced into the inlet 25 at a flow rate of 0.11 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 86°C, and the monomer polymerization reaction was carried out.

[0484] The process using the reactor 104 described above is the (3rd) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0485] For reactor 105 ( Figure 2In a reactor (10N) with N=5, the width of the first flow path 2 and the first inlet flow path 3 was set to 100 μm, and the length of the flow path from the inlet 25 of the first flow path 2 to the outlet 22 was set to 2895 mm (flow path volume: 60.0 μL). The liquid delivery pump 40b used was a YSP-301 syringe pump (manufactured by YMC Corporation). Liquid (liquid 2f, solvent concentration: 74.0 mass%) obtained by dissolving MMA (same as the above-mentioned MMA) in propylene glycol monomethyl ether acetate (same as the above-mentioned MMPGAC) to achieve a concentration of 9.0 wt% and PhMA (same as the above-mentioned PhMA) to achieve a concentration of 17.0 wt% was introduced into the raw material tank 30b. Liquid 2f was introduced into the inlet 25 at a flow rate of 0.11 μL / min. In addition, the polymerization reaction temperature (temperature of heater 20) was set to 85°C, and the monomer polymerization reaction was carried out.

[0486] The process using the reactor 104 described above is the (3rd) additional polymerization process involved in the polymer manufacturing method of the above embodiment.

[0487] The flow path width of each conduit, such as the conduit 60c connecting each reactor, is set to 0.26 mm.

[0488] Using the polymer manufacturing system described above, a copolymer (random copolymer) of methyl methacrylate and phenyl methacrylate was manufactured.

[0489] The injection amounts of monomers, polymerization initiators, and solvents in Example 1 above are summarized in Table 2.

[0490] It should be noted that the "mmol ratio" item is set in the total quantity column of Table 2, which represents the value obtained by dividing the mass % of each monomer by the molecular weight and multiplying by 1000.

[0491] In Example 2, x3, represented by the following formula, was calculated. The results show that x3 in the 1st, 2nd, 3rd, and 4th additional polymerization steps are -14.7, -38.2, -47.1, and -47.1 in MMA, and 0, 0, 0, and 0 in PhMA.

[0492] x3=(x1 / x2-1)×100

[0493] x1: Parts by weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer.

[0494] x2: Parts by weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

[0495] Empty columns in Table 2 indicate that no columns have been added.

[0496]

[0497] [Determination of the content of MMA units in polymers]

[0498] The amount of monomer consumed was calculated by HPLC, and all the monomers that had undergone the reaction were considered to have become polymers, thereby calculating the content of MMA units in the polymers.

[0499] A graph created by setting the horizontal axis as the MMA consumption rate and the vertical axis as the MMA unit content in the polymer, as shown below. Figure 5 As shown. It should be noted that the content of MMA units in the polymer is obtained by performing the above-described measurement method on the liquid in the reaction process. In addition, the MMA consumption rate refers to the consumption rate of MMA as a monomer raw material, which is the mass ratio of monomers supplied for polymerization when the amount of MMA used in the total reaction is set to 100% by mass.

[0500] according to Figure 5 As can be seen, in Comparative Example 1, as described above, the MMA ratio in the polymer changed along with the monomer MMA consumption rate. In contrast, in Example 2, starting from the portion where the monomer consumption rate was lower than in Example 1, the MMA ratio in the polymer reached a constant at approximately 50%. It should be noted that in Example 2, measurements were only performed up to approximately 60% of the monomer consumption rate. Figure 5 The results of subsequent consumption rate measurements are not shown.

[0501] [Determination of polydispersity index Mw / Mn]

[0502] The polydispersity index Mw / Mn of the polymer was calculated using the same method as in Experiment 1 above.

[0503] The polydispersity index was determined, and the results showed that the polydispersity index of the polymer obtained in Example 2 was 1.67, and the polydispersity index of the polymer obtained in Comparative Example 1 was 1.80.

[0504] [Comparison of the polymerizability of monomers]

[0505] In this experiment, it can also be seen that since the MMA:PhMA of the target polymer is 1:1, the first two additional polymerization steps in the first half of the four additional polymerization steps are carried out in a manner that satisfies the above condition (1).

[0506] [M / I ratio]

[0507] Regarding Examples 1-2 and Comparative Example 1, the M / I ratio in the inlet section 25 of each reactor 10 is shown in Table 3.

[0508] Furthermore, regarding Example 1 and Comparative Example 1, the M / I ratios at residence times of 0, 20, 44, 71, 80, and 100 seconds when the residence time in the overall reaction flow path of the reactor is set to 100 seconds are shown in Table 4. It should be noted that when the total residence time in the reaction flow path of reactors 101-104 in Example 1 is set to 100 seconds, the M / I ratios at residence times of 0, 20, 44, and 71 seconds refer to the M / I ratios at the inlet sections of reactors 101-104. Therefore, the M / I ratios at residence times of 0, 20, 44, and 71 seconds in Comparative Example 1 correspond to the M / I ratios at the inlet sections of reactors 101-104 in Example 1, respectively.

[0509] Furthermore, regarding Example 2 and Comparative Example 1, when the residence time in the overall reaction flow path of the reactor is set to 100, the M / I ratios at residence times of 0, 15, 34, 55, 78, 80, and 100 are shown in Table 5. It should be noted that when the total residence time in the reaction flow path of reactors 101-105 in Example 2 is set to 100, the M / I ratios at residence times of 0, 15, 34, 55, and 78 refer to the M / I ratios at the inlet sections of reactors 101-105. Therefore, the M / I ratios at residence times of 0, 15, 34, 55, and 78 in Comparative Example 1 correspond to the M / I ratios at the inlet sections of reactors 101-105 in Example 2.

[0510] According to Tables 4 and 5, if we calculate (M / I ratio at residence time 0) / (M / I ratio at residence time 80), the values ​​are 1.65, 3.38, and 4.39 in Examples 1-2 and Comparative Example 1, respectively.

[0511] Furthermore, according to Tables 4 and 5, if the ratio of (M / I ratio when residence time is 0) to (M / I ratio when residence time is 100) is calculated, the values ​​in Examples 1-2 and Comparative Example 1 are 2.02, 4.86, and 20.28, respectively.

[0512]

[0513]

[0514]

Claims

1. A method for manufacturing a polymer, the method comprising: The polymerization process includes a polymerization treatment in which a polymerization initiator and two or more monomers are subjected to a polymerization reaction in a liquid to obtain a polymer reactant. and An additional polymerization step is performed, in which additives are added to carry out a further polymerization reaction, and this additional polymerization step is performed at least once. The added ingredient contains at least one of the two or more monomers. The amount of the added component is controlled in each additional polymerization step so that the composition ratio of monomer units in the polymer reactants obtained in each additional polymerization step reaches a given ratio.

2. The method for manufacturing the polymer according to claim 1, wherein, The amount of the added ingredient is based on a molar basis.

3. The method for manufacturing the polymer according to claim 1 or 2, wherein, In the case of performing the additional polymerization step n times (n≥1), the k-th (1≤k≤n) additional polymerization step processes the liquid containing the polymerization reactants obtained in the polymerization step (in the case of k=1), or the liquid containing the polymerization reactants obtained in the (k-1)-th additional polymerization step (in the case of k≥2). The addition of the additives in the k-th additional copolymerization process is controlled under the following M ki M ka and M kf Simultaneously M ki : The molar amount of each monomer unit in the reactive polymer contained in the liquid at the start of the k-th additional polymerization step; M ka : The molar amount of each monomer added in the k-th additional polymerization step; M kf : The molar amount of each monomer unit in the reactive polymer contained in the liquid at the end of the k-th additional polymerization step.

4. The method for manufacturing the polymer according to claim 1 or 2, wherein, When the added component comprises two or more monomers, the amount of each monomer added in at least one of the additional polymerization steps is determined based on the polymerizability of each monomer as evaluated by the following evaluation method. Evaluation method: When a polymer is produced by polymerizing each monomer using a solution containing the same molar amount of each monomer, and the molar amounts of each monomer unit in the polymer are compared, the monomer constituting the monomer unit with the larger molar amount is considered the monomer with high polymerizability, and the monomer constituting the monomer unit with the smaller molar amount is considered the monomer with low polymerizability.

5. The method for manufacturing the polymer according to claim 4, wherein, The addition of the additive component in at least one of the additional polymerization steps is carried out in a manner that at least satisfies the following condition (1). Condition (1): If a / b is less than A / B, then let α > β. α: The molar amount of monomer A added; β: The molar amount of monomer B added; A: The molar amount of monomer A units in the target polymer; B: The molar amount of monomer B units in the target polymer; a: The molar amount of monomer A when the evaluation method was performed using monomer A and monomer B; b: The molar amount of monomer B when the evaluation method was performed using monomer A and monomer B.

6. The method for manufacturing the polymer according to claim 1, wherein, In at least one of the additional polymerization steps, at least one monomer X contained in the added component that is repeated with the two or more monomers respectively satisfies the following condition (2). Condition (2): x1 and x2 are different. x1: The weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer; x2: The weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

7. The method for manufacturing the polymer according to claim 6, wherein, The monomers X respectively satisfy the following condition (3), Condition (3): The value x3, represented by (x1 / x2-1)×100, is less than -5 and greater than 5. x1: The weight of monomer X in the liquid during the polymerization process relative to 100 parts by weight of the total monomer; x2: The weight of monomer X in each additional polymerization step relative to 100 parts by weight of the total monomer.

8. The method for manufacturing the polymer according to claim 1 or 2, wherein, As the monomer used in the polymerization step, at least one monomer selected from the group consisting of: polymerizable monomers containing (meth)acryloyl groups, polymerizable monomers containing isocyanate groups, polymerizable monomers containing carboxyl groups, polymerizable monomers containing hydroxyl groups, polymerizable monomers containing epoxy groups, and polymerizable monomers containing... Polymerizable monomers with azoline group, polymerizable monomers containing maleimide group, polymerizable monomers containing amino group, styrene monomers, fluorinated vinyl monomers, silicone vinyl monomers, vinyl ester monomers, diene monomers, vinyl chloride, vinylidene chloride, allyl chloride, and vinyl ethyl ether.

9. The method for manufacturing the polymer according to claim 1 or 2, wherein, The polymerization initiator is a free radical polymerization initiator.

10. The method for manufacturing the polymer according to claim 1, wherein, At least one of the polymerization steps selected from the above polymerization step and the additional polymerization step performed at least once is carried out using an apparatus having a reaction flow path for the polymerization reaction of monomers.

11. The method for manufacturing the polymer according to claim 8, wherein, The apparatus is a microfluidic reactor, and the reaction flow path is a microflow path.

12. A method for manufacturing a composition, the method comprising: The composition is obtained using a polymer manufactured by the method for manufacturing the polymer according to claim 1.

13. A method for manufacturing a molded article, the method comprising: The process of molding a polymer manufactured by the method of manufacturing the polymer according to claim 1 or a composition manufactured by the method of manufacturing the composition according to claim 12.

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