Polymer manufacturing method

Abstract

To provide a manufacturing method of polymer for obtaining a polymer having a uniform copolymerization composition with a narrow molecular-weight distribution.SOLUTION: A manufacturing method of polymer comprises the step of radically polymerizing monomer components including two or more monomers in the presence of a polymerization initiator with use of a microreactor having a channel in which a plurality of liquids can be mixed. The microreactor comprises a first introduction port for introducing a monomer component and another introduction port located downstream the first introduction port. The monomer components are introduced into the first introduction port and the other introduction port.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing polymers. [Background technology]

[0002] The most common method for producing (meth)acrylate polymers is known as batch polymerization, which involves dissolving raw material monomers, polymerization initiators, and optionally chain transfer agents in a polymerization solvent and then heating them to polymerize them. However, batch polymerization has the drawback that it is difficult to control the reaction temperature throughout the entire reaction medium, leading to differences in radical generation due to subtle changes in reaction temperature, and resulting in a broad molecular weight distribution of the resulting polymer (non-uniform molecular weight of the polymer). Furthermore, the difficulty in controlling the reaction temperature also led to differences in quality between batches.

[0003] Furthermore, when two or more monomers with different reactivity levels are used as raw materials, the polymer formed in the early stages of the polymerization reaction will have a higher proportion of units derived from the more reactive monomer, while the polymer formed in the later stages of the polymerization reaction will have a higher proportion of units derived from the less reactive monomer. Because the reaction system of a single polymerization reaction is large, it is difficult to control the relative proportions of monomers, making it susceptible to the effects described above, and thus resulting in the disadvantage of a non-uniform copolymer composition of the final polymer.

[0004] As a means of solving the above problem, a method of polymerization is called dropwise polymerization (semi-batch polymerization), in which raw material monomers, polymerization initiators, and chain transfer agents are mixed or supplied separately to a system maintained at a constant temperature. Known dropwise polymerization methods include, for example, a method of preheating the monomers and adding them dropwise, or a method of adding the monomers dropwise into a polymerization solvent maintained at a constant temperature (Patent Documents 1 and 2).

[0005] Compared to batch polymerization, dropwise polymerization is effective because it requires a smaller reaction system, allowing for easy control of the relative proportions of two or more monomers in the reaction system, thus yielding a uniform polymer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2004-269855 [Patent Document 2] Japanese Patent Publication No. 2004-355023 [Overview of the project] [Problems that the invention aims to solve]

[0007] Photoresist resins are required to have a narrow molecular weight distribution, in addition to optical properties, chemical properties, and physical properties such as coatability and adhesion to substrates or underlying films, from the viewpoint of improving solubility in developing solutions. In particular, in the manufacturing process of semiconductor materials where fine and precise shapes are required, a uniform copolymer composition of the polymer and a narrow molecular weight distribution enable precise control of solubility in developing solutions and further enable ultrafine processing. Furthermore, as resist patterns become finer, the demands on the quality of photoresist resins are increasing, and there is a need for photoresist resins with small differences in molecular weight between lots. For this reason, the dropwise polymerization method described above is generally used as a manufacturing method for photoresist resins. However, controlling the reaction temperature is difficult with the dropwise polymerization method, making it insufficient as a manufacturing method for photoresist resins where higher uniformity is required.

[0008] Furthermore, while a polymerization method using a microreactor is known as one of the flow polymerization methods, although this method excels in controlling the reaction temperature, the polymerization reaction proceeds in the same manner as the conventional batch method (for example, the aforementioned batch polymerization method), and therefore is insufficient from the viewpoint of uniformity of the copolymer composition in photoresist resins.

[0009] Thus, despite the strong demand for polymers with a uniform copolymer composition and a narrow molecular weight distribution, methods for producing such polymers have not yet been established.

[0010] Therefore, an object of the present invention is to provide a method for producing a polymer that has a uniform copolymer composition and a narrow molecular weight distribution. [Means for solving the problem]

[0011] As a result of diligent research to achieve the above objective, the inventors of this invention have found that by radical polymerization of a monomer component containing two or more monomers under specific reaction conditions in the presence of a polymerization initiator, a polymer with a uniform copolymer composition and a narrow molecular weight distribution can be obtained. This invention was completed based on these findings.

[0012] In other words, the present invention is a method for producing a polymer by radical polymerization of a monomer component containing two or more monomers in the presence of a polymerization initiator, using a microreactor equipped with a channel capable of mixing multiple liquids. The microreactor comprises a first inlet for introducing monomer components and another inlet located downstream of the first inlet. The present invention provides a method for producing a polymer, characterized by introducing monomer components into the first inlet and the other inlet.

[0013] The monomer components introduced into the first inlet and the other inlet preferably contain two or more (meth)acrylic monomers.

[0014] Preferably, the monomers contained in the monomer component introduced into the first inlet and the other inlet are the same, and the error in the content of each monomer is within ±5%.

[0015] In the present invention, radical polymerization is preferably carried out in the presence of a polymerization initiator and a chain transfer agent.

[0016] In the present invention, it is preferable that the chain transfer agent is a chain transfer agent that does not contain a cyano group but contains a thiocarbonylthio group, and that the polymerization initiator is a polymerization initiator that does not contain a cyano group.

[0017] In the present invention, it is preferable that the chain transfer agent is a chain transfer agent containing a cyano group and a thiocarbonylthio group.

[0018] In this invention, it is preferable that the molecular weight distribution (Mw / Mn) of the polymer is 1.45 or less. [Effects of the Invention]

[0019] According to the present invention, it is possible to produce polymers with a uniform copolymer composition and a narrow molecular weight distribution. [Brief explanation of the drawing]

[0020] [Figure 1] Figure 1 is a conceptual diagram showing the microreactor used in the example. [Modes for carrying out the invention]

[0021] The present invention relates to a method for producing a polymer by radical polymerization of a monomer component containing two or more monomers in the presence of a polymerization initiator, using a microreactor equipped with a channel capable of mixing multiple liquids, wherein the microreactor comprises a first inlet for introducing the monomer component and another inlet located downstream of the first inlet, and the monomer component is introduced into the first inlet and the other inlet. The other inlet may be a second inlet, a third inlet, a fourth inlet, and so on, up to an Nth inlet (where N is an integer of 2 or more). In the present invention, radical polymerization may be performed in the presence of a polymerization initiator and a chain transfer agent.

[0022] In the channel located between the first and second inlets, the monomer component introduced through the first inlet undergoes radical polymerization (referred to as the first reaction). In the channel located downstream of the second inlet (or, if the microreactor has a third inlet, the channel located between the second and third inlets), the reactants produced in the first reaction and the monomer component introduced through the second inlet undergo radical polymerization (referred to as the second reaction). Furthermore, in the channel located downstream of the third inlet (or, if the microreactor has a fourth inlet, the channel located between the third and fourth inlets), the reactants obtained in the second reaction and the monomer component introduced through the third inlet undergo radical polymerization (referred to as the third reaction). Thus, in the channel located downstream of the Nth inlet, the reactants produced in the channel located between the N-1 inlet and the Nth inlet and the monomer component introduced through the Nth inlet undergo radical polymerization (referred to as the Nth reaction, where N is the same as above).

[0023] The reactants produced in the first reaction will have their polymer chains extended by the polymer chain elongation reaction described later. In other words, the reactants act as nuclei for the polymer. For this reason, the first reaction can be rephrased as a "polymer nucleation reaction."

[0024] The Nth reaction (reactions from the second reaction onward) is primarily a reaction that extends the polymer chain of the reactant produced by the preceding reaction. For this reason, the Nth reaction can be rephrased as a "polymer chain extension reaction." However, the Nth reaction may also include reactions other than those that extend the polymer chain of the reactant produced by the preceding reaction, such as reactions that form new reactants that can serve as polymer nuclei. In other words, the monomer component introduced through the Nth inlet does not have to be used only for the polymer chain extension reaction; it may also form a new polymer (polymer nucleus) by radical polymerization with unreacted monomer components.

[0025] Polymers are formed by the radical polymerization of monomer components containing two or more monomers. However, the ratio of monomer units in the polymer varies depending on the reaction conditions, such as the reactivity, concentration, and time of the monomers used. For example, if the reactivity of the monomers used differs significantly, the polymer formed in the early stages of the polymerization reaction will have a higher proportion of units derived from the highly reactive monomer, while the polymer formed in the later stages of the polymerization reaction will have a higher proportion of units derived from the less reactive monomer. Thus, the ratio of monomer units in the polymer differs depending on the reaction conditions, and the proportion of unreacted monomers also differs.

[0026] The above situation can also occur in the first reaction, i.e., the polymer nucleation reaction. However, by introducing monomer components in the polymer chain extension reaction, it is possible to adjust the concentration differences of each monomer produced in the first reaction and control the process so that a polymer with the same composition is always produced.

[0027] As polymerization initiators, known or conventional radical polymerization initiators can be used, such as polymerization initiators containing a cyano group or polymerization initiators that do not contain a cyano group. One polymerization initiator may be used, or two or more may be used.

[0028] Examples of polymerization initiators containing a cyano group include azo compounds containing a cyano group, such as azobisisobutyronitrile (2,2'-azobis(isobutyronitrile)), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), and 4,4'-azobis(4-cyanovaleric acid).

[0029] As polymerization initiators that do not contain cyano groups, known or conventional polymerization initiators can be used, for example, azo compounds that do not contain cyano groups, such as dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), and dibutyl-2,2'-azobisisobutyrate. Other examples include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals such as 1,1-bis(tert-hexylperoxy)3,3,5-trimethylcyclohexane and 1,1-bis(tert-hexylperoxy)cyclohexane; hydroperoxides or dialkyl peroxides such as p-menthane hydroperoxide and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxides such as isobutyryl peroxide and 3,3,5-trimethylhexanoyl peroxide; peroxyesters such as 1,1,3,3-tetramethylbutyl peroxyneodecanate and tert-hexylperoxyneodecanate; and peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate, which do not contain cyano groups. Other examples include redox compounds that do not contain cyano groups, such as hydrogen peroxide and ammonium persulfate.

[0030] As the chain transfer agent, known or conventional chain transfer agents used in radical polymerization can be used, for example, chain transfer agents containing a thiocarbonylthio group (chain transfer agents containing a cyano group and a thiocarbonylthio group, chain transfer agents that do not contain a cyano group but contain a thiocarbonylthio group), etc. One type of chain transfer agent may be used, or two or more types may be used.

[0031] Examples of chain transfer agents containing cyano groups and thiocarbonylthio groups include cyano-containing didithiobenzoate chain transfer agents such as 2-cyano-2-propyl 4-cyanobenzodithioate, 4-cyano-4-(phenylcarbonothiothio)pentanoic acid, 2-cyano-2-propylbenzodithioate, and 4-cyano-4-(phenylcarbonothiothio)pentanoic acid N-succinimidyl ester; and 4-cyano-4-[(dodecyl Trithiocarbonate chain transfer agents containing cyano groups such as sulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol, poly(ethylene glycol)methyl ether 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, poly(ethylene glycol)methyl ether (4-cyano-4-pentanoate dodecyltrithiocarbonate), poly(ethylene glycol)methyl ether (4-cyano-4-pentanoate dodecyltrithiocarbonate), poly(ethylene glycol)methyl ether (4-cyano-4-pentanoate dodecyltrithiocarbonate), cyanomethyldodecyltrithiocarbonate, etc.; cyanomethylmethyl(phenyl)carbamodithioate, cyanomethyl Examples of chain transfer agents include dithiocarbamate-based chain transfer agents containing a cyano group, such as tyldiphenylcarbamodithioate, 1-succinimidyl-4-cyano-4-[N-methyl-N-(4-pyridyl)carbamodiolthio]pentanoate, 2-cyanopropan-2-yl N-methyl-N(pyridine-4-yl)carbamodithioate, and cyanomethylmethyl(4-pyridyl)carbamodithioate; and xanthanate-based chain transfer agents containing a cyano group. Among these, 4-cyano-4-(phenylcarbonodiolthio)pentanoic acid, 2-cyano-2-propylbenzodithioate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, and 2-cyano-2-propyldodecyltrithiocarbonate are preferred from the viewpoint of the molecular weight distribution of the resulting polymer.

[0032] Examples of chain transfer agents that do not contain a cyano group but contain a thiocarbonylthio group include cyano-free didithiobenzoate chain transfer agents such as 2-phenyl-2-propylbenzodithioate, 1-(methoxycarbonyl)ethylbenzodithioate, benzylbenzodithioate, ethyl-2-methyl-2-(phenylthiocarbonylthio)propionate, methyl-2-phenyl-2-(phenylcarbonothio)acetate, ethyl-2-(phenylcarbonothio)propionate, bis(thiobenzoyl)disulfide, and other cyano-free didithiobenzoate-based chain transfer agents; 2-(dodecylthiocarbonylthio)propionic acid, 2-(dodecylthiocarbonylthio)-2-methylpropionic acid, methyl-2-(dodecylthiocarbonylthio)-2-methylpropionate, and 2-(dodecylthiocarbonylthio)-2-methylpropionic acid N-hydroxysuccinimide ester, poly(ethylene glycol) methyl ether (dodecyl trithiocarbonate 2-methyl-2-propionic acid), poly(ethylene glycol) bis[2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate], 3-azido-1-propanol ester of 2-(dodecylthiocarbonylthiooylthio)-2-methylpropionic acid, pentafluorophenyl ester of 2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether 2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate, poly(ethylene glycol) methyl ether Trithiocarbonate chain transfer agents that do not contain cyano groups, such as 2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate, poly(ethylene glycol)bis[2-(dodecylthiocarbonylthiooylthio)-2-methylpropionate], and bis(dodecylsulfanylthiocarbonyl) disulfide; dithiocarbamate chain transfer agents that do not contain cyano groups, such as benzyl 1H-pyrrole-1-carbodichioic acid, methyl 2-propionate methyl(4-pyridinyl)carbamodithioate, and N,N'-dimethylN,N'-di(4-pyridinyl)thiuram disulfide;Examples include xanthanthate-based chain transfer agents that do not contain cyano groups. Among these, ethyl-2-methyl-2-(phenylthiocarbonylthio)propionate is preferred from the viewpoint of the molecular weight distribution of the resulting polymer.

[0033] In the present invention, when a chain transfer agent containing a cyano group and a thiocarbonylthio group is used as the chain transfer agent, the polymer obtained is a polymer having cyano groups at its terminals (polymer terminals). Since cyano groups are poorly soluble in solvents (e.g., photoresist solvents), polymers having cyano groups at their terminals tend to have poor solubility in solvents. However, in the aforementioned polymer, because the chain transfer agent has a high ability to adjust the degree of polymerization of the polymer, the copolymer composition tends to be uniform and the polymer tends to have a narrow molecular weight distribution. As a result, the aforementioned polymer tends to have high solubility in solvents (e.g., photoresist solvents).

[0034] On the other hand, if a chain transfer agent that does not contain cyano groups but contains thiocarbonylthio groups is used as the chain transfer agent, and a polymerization initiator that does not contain cyano groups is used as the polymerization initiator, a polymer without cyano groups at the terminals can be obtained. Therefore, the polymer tends to have high solubility in solvents.

[0035] The present invention may be carried out in the absence of a solvent or in the presence of a solvent (polymerization solvent). Examples of solvents include glycol-based solvents (glycol-based compounds), ester-based solvents, ketone-based solvents, ether-based solvents, amide-based solvents, sulfoxide-based solvents, hydrocarbon-based solvents, and mixtures thereof. Only one polymerization solvent may be used, or two or more may be used.

[0036] Examples of glycol-based solvents include propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of ester-based solvents include lactate ester solvents such as ethyl lactate; propionic acid ester solvents such as methyl 3-methoxypropionate; and acetate ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. Examples of ketone-based solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone. Examples of ether-based solvents include linear ethers such as diethyl ether, diisopropyl ether, dibutyl ether, and dimethoxyethane; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of amide-based solvents include N,N-dimethylformamide. Examples of sulfoxide-based solvents include dimethyl sulfoxide. Hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. Among these, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone; and mixed solvents thereof are preferably used.

[0037] (Polymer nucleation reaction) The polymer nucleation reaction of the present invention, i.e., the first reaction, is a reaction in which a monomer component introduced into a microreactor from a first inlet undergoes radical polymerization. The monomer component introduced from the first inlet undergoes radical polymerization initiated by a polymerization initiator present in the microreactor system, and a reactant (radical polymer) is formed. The means of introducing the monomer component into the microreactor are not particularly limited, but one example is introducing it into the microreactor via an introduction channel (hereinafter sometimes referred to as the "monomer introduction channel").

[0038] The means for introducing the polymerization initiator into the microreactor are not particularly limited, but for example, one means is to introduce it into the microreactor via an introduction channel (hereinafter sometimes referred to as the "polymerization initiator introduction channel"). The introduction of the polymerization initiator into the microreactor is not particularly limited, but for example, one means is to introduce it into the microreactor via [1] before introducing the monomer component into the microreactor, [2] simultaneously with introducing the monomer component into the microreactor, or [3] after introducing the monomer component into the microreactor. In particular, [2] is preferred because it makes it possible to efficiently mix the monomer component and the polymerization initiator, and makes it easy to control the reaction time and reaction temperature.

[0039] When radical polymerization is carried out in the presence of a polymerization initiator and a chain transfer agent, the means for introducing the chain transfer agent are the same as those described for introducing the polymerization initiator, for example, by introducing it into the microreactor via an introduction channel (hereinafter sometimes referred to as the "chain transfer agent introduction channel"). Note that the introduction channel may be the same as the polymerization initiator introduction channel. That is, a solution containing the polymerization initiator and the chain transfer agent may be prepared in advance, and the solution may be introduced into the microreactor via an introduction channel (hereinafter sometimes referred to as the "polymerization initiator etc. introduction channel"). By using a chain transfer agent, the polymerization reaction can be controlled, making it possible to obtain a polymer with a more uniform copolymer composition and a narrower molecular weight distribution.

[0040] The reaction temperature of this reaction (polymer nucleation reaction), that is, the temperature of the flow channel located between the first inlet and the second inlet, is not particularly limited and can be appropriately selected depending on the purpose. For example, 0 to 200°C is preferred, 20 to 180°C is more preferred, 40 to 160°C is even more preferred, 60 to 140°C is particularly preferred, and 80 to 120°C is most preferred.

[0041] The molar concentration of the monomer component (total molar concentration of monomers) in this reaction is not particularly limited and can be appropriately selected depending on the purpose. However, for example, 0.01 to 5.0 mol / L is preferred, 0.05 to 3.0 mol / L is more preferred, and 0.1 to 2.0 mol / L is particularly preferred. When the concentration is within the above range, the amount of polymer produced per unit time tends to be good. On the other hand, if the concentration is higher than 5.0 mol / L, problems arise such as an increase in the viscosity of the reaction solution and failure of the monomer component to dissolve. Also, if the concentration is less than 0.01 mol / L, problems arise such as a decrease in the reaction rate and a decrease in the amount of polymer produced (the reaction does not proceed sufficiently). Note that the above refers to the molar concentration of the monomer component in the channel immediately after introduction into the microreactor.

[0042] The flow rate of the reaction solution in this reaction is not particularly limited and can be appropriately selected depending on the purpose, but for example, 0.001 to 10 mL / min is preferred, 0.005 to 3 mL / min is more preferred, and 0.01 to 1 mL / min is particularly preferred. When the flow rate is within the above range, rapid mixing of the monomer component and polymerization initiator tends to be achieved, and pressure loss tends to be suppressed. Note that the above refers to the flow rate of the reaction solution in the flow path immediately after introduction into the microreactor.

[0043] The residence time in this reaction is not particularly limited and can be appropriately selected depending on the purpose, but for example, 1 to 180 minutes is preferred, 5 to 120 minutes is more preferred, and 8 to 90 minutes is particularly preferred. When the residence time is within the above range, the average molecular weight of the resulting polymer tends to be narrower.

[0044] The concentration of the polymerization initiator in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of the monomer components. For example, 0.0001 to 3.0 mol / L is preferred, 0.0005 to 1.5 mol / L is more preferred, 0.001 to 0.5 mol / L is even more preferred, and 0.005 to 0.2 mol / L is particularly preferred. By keeping the concentration within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of the polymerization initiator in the flow path immediately after introduction into the microreactor.

[0045] The concentration of the chain transfer agent in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of the monomer components. For example, 0.0001 to 3.0 mol / L is preferred, 0.0005 to 1.5 mol / L is more preferred, 0.001 to 0.5 mol / L is even more preferred, and 0.005 to 0.2 mol / L is particularly preferred. By keeping the concentration within the above range, blockage of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of the chain transfer agent in the flow path immediately after introduction into the microreactor.

[0046] The total concentration of polymerization initiator and chain transfer agent in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of monomer components. For example, 0.0001 to 3.0 mol / L is preferred, 0.0005 to 1.5 mol / L is more preferred, 0.001 to 0.5 mol / L is even more preferred, and 0.005 to 0.2 mol / L is particularly preferred. By keeping the concentration within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above concentration refers to the concentration in the flow path immediately after introduction into the microreactor.

[0047] The concentration ratio of polymerization initiator and chain transfer agent to monomer in the present invention (polymerization initiator and chain transfer agent / monomer) is not particularly limited, but for example, 0.001 to 100.0 mol% is preferred, 0.01 to 50.0 mol% is more preferred, 0.05 to 30.0 mol% is even more preferred, and 0.1 to 20.0 mol% is particularly preferred. By having the concentration ratio within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of polymerization initiator and chain transfer agent in the flow path immediately after introduction into the microreactor.

[0048] (polymer chain elongation reaction) The polymer chain extension reaction, or the Nth reaction (where N is an integer greater than or equal to 2), is a reaction in which the reactants produced in the channel located between the N-1 inlet and the Nth inlet undergo radical polymerization in the channel located downstream of the Nth inlet, and the monomer component introduced through the Nth inlet. The means of introducing the monomer component into the microreactor are not particularly limited, but one example is introducing it into the microreactor via an introduction channel. For example, the second reaction is a reaction in which the reactants produced in the channel located between the first inlet and the second inlet undergo radical polymerization in the channel located downstream of the second inlet (or between the second and third inlets if the microreactor has a third inlet), and the monomer component introduced through the second inlet. Another example of a means of introducing the monomer component into the microreactor is introducing it into the microreactor via an introduction channel.

[0049] It is preferable that the monomer components introduced into the first inlet and the other inlets contain the same monomers, more preferably that the monomers are the same and the error in the content of each monomer is within ±5%, even more preferably that the monomers are the same and the error in the content of each monomer is within ±1%, and particularly preferable that the monomers and their content are the same (substantially the same). Note that "error in monomer content" means the error in the content (weight %) of a specific monomer contained in the monomer component introduced into the other inlet, based on the content (weight %) of that specific monomer contained in the monomer component introduced into the first inlet. For example, if the monomer A content in the monomer component introduced into the first inlet is 50% by weight and the monomer A content in the monomer component introduced into the other inlet is 51% by weight, the error (%) is (51 / 50-1)×100=2%. Furthermore, "error in the content of each monomer is within ±5%" means that for all monomers contained in the monomer component, the error in the content of each is within ±5%. For example, if the monomer component contains monomer A and monomer B, this means that the error in the content of monomer A is within ±5%, and the error in the content of monomer B is within ±5%.

[0050] The reaction temperature of this reaction (polymer chain extension reaction), that is, the temperature of the channel located downstream of the Nth inlet (for example, between the second and third inlets), is not particularly limited and can be appropriately selected depending on the purpose. For example, 0 to 200°C is preferred, 20 to 180°C is more preferred, 40 to 160°C is even more preferred, 60 to 140°C is particularly preferred, and 80 to 120°C is most preferred. The reaction temperature of this reaction may be the same as the reaction temperature of the polymer nucleation reaction.

[0051] The molar concentration of the monomer component (total molar concentration of monomers) in this reaction is not particularly limited and can be appropriately selected depending on the purpose. However, for example, 0.01 to 5.0 mol / L is preferred, 0.05 to 3.0 mol / L is more preferred, and 0.1 to 2.0 mol / L is particularly preferred. When the concentration is within the above range, the amount of polymer produced per unit time tends to be good. On the other hand, if the concentration is higher than 5.0 mol / L, problems arise such as an increase in the viscosity of the reaction solution and failure of the monomer component to dissolve. Also, if the concentration is less than 0.01 mol / L, problems arise such as a decrease in the reaction rate and a decrease in the amount of polymer produced (the reaction does not proceed sufficiently). Note that the above refers to the molar concentration of the monomer component in the channel immediately after introduction into the microreactor.

[0052] The flow rate of the reaction solution in this reaction is not particularly limited and can be appropriately selected depending on the purpose, but for example, 0.001 to 10 mL / min is preferred, 0.005 to 3 mL / min is more preferred, and 0.01 to 1 mL / min is particularly preferred. When the flow rate is within the above range, rapid mixing of the monomer component and polymerization initiator tends to be achieved, and pressure loss tends to be suppressed. Note that the above refers to the flow rate of the reaction solution in the flow path immediately after introduction into the microreactor.

[0053] The residence time in this reaction is not particularly limited and can be appropriately selected depending on the purpose, but for example, 1 to 180 minutes is preferred, 5 to 120 minutes is more preferred, and 8 to 90 minutes is particularly preferred. When the residence time is within the above range, the average molecular weight of the resulting polymer tends to be narrower.

[0054] The concentration of the polymerization initiator in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of the monomer components. For example, 0.0001 to 3.0 mol / L is preferred, 0.0005 to 1.5 mol / L is more preferred, 0.001 to 0.5 mol / L is even more preferred, and 0.005 to 0.2 mol / L is particularly preferred. By keeping the concentration within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of the polymerization initiator in the flow path immediately after introduction into the microreactor.

[0055] The concentration of the chain transfer agent in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of the monomer components. For example, 0.0001 to 3.0 mol / L is preferred, 0.0005 to 1.5 mol / L is more preferred, 0.001 to 0.5 mol / L is even more preferred, and 0.005 to 0.2 mol / L is particularly preferred. By keeping the concentration within the above range, blockage of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of the chain transfer agent in the flow path immediately after introduction into the microreactor.

[0056] The total concentration of polymerization initiator and chain transfer agent in this reaction is not particularly limited and can be appropriately selected depending on the composition and concentration of monomer components. For example, 0.0001 to 1.0 mol / L is preferred, 0.0003 to 0.5 mol / L is more preferred, 0.0005 to 0.3 mol / L is even more preferred, and 0.001 to 0.1 mol / L is particularly preferred. By keeping the concentration within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration of polymerization initiator and chain transfer agent in the flow path immediately after introduction into the microreactor.

[0057] The concentration ratio of polymerization initiator and chain transfer agent to monomer in this reaction (polymerization initiator and chain transfer agent / monomer) is not particularly limited, but for example, 0.001 to 100.0 mol% is preferred, 0.01 to 50.0 mol% is more preferred, 0.05 to 30.0 mol% is even more preferred, and 0.1 to 20.0 mol% is particularly preferred. By keeping the concentration ratio within the above range, clogging of the microreactor's flow path can be suppressed, and the average molecular weight of the resulting polymer tends to be narrower. Note that the above refers to the concentration ratio of polymerization initiator and chain transfer agent to monomer in the flow path immediately after introduction into the microreactor.

[0058] The method for recovering the polymer is not particularly limited, but one example is a method using precipitation (including reprecipitation). For example, the polymer can be precipitated by adding the reaction solution to a solvent (precipitation solvent), or by redissolving the polymer in a suitable solvent and adding this solution to a solvent (reprecipitation solvent) to reprecipitation, or by diluting the reaction solution by adding a solvent (reprecipitation solvent or polymerization solvent) to obtain the desired polymer. The precipitation or reprecipitation solvent may be an organic solvent, water, or a mixed solvent.

[0059] The precipitation or reprecipitation solvent is not particularly limited, and may be the same solvent as the polymerization solvent or a different solvent. Examples of precipitation or reprecipitation solvents include organic solvents exemplified as polymerization solvents (glycol-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents, amide-based solvents, sulfoxide-based solvents, hydrocarbon-based solvents); halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, etc.); nitro compounds (nitromethane, nitroethane, etc.); nitriles (acetonitrile, benzonitrile, etc.); carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.); carboxylic acids (acetic acid, etc.); and mixed solvents containing these solvents.

[0060] In particular, solvents containing at least hydrocarbons (especially aliphatic hydrocarbons such as hexane and heptane) or alcohols (especially methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.) are preferred as precipitation or reprecipitation solvents. In such solvents containing at least hydrocarbons, the ratio of hydrocarbons (e.g., aliphatic hydrocarbons such as hexane and heptane) to other solvents (e.g., esters such as ethyl acetate, etc.) is, for example, former / latter (volume ratio: 25°C) = 10 / 90~99 / 1, preferably former / latter (volume ratio: 25°C) = 30 / 70~98 / 2, and even more preferably former / latter (volume ratio: 25°C) = 50 / 50~97 / 3.

[0061] Furthermore, as precipitation or reprecipitation solvents, mixed solvents of alcohol (especially methanol) and water, and mixed solvents of glycol-based solvents (especially polyethylene glycol) and water are also preferred. In this case, the ratio (volume ratio: 25°C) of the organic solvent (alcohol or glycol-based solvent) to water is, for example, former / latter (volume ratio: 25°C) = 10 / 90~99 / 1, preferably former / latter (volume ratio: 25°C) = 30 / 70~98 / 2, and even more preferably former / latter (volume ratio: 25°C) = 50 / 50~97 / 3.

[0062] The polymer obtained by precipitation (including reprecipitation) may be subjected to rinsing or washing by stirring and dispersing the polymer with a solvent (sometimes referred to as "repulping"), as needed. Rinsing may also be performed after repulping. By repulping the polymer produced by polymerization with a solvent or by rinsing, residual monomers and low molecular weight oligomers adhering to the polymer can be efficiently removed.

[0063] In the present invention, solvents containing at least hydrocarbons (especially aliphatic hydrocarbons such as hexane and heptane), alcohols (especially methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), or esters (especially ethyl acetate, etc.) are preferred as repulping and rinsing solvents.

[0064] After precipitation (including reprecipitation), repulping, or rinsing, the solvent may be removed by decantation, filtration, or other means as needed, followed by drying.

[0065] (Microreactor) A microreactor can be used that has a flow path capable of mixing multiple liquids. The microreactor has multiple inlets at different positions along the flow path, including at least an inlet (first inlet) for introducing monomer components into the microreactor, and other inlets (nth inlet) located downstream of the first inlet for introducing monomer components into the microreactor. The microreactor may have one or more of these other inlets. In addition, if necessary, an introduction passage may be provided that communicates with the flow path and introduces liquid into the flow path via the first inlet or the other inlets. Examples of such introduction passages include the polymerization initiator introduction passage, the chain transfer agent introduction passage, the polymerization initiator etc. introduction passage, and the monomer introduction passage. When the microreactor has an introduction passage, the inlets (e.g., first inlet, second inlet) refer to the confluence of the introduction passage and the flow path. Furthermore, if necessary, the microreactor may also include components other than the flow path, inlets, and introduction passage.

[0066] The cross-sectional shape of the flow path is not particularly limited and can be selected as appropriate depending on the purpose, for example, circular, rectangular, semicircular, triangular, etc.

[0067] The microreactor may be equipped with an inlet for introducing a polymerization initiator into the microreactor upstream of the first inlet, at the same position as the first inlet, or downstream of the first inlet (between the first and second inlets). However, from the viewpoint of maintaining a constant concentration of the polymerization initiator in the flow path, it is preferable to have an inlet for introducing a polymerization initiator into the microreactor at the same position as the first inlet. Similarly, when using a chain transfer agent, an inlet for introducing a chain transfer agent into the microreactor may be equipped with an inlet for introducing a chain transfer agent into the microreactor upstream of the first inlet, at the same position as the first inlet, or downstream of the first inlet. However, it is preferable to have an inlet for introducing a chain transfer agent into the microreactor at the same position as the first inlet.

[0068] The microreactor may or may not have an inlet for introducing a polymerization initiator into the microreactor at the same location as the Nth inlet (for example, the second inlet) or downstream of the Nth inlet. When introducing a polymerization initiator into the microreactor, it is preferable to have an inlet for introducing the polymerization initiator into the microreactor at the same location as the Nth inlet, from the viewpoint of maintaining a constant concentration of the polymerization initiator in the flow path. Similarly, when using a chain transfer agent, an inlet for introducing the chain transfer agent into the microreactor may be provided at the same location as the Nth inlet or downstream of the Nth inlet, but it is preferable to have an inlet for introducing the chain transfer agent into the microreactor at the same location as the first inlet.

[0069] As long as the microreactor has a channel capable of mixing multiple liquids, it is not particularly limited and can be appropriately selected according to the purpose. Examples include micromixers (substrate-type micromixers, pipe-fitting-type micromixers, etc.) and branched tubes.

[0070] A substrate-type micromixer consists of a substrate with channels formed inside or on its surface, and is sometimes referred to as a microchannel. The substrate-type micromixer is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to the purpose. Examples include the mixer with fine channels for mixing described in International Publication No. 96 / 30113; and the mixer described in Chapter 3 of the document "Microreactors," by W. Ehrfeld, V. Hessel, and H. Lowe, published by Wiley-VCH.

[0071] In a substrate-type micromixer, it is preferable that, in addition to the main flow channel, an introduction channel is formed which communicates with the main flow channel and introduces multiple liquids into the main flow channel. That is, it is preferable that the upstream side of the main flow channel branches according to the number of introduction channels. The number of introduction channels is not particularly limited and can be appropriately selected according to the purpose, but it is preferable to introduce multiple liquids to be mixed from separate introduction channels and then merge them in the main flow channel for mixing. Alternatively, one liquid may be pre-filled in the main flow channel, and the other liquids may be introduced through the introduction channels.

[0072] A pipe-fit type micromixer is equipped with internally formed flow channels and, if necessary, connecting means for connecting the internally formed flow channels to a tube. The connection method of the connecting means is not particularly limited and can be appropriately selected from known tube connection methods depending on the purpose, such as screw-in type, union type, butt-weld type, slip-on welding type, socket welding type, flange type, buckle type, flare type, mechanical type, etc.

[0073] In a pipe-joint type micromixer, it is preferable that, in addition to the main flow channel, an introduction channel is formed inside the main flow channel that communicates with the main flow channel and introduces multiple liquids into the main flow channel. That is, it is preferable that the upstream side of the main flow channel is branched according to the number of introduction channels. If there are two introduction channels, for example, a T-shaped or Y-shaped pipe-joint type micromixer can be used, and if there are three introduction channels, for example, a cross-shaped configuration can be used. Alternatively, one liquid may be pre-filled in the main flow channel, and the other liquids may be introduced through the introduction channels.

[0074] The material of the micromixer (e.g., the flow path) is not particularly limited and can be appropriately selected according to requirements such as heat resistance, pressure resistance, solvent resistance, and ease of processing. Examples include stainless steel, titanium, copper, nickel, aluminum, silicon, and fluororesins such as Teflon®, PFA (perfluoroalkoxy resin), TFAA (trifluoroacetamide), and PTFE (polytetrafluoroethylene).

[0075] Since micromixers precisely control the flow of the reaction solution through their microstructure, it is preferable that they be manufactured using microfabrication technology. Microfabrication technology is not particularly limited and can be appropriately selected depending on the purpose. Examples include (a) LIGA technology combining X-ray lithography and electroplating, (b) high aspect ratio photolithography using EPON SU8, (c) mechanical micro-cutting (such as micro-drilling using a drill with a micro-order diameter that rotates at high speed), (d) high aspect ratio silicon processing using Deep RIE, (e) Hot Embossing, (f) stereolithography, (g) laser processing, and (h) ion beam processing.

[0076] Commercially available micromixers can be used, including, for example, microreactors with interdigital channel structures, single mixers and caterpillar mixers from Institute Huell Microtechnik Mainz (IMM); microglass reactors from Microglass; Saitos from CPC Systems; YM-1 and YM-2 mixers from Yamabushi; mixing tees and tees (T-connectors) from Shimadzu GLC; IMT chip reactors from Micro Chemical Technology; Micro-High Mixer developed by Toray Engineering; and Union Tee from Swagelok.

[0077] As a microreactor, a micromixer may be used alone, or a tube reactor may be connected downstream to extend the flow path. By connecting the tube reactor downstream of the micromixer, the length of the flow path can be adjusted. The residence time (reaction time) of the mixed liquid is proportional to the length of the flow path.

[0078] A tube reactor is a reactor that precisely controls the time required for a solution rapidly mixed by a micromixer to carry out a subsequent reaction (residence time control). The tube reactor is not particularly limited; for example, the inner diameter, outer diameter, length, and material of the tube can be appropriately selected according to the desired reaction. Commercially available tube reactors can be used. The material of the tube reactor is not particularly limited; the materials exemplified for the micromixer can be suitably used.

[0079] The flow path has the function of mixing multiple liquids by diffusion and removing reaction heat. The method of mixing liquids within the flow path is not particularly limited and can be appropriately selected according to the purpose, for example, laminar flow mixing and turbulent flow mixing. Among these, laminar flow mixing (static mixing) is preferred because it allows for more efficient reaction control and heat removal. Since the flow path of a microreactor is minute, the multiple liquids introduced from the inlet naturally tend to flow in a laminar-dominated manner and are mixed by diffusion in a direction perpendicular to the flow. In laminar flow mixing, a configuration that divides the laminar flow cross-section of the flowing liquid by providing branching points and merging points within the flow path may be used to increase the mixing speed. When performing turbulent flow mixing (dynamic mixing) in the flow path of a microreactor, the flow can be changed from laminar to turbulent by adjusting the flow rate and the shape of the flow path (three-dimensional shape of the wetted part, shape such as bends in the flow path, wall roughness, etc.). Turbulent flow mixing has the advantage of better mixing efficiency and a faster mixing speed compared to laminar flow mixing.

[0080] Here, a smaller inner diameter of the flow path shortens the diffusion distance of molecules, thus reducing the mixing time and improving mixing efficiency. Furthermore, the ratio of surface area to volume increases, making temperature control, such as heat removal from the reaction, easier. On the other hand, if the inner diameter of the flow path is too small, the pressure loss when flowing the liquid increases, and a special high-pressure pump is required for liquid transfer, which can increase manufacturing costs. In addition, there is a higher tendency for blockage of the flow path by reactants. Furthermore, the structure of the micromixer may be limited due to the restricted liquid flow rate.

[0081] The inner diameter of the flow channel is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to the purpose. For example, 50 μm to 15 mm is preferred, 100 μm to 10 mm is more preferred, 200 μm to 5 mm is even more preferred, and 500 μm to 3 mm is particularly preferred. If the inner diameter is less than 50 μm, the pressure loss may increase. If the inner diameter exceeds 15 mm, the surface area per unit volume becomes small, and as a result, rapid mixing and heat removal of the reaction may become difficult. On the other hand, when the inner diameter is within the above range, mixing of the monomer component introduced into the flow channel and the polymerization initiator (and chain transfer agent) proceeds rapidly, and heat removal of the reaction can be done efficiently, making it easier to control the heat of the reaction.

[0082] There are no particular restrictions on the cross-sectional area of ​​the channel, and it can be appropriately selected depending on the purpose, but for example, 5000 μm 2 ~800mm 2 Preferably, 0.75 mm 2 ~30mm 2 This is more preferable. When the cross-sectional area is within the above range, mixing of the monomer component introduced into the flow path with the polymerization initiator (and chain transfer agent) proceeds rapidly, and the reaction heat can be efficiently removed, making it easier to control the reaction heat.

[0083] The total length of the channel in the microreactor is not particularly limited and can be adjusted as appropriate according to the optimal reaction time, but for example, 0.5 to 500 m is preferred, and 1 to 400 m is more preferred. For example, the length of the channel in the polymer nucleation reaction (first reaction) is preferred, for example, 0.1 to 125 m, more preferably 0.3 to 100 m, and even more preferably 0.5 to 80 m. For example, the length of the channel in the polymer chain extension reaction (second reaction) is preferred, for example, 0.1 to 125 m, more preferably 0.3 to 100 m, and even more preferably 0.5 to 80 m.

[0084] The introduction channel communicates with the flow channel and has the function of introducing multiple liquids into the flow channel. The other end of the introduction channel, separate from the side communicating with the flow channel, is typically connected to a container containing the liquids to be mixed.

[0085] The inner diameter of the inlet passage is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to the purpose. For example, 50 μm to 15 mm is preferred, 100 μm to 10 mm is more preferred, 200 μm to 5 mm is even more preferred, and 500 μm to 3 mm is particularly preferred. If the microreactor has multiple inlet passages, the inner diameters of each inlet passage may be the same or different from each other.

[0086] Other components besides the flow path and introduction path are not particularly limited and can be appropriately selected according to the purpose, but examples include a pump used for liquid transfer, temperature control means, reaction acceleration means, sensors, and a tank for storing the manufactured polymer.

[0087] The pump is not particularly limited and can be appropriately selected from those used industrially, but it is preferable to use one that does not produce pulsation during fluid transfer, such as plunger pumps, gear pumps, rotary pumps, and diaphragm pumps.

[0088] The temperature control means is not particularly limited and can be appropriately selected according to the reaction temperature. Examples include a constant temperature bath, a circulating fan, and a heat exchanger. For example, when the reaction temperature is 80°C, it is preferable to use an oil bath. Furthermore, when cooling to recover the obtained polymer, a constant temperature bath filled with water or ice water is preferred.

[0089] The reaction-promoting means can be appropriately selected depending on the liquids to be mixed and the desired reaction, but examples include vibration energy application means, heating means, light irradiation means, voltage application means, etc. An example of a microreactor equipped with a voltage application means is the microflow electrochemical reactor disclosed in Japanese Patent Application Publication No. 2006-104538. The sensor is not particularly limited and examples include a temperature sensor, a flow rate sensor, a pressure sensor for measuring the pressure in the flow path, etc.

[0090] (Monomer components) The monomer component of the present invention is characterized by containing two or more monomers. Examples of monomers that make up the monomer component include (meth)acrylic monomers, aromatic vinyl monomers, vinyl carboxylate esters, conjugated diene monomers, olefin monomers, vinyl halides, and vinylidene halides, but (meth)acrylic monomers are preferred from the viewpoint of their reactivity. That is, it is preferable that the monomer component introduced into the first inlet and the other inlet contains two or more (meth)acrylic monomers.

[0091] Examples of (meth)acrylic monomers include (meth)acrylic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate; cycloalkyl (meth)acrylates such as 1-methylcyclopentyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-isopropylcyclopentyl (meth)acrylate, 1-propylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, and 1-propylcyclohexyl (meth)acrylate; and (meth)acrylates having cyclic ester groups such as γ-butyrolactone (meth)acrylate. Examples include (meth)acrylates having a cyclic ether group, such as 3,4-epoxycyclohexyl (meth)acrylate, glycidyl (meth)acrylate, β-methylglycidyl acrylate, and oxetanyl (meth)acrylate; (meth)acrylic acid esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caplocactone-modified 2-hydroxyethyl (meth)acrylate; and ethylene glycol (meth)acrylates such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, isooctyloxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. In addition to the above, monomers described later in the section on photoresist resins are also examples.

[0092] Examples of aromatic vinyl monomers include styrene, alkylstyrene (vinyltoluenes such as o-, m-, and p-methylstyrene, vinylxylenes such as 2,4-dimethylstyrene, p-ethylstyrene, p-isopropylstyrene, p-butylstyrene, pt-butylstyrene, etc.), α-alkylstyrene (α-methylstyrene, α-methyl-p-methylstyrene, etc.), alkoxystyrene (o-, m-, and p-methoxystyrene, pt-butoxystyrene, etc.), halostyrene (o-, m-, and p-chlorostyrene, p-bromostyrene, etc.), styrene sulfonic acid, or alkali metal salts thereof.

[0093] Examples of vinyl carboxylates include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, etc. 1-10 Examples include vinyl carboxylates.

[0094] Examples of conjugated diene monomers include butadiene, isoprene, chloroprene, neoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperiene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, etc. 4-16 Examples include dienes.

[0095] Examples of olefin monomers include ethylene, propylene, and butene (isobutene, etc.). 2-10 Alkenes and the like can be cited as examples.

[0096] Examples of vinyl halides include vinyl fluoride, vinyl chloride, and vinyl bromide. Examples of vinylidene halides include vinylidene fluoride, vinylidene chloride, and vinylidene bromide.

[0097] The present invention is particularly suitable for the production of a resin for a photoresist because a polymer having a uniform copolymer composition and a narrow molecular weight distribution can be obtained. Therefore, it is preferable that the monomer component includes a monomer having a group (which may be referred to as an "acid-decomposable group") in which a part thereof is eliminated by the action of an acid to generate a polar group. Thereby, the polarity of the polymer (resin for photoresist) increases due to the action of an acid, and the solubility in an alkaline developer increases.

[0098] Examples of the polar group include phenolic hydroxyl group, carboxy group, fluorinated alcohol group (preferably hexafluoroisopropanol group), sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl)methylene group and other acidic groups; alcoholic hydroxyl group and the like. Among them, carboxy group, fluorinated alcohol group (preferably hexafluoroisopropanol group), and sulfonic acid group are preferable.

[0099] As the acid-decomposable group, a group in which a hydrogen atom of the polar group is substituted with a group that is eliminated by an acid is preferable. Examples of the acid-decomposable group include -C(R I )(R II )(R III ), -C(R IV )(R V )(OR VI ) and the like. In the above formula, R I to R III , R VI each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R IV and R V each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R I to R IIIAt least two of these groups may bond to each other to form a ring. Also, R IV and R V These elements may be joined together to form a ring.

[0100] The number of carbon atoms in the acid-degradable group is not particularly limited, but is preferably 4 or more, and more preferably 5 or more. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 20.

[0101] The aforementioned R I ~R VI The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, n-butyl group, s-butyl group, t-butyl group, hexyl group, octyl group, etc.

[0102] The aforementioned R I ~R VI The cycloalkyl group may be either a monocyclic hydrocarbon group or a polycyclic (bridged ring) hydrocarbon group. Preferred monocyclic hydrocarbon groups are cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Preferred polycyclic hydrocarbon groups are cycloalkyl groups having 6 to 20 carbon atoms, such as adamantyl, norbornyl, isobolonyl, camphanyl, dicyclopentyl, α-pinel, tricyclodecanyl, tetracyclododecyl, and androstanyl groups. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0103] The aforementioned R I ~R VI The aryl group is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, naphthyl group, or anthryl group.

[0104] The aforementioned R I ~R VI The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, or a naphthylmethyl group.

[0105] The aforementioned R I ~R VI The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, or a cyclohexenyl group.

[0106] The aforementioned R I ~R III A ring formed by at least two of the groups being bonded to each other, and R IV and R V A cycloalkane ring is preferred as the ring formed by the bonding of these elements. The cycloalkane ring is preferably a monocyclic cycloalkane ring such as a cyclopropane ring, cyclobutane ring, cyclopentane ring, or cyclohexane ring; or a polycyclic cycloalkane ring such as a norbornane ring, tricyclodecane ring, tetracyclododecane ring, or adamantane ring.

[0107] Note, R I ~R VI The alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, and cycloalkane ring in each of these may each have substituents.

[0108] Among the acid-degradable groups, t-butyl groups, t-amyl groups, and groups represented by the following formulas (I) to (IV) are preferred.

[0109] [ka]

[0110] R in equations (I) to (IV) above 2 ~R 7 , R a , n, p, and ring Z 1 These are the R values ​​in equations (a1) to (a4) described below. 2 ~R 7 , R a , n, p, and ring Z 1 It indicates the same thing.

[0111] The acid-degradable group may be provided via a spacer. The spacer is the same as the linking group exemplified and described as A in formula (1) described later.

[0112] Examples of monomers having the acid-degradable group include monomers represented by the following formula (1).

[0113] [ka]

[0114] In equation (1) above, R 1 R represents the acid-degradable group. In formula (1), R represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the C1-C6 alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isoamyl, s-amyl, t-amyl, and hexyl groups. Examples of the C1-C6 alkyl group having a halogen atom include a group in which one or more hydrogen atoms constituting the alkyl group, such as trifluoromethyl and 2,2,2-trifluoroethyl, are replaced by halogen atoms (halo(C) 1-6 Examples include alkyl groups.

[0115] In formula (1) above, A represents a single bond or a linking group. Examples of the linking group include a carbonyl group (-C(=O)-), an ether bond (-O-), an ester bond (-C(=O)-O-), an amide bond (-C(=O)-NH-), a carbonate bond (-OC(=O)-O-), a group formed by linking multiple such bonds, and an alkylene group bonded to these. Examples of the alkylene group include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups, as well as divalent alicyclic hydrocarbon groups (especially divalent cycloalkylene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups.

[0116] Among the monomers represented by formula (1), at least one monomer selected from the group consisting of monomers represented by the following formulas (a1) to (a4) is preferred. The "at least one monomer selected from the group consisting of monomers represented by formulas (a1) to (a4)" may be referred to as "monomer a".

[0117] [ka]

[0118] In the monomers represented by formulas (a1) to (a4), R represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom, similar to R in formula (1), and A represents a single bond or a linking group. Among the A in formulas (a1) to (a4), a single bond or a group in which an alkylene group and a carbonyloxy group are bonded (alkylene-carbonyloxy group) is preferred. 2 ~R 4 R represents an alkyl group having 1 to 6 carbon atoms, which may have substituents, and which may be identical or different. 2 and R 3 They may be joined to each other to form a ring. 5 , R 6R represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or substituents, and is identical or different to the other. 7 -COOR c The base is indicated, and the R c R represents a tertiary hydrocarbon group, tetrahydrofuranyl group, tetrahydropyranyl group, or oxepanyl group, which may have substituents. n represents an integer from 1 to 3. If n is 2 or 3, then 2 or 3 R 7 These may be the same or different. a is ring Z 1 A substituent bonded to ring Z, which may be the same or different, represents an oxo group, an alkyl group, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a carboxyl group which may be protected by a protecting group. p represents an integer from 0 to 3. Ring Z 1 represents an alicyclic hydrocarbon ring with 3 to 20 carbon atoms. When p is 2 or 3, there are 2 or 3 R a These may be the same or different.

[0119] The aforementioned R a Examples of alkyl groups in this context include C1-C6 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, isoamyl, s-amyl, t-amyl, and n-hexyl groups.

[0120] The aforementioned R a Examples of hydroxyalkyl groups in this context include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl groups, etc. 1-6 Examples include alkyl groups.

[0121] The aforementioned R a Examples of protecting groups that the hydroxyl group and hydroxyalkyl group may have include C1, methyl, ethyl, t-butyl, etc. 1-4Alkyl group; a group that forms an acetal bond with the oxygen atom constituting the hydroxyl group (for example, a methoxymethyl group, etc.) 1-4 Alkyl-OC 1-4 Examples include alkyl groups; and groups that form an ester bond with the oxygen atom constituting the hydroxyl group (e.g., acetyl group, benzoyl group, etc.).

[0122] The aforementioned R a Examples of protecting groups for the carboxyl group in C include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, isoamyl, s-amyl, t-amyl, and hexyl groups. 1-6 Alkyl groups include 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, and 2-oxepanyl group.

[0123] The aforementioned R 2 ~R 6 Examples of C1-C6 alkyl groups in this invention include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isoamyl, s-amyl, t-amyl, and hexyl groups. In this invention, among others, C 1-4 Alkyl alkyl groups are preferred, more preferably C 1-3 Alkyl alkyl groups, more preferably C 1-2 It is an alkyl group.

[0124] The aforementioned R 2 ~R 6 The substituents that the C1-C6 alkyl group in the compound may have include, for example, a halogen atom, a hydroxyl group, a substituted hydroxyl group (e.g., methoxy, ethoxy, propoxy, etc.). 1-4 Examples include alkoxy groups, cyano groups, etc. Examples of substituent alkyl groups having 1 to 6 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, and other alkyl groups in which one or more hydrogen atoms constituting the alkyl group are replaced by halogen atoms (H1C 1-6An alkyl group; a hydroxymethyl, 2-hydroxyethyl, methoxymethyl, 2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, cyanomethyl, 2-cyanoethyl group, etc. may be mentioned.

[0125] R 2 and R 3 When they are bonded to each other to form a ring, examples of the ring include an alicyclic hydrocarbon ring having 3 to 12 carbon atoms which may have a substituent.

[0126] The said R c Examples of the tertiary hydrocarbon group in R include a t-butyl group, a t-amyl group, etc.

[0127] The said R c Examples of the substituent which the tertiary hydrocarbon group in R may have include a halogen atom, a hydroxy group, a substituted hydroxy group (e.g., a C 1-4 alkoxy group such as a methoxy, ethoxy, propoxy group, etc.), a cyano group, etc.

[0128] The alicyclic hydrocarbon ring having 3 to 20 carbon atoms in the said ring Z 1 Examples include cycloalkane rings having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 12 members) such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring; cycloalkene rings having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 10 members) such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, etc., which are monocyclic alicyclic hydrocarbon rings; an adamantane ring; a norbornane ring, a norbornene ring, a bornane ring, an isobornane ring, tricyclo[5.2.1.0 2,6 decane ring, tetracyclo[4.4.0.1 2,5 .1 7,10 dodecane ring, etc., which are rings containing a norbornane ring or a norbornene ring; a perhydroindene ring, a decalin ring (perhydronaphthalene ring), a perhydrofluorene ring (tricyclo[7.4.0.0 3,8A ring in which a polycyclic aromatic condensed ring such as a tridecane ring or a perhydroanthracene ring is hydrogenated (preferably a fully hydrogenated ring); tricyclo[4.2.2.1 2,5 Bridged hydrocarbon rings such as bicyclic, tricyclic, and tetracyclic rings such as 2,5 undecane ring (for example, bridged hydrocarbon rings having about 6 to 20 carbon atoms), and bridged cyclic hydrocarbon rings having about 2 to 6 rings such as these can be mentioned.

[0129] Moreover, it is preferable that the monomer component includes a monomer having an alicyclic skeleton having at least [-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-O-C(=O)-]. When using the monomer having an alicyclic skeleton, higher substrate adhesion and etching resistance can be imparted to the polymer (resin for photoresist). In addition, the monomer having an alicyclic skeleton having at least [-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-O-C(=O)-] may be referred to as "monomer b".

[0130] Among them, the monomer b is preferably at least one monomer selected from the group consisting of monomers represented by the following formulas (b1) to (b5). In the following formulas (b1) to (b5), R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and A represents a single bond or a linking group. X represents a non-bond, a methylene group, an ethylene group, an oxygen atom, or a sulfur atom. Y represents a methylene group or a carbonyl group. Z represents a divalent organic group (for example, the alkylene groups exemplified and described as the alkylene group which may be included in A in the monomers represented by the formulas (a1) to (a4), particularly a linear alkylene group having 1 to 3 carbon atoms), etc.). V 1 ~V 3 are the same or different and represent -CH2-, [-C(=O)-], or [-C(=O)-O-]. However, at least one of V 1 ~V 3 is [-C(=O)-O-]. R 8 ~R 14These represent, either identically or differently, a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a carboxyl group which may be protected by a protecting group, or a cyano group.

[0131] [ka]

[0132] Examples of R and A in the monomers represented by formulas (b1) to (b5) are the same as those of R and A in the monomers represented by formulas (a1) to (a4). Also, R in the monomers represented by formulas (b1) to (b5) 8 ~R 14 The alkyl group, optionally protected hydroxyl group, optionally protected hydroxyalkyl group, and optionally protected carboxyl group in the monomer represented by formula (a1) to (a4) are R a Similar examples can be given to the case in [the previous example].

[0133] The aforementioned R 8 ~R 14 Examples of alkyl groups in this context include trifluoromethyl, 2,2,2-trifluoroethyl, and other groups in which one or more hydrogen atoms constituting the alkyl group are replaced by fluorine atoms [fluoro(C) 1-6 Examples include alkyl groups.

[0134] In the monomer represented by formulas (b1) to (b4), the R 8 ~R 11 Each of these may have one or two or more, and 1 to 3 is preferred. Also, in the monomer represented by formulas (b1) to (b4), the R 8 ~R 11 If there are two or more of the above R 8 ~R 11 These may be the same or different.

[0135] Among monomers b, those represented by formula (b1) and R 8 is a group having a cyano group, an amide group, an imide group, or fluoro(C) 1-6 Monomers that are electron-withdrawing groups such as alkyl groups; monomers represented by formula (b2); monomers represented by formula (b3) in which Y is a carbonyl group; monomers represented by formula (b4); and monomers represented by formula (b5) are preferred because they can impart excellent substrate adhesion and etching resistance to polymers (photoresist resins), have excellent solubility in alkaline developers, and can form fine patterns with high precision.

[0136] In the above formula (b1), R 8 is a group having a cyano group, an amide group, an imide group, or fluoro(C) 1-6 ) If it is an electron-withdrawing group such as an alkyl group, then R 8 It is particularly preferable that it is bonded to at least the carbon atoms marked with an asterisk in formula (b1).

[0137] The monomer component may further contain monomer c. Monomer c is a monomer represented by the following formula (c1). When the monomer component contains monomer c, higher transparency and etching resistance can be imparted to the polymer (photoresist resin). In the formula, R represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. A represents a single bond or a linking group. b represents a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a carboxyl group which may be protected by a protecting group, or a cyano group which may be protected by a protecting group, with hydroxyl groups and cyano groups being preferred. q represents an integer from 1 to 5. Ring Z 2 This represents an alicyclic hydrocarbon ring with 6 to 20 carbon atoms. If q is an integer between 2 and 5, then 2 to 5 R b These may be the same or different.

[0138] [ka]

[0139] Examples of R and A in the monomer represented by formula (c1) are the same as those of R and A in the monomers represented by formulas (a1) to (a4). Also, R in the monomer represented by formula (c1) b The hydroxyl group, hydroxyalkyl group, and carboxyl group that may be protected by a protecting group in the monomer represented by formulas (a1) to (a4) are R a Similar examples can be given to the case in [the previous example].

[0140] Ring Z in the monomer represented by formula (c1) 2 This refers to an alicyclic hydrocarbon ring having 6 to 20 carbon atoms, for example, a cycloalkane ring with 6 to 20 members (preferably 6 to 15 members, particularly preferably 6 to 12 members) such as a cyclohexane ring or a cyclooctane ring; a monocyclic alicyclic hydrocarbon ring with 6 to 20 members (preferably 6 to 15 members, particularly preferably 6 to 10 members) such as a cyclohexene ring; an adamantane ring; a norbornane ring, norbornene ring, bornane ring, isobornane ring, tricyclo[5.2.1.0 2,6 ] Decane ring, tetracyclo[4.4.0.1 2,5 .1 7,10 ] Rings containing norbornane rings such as dodecane rings; perhydroindene rings, decalin rings (perhydronaphthalene rings), perhydrofluorene rings (tricyclo[7.4.0.0 3,8 [Tridecane ring), perhydroanthracene ring, or other polycyclic aromatic condensed rings are hydrogenated (preferably fully hydrogenated rings); tricyclo[4.2.2.1 2,5 Examples include bridged hydrocarbon rings of 2 to 6 rings, such as bicyclic, tricyclic, and tetracyclic systems like undecane rings (for example, bridged hydrocarbon rings with about 6 to 20 carbon atoms). The aforementioned ring Z 2 Among these, rings containing a norbornane ring or an adamantane ring are preferred.

[0141] (polymer) The polymer obtained in this invention has a homogeneous copolymer composition and a narrow molecular weight distribution, and therefore possesses characteristics such as extremely high solubility in solvents. For this reason, the polymer can be suitably used as a resin for photoresists and the like.

[0142] The weight-average molecular weight (Mw) of the polymer is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,500 to 40,000, even more preferably 2,000 to 20,000, particularly preferably 2,500 to 10,000, and most preferably 3,000 to 6,000. The molecular weight distribution (Mw / Mn) of the polymer is not particularly limited, but is preferably 2.00 or less, more preferably 1.45 or less, and even more preferably 1.20 or less. When the polymer obtained in this invention is used as a resin for photoresists, a molecular weight distribution (Mw / Mn) of 1.45 or less is preferable because it has excellent solubility in alkaline developers and can form fine patterns with high precision. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification can be measured, for example, by GPC using polystyrene as a standard substance.

[0143] (Resin composition for photoresists) The polymer obtained in this invention can be used as a resin for photoresists, as described above. That is, a composition containing the polymer obtained in this invention and a radiation-sensitive acid generator can be used as a resin composition for photoresists.

[0144] As a radiation-sensitive acid generator, conventional or known compounds that efficiently generate acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays can be used, and are compounds consisting of a parent nucleus and the acid generated. Examples of the parent nucleus include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), onium salt compounds such as phosphonium salts, diazonium salts, and pyridinium salts, sulfonimide compounds, sulfon compounds, sulfonic acid ester compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oximesulfonate compounds, and hydrazine sulfonate compounds. Examples of the acid generated upon exposure include alkyl or alkylfluoride sulfonic acid, alkyl or alkylfluoride carboxylic acid, and alkyl or alkylfluoride sulfonylimide acid. One or more of these may be used.

[0145] The amount of radiation-sensitive acid generator used can be appropriately selected according to the strength of the acid generated by irradiation and the ratio of each repeating unit in the photoresist resin. For example, it can be selected from a range of 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably 2 to 20 parts by weight, per 100 parts by weight of the photoresist resin.

[0146] A photoresist resin composition can be prepared, for example, by mixing the photoresist resin and a radiation-sensitive acid generator in a resist solvent. As the resist solvent, glycol-based solvents, ester-based solvents, ketone-based solvents, or mixtures thereof, as exemplified as polymerization solvents, can be used.

[0147] The concentration of the photoresist resin in the photoresist resin composition is not particularly limited, but is, for example, 3 to 40% by weight. The photoresist resin composition may also contain alkali-soluble components such as alkali-soluble resins (e.g., novolac resins, phenolic resins, imide resins, carboxyl group-containing resins), colorants (e.g., dyes), etc.

[0148] (Pattern formation method) By applying the aforementioned photoresist resin composition onto a substrate or base material, drying it, and then exposing the coating film (resist film) to a predetermined mask (or further baking after exposure) to form a latent image pattern, followed by alkaline dissolution, a fine pattern can be formed with high precision.

[0149] Examples of substrates or base materials include silicon wafers, metals, plastics, glass, and ceramics. The photoresist resin composition can be applied using conventional coating methods such as spin coaters, dip coaters, and roller coaters. The thickness of the coating film is, for example, 0.05 to 20 μm, preferably 0.1 to 2 μm.

[0150] Exposure can utilize radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays.

[0151] Upon exposure, acid is generated from the radiation-sensitive acid generator. This acid rapidly removes protective groups (acid-degradable groups) such as carboxyl groups from the alkali-soluble polymerization units (repeating units with acid-degradable groups) of the photoresist resin composition, generating carboxyl groups and other groups that contribute to solubilization. Therefore, a predetermined pattern can be formed with high precision by development with an alkaline developer. [Examples]

[0152] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin were determined by GPC (gel permeation chromatography) measurement using tetrahydrofuran solvent. Polystyrene was used as the standard sample, and a refractive index detector (RI detector) was used as the detector. For the GPC measurement, three Showa Denko K.K. columns (product name "KF-806L") connected in series were used, and the measurement was performed under the conditions of column temperature 40°C, RI temperature 40°C, and tetrahydrofuran flow rate 0.8 mL / min. The molecular weight distribution (Mw / Mn) was calculated from the above measurement values.

[0153] The microreactor used in this embodiment is the microreactor shown in Figure 1, which includes a micromixer consisting of a T-shaped pipe fitting and a tube reactor connected downstream of the micromixer. Specifically, the microreactor includes a polymerization initiator introduction channel 1, which is an introduction channel for a polymerization initiator, or a polymerization initiator and a chain transfer agent; a first monomer introduction channel 2; a micromixer 3, which is the confluence (mixing) section of these introduction channels; a tube reactor 5, which is a flow channel connected downstream of the micromixer 3; a second monomer introduction channel 4; a micromixer 6, which is the confluence (mixing) section of the tube reactor 5 and the second monomer introduction channel 4; and a tube reactor 7, which is a flow channel connected downstream of the micromixer 6. The microreactor used in this embodiment is further equipped with pumps for liquid delivery upstream of the polymerization initiator introduction channel 1, the first monomer introduction channel 2, and the second monomer introduction channel 4, but these are omitted in Figure 1. Furthermore, the connection between the tube reactor 5 and the micromixer 6, and the downstream end of the tube reactor 7, are equipped with reaction solution collection sections, but these are omitted in Figure 1.

[0154] The micromixer used was a custom-made product manufactured by Sanko Seiki Kogyo Co., Ltd. (It is possible to obtain an equivalent product by requesting its manufacture based on the description in this embodiment). The mixer was made of stainless steel, had a T-shape, and an inner diameter of 400 μm. Tube reactors 5 and 7 used stainless steel tubing manufactured by GL Sciences Co., Ltd. A Harvard Model 11 Plus syringe pump was used for liquid delivery. The reaction temperature was controlled by immersing the entire microreactor in a constant temperature bath.

[0155] [Examples 1 and 2] (First stage reaction) AIBN (azobisisobutyronitrile) was introduced into the microreactor as a polymerization initiator, and an equimolar mixture of GBLMA (γ-butyrolactone (meth)acrylate) and MCPMA (1-methylcyclopentyl (meth)acrylate) was introduced into the microreactor via the polymerization initiator introduction channel and the first monomer introduction channel, respectively. The reaction solution was then collected, and the amount of residual monomer and the gravimetric molecular weight of the reactant (polymer) were measured. The monomer conversion rate, gravimetric molecular weight and molecular weight distribution of the polymer, and microreactor flow rate conditions in the first reaction stage are as shown in Table 1.

[0156] (Second stage reaction) After the first reaction stage, an equimolar mixture of GBLMA and MCPMA was introduced into the microreactor via a second monomer introduction channel as a second monomer component. The reaction solution was then collected, and the amount of remaining monomer and the gravimetric molecular weight of the reactants (polymer) were measured. The conditions for monomer conversion rate, gravimetric molecular weight and molecular weight distribution of the polymer, and microreactor flow rate in the second reaction stage are shown in Table 2.

[0157] [Example 3] (First stage reaction) A mixture of AIBN (azobisisobutyronitrile) as a polymerization initiator and RAFT-A (2-cyano-2-propyl 4-cyanobenzodithioate) as a chain transfer agent, and an equimolar mixture of GBLMA (γ-butyrolactone (meth)acrylate) and MCPMA (1-methylcyclopentyl (meth)acrylate) as the first monomer component were introduced into the microreactor via the polymerization initiator introduction channel and the first monomer introduction channel, respectively. Subsequently, the reaction solution was collected, and the amount of residual monomer and the gravimetric molecular weight of the reactant (polymer) were measured. The conditions for monomer conversion rate, gravimetric molecular weight and molecular weight distribution of the polymer, and microreactor flow rate in the first reaction stage are as shown in Table 1.

[0158] (Second stage reaction) After the first reaction stage, an equimolar mixture of GBLMA and MCPMA was introduced into the microreactor via a second monomer introduction channel as a second monomer component. The reaction solution was then collected, and the amount of remaining monomer and the gravimetric molecular weight of the reactants (polymer) were measured. The conditions for monomer conversion rate, gravimetric molecular weight and molecular weight distribution of the polymer, and microreactor flow rate in the second reaction stage are shown in Table 2.

[0159] [Examples 4-24] Except for changing the polymerization initiator, chain transfer agent, and reaction conditions to those described in Tables 1 and 2, the procedure was the same as in Example 3. The weight molecular weight and other properties of the polymers obtained in the first and second reaction steps were measured and are listed in Tables 1 and 2, respectively.

[0160] [Table 1]

[0161] [Table 2] [Explanation of symbols]

[0162] 1. Introduction route for polymerization initiator, etc. 2. First monomer introduction path 3 Micromixer 4. Second monomer introduction route 5-Tube Reactor 6 Micro Mixer 7 Tube Reactor

Claims

1. A method for producing a polymer, comprising using a microreactor equipped with a channel capable of mixing multiple liquids, and radically polymerizing a monomer component containing two or more monomers in the presence of a polymerization initiator containing a cyano group, The monomer component is a monomer having an acid-degradable group and [-C(=O)-O-], [-S(=O) ２ It contains a monomer having an alicyclic skeleton having at least [-O-] or [-C(=O)-O-C(=O)-], The monomer having the acid-degradable group is one of the following formulas (a1) to (a4) 【Chemistry 1】 (In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A represents a single bond or a linking group. R ２ ~R ４ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms which may have a substituent. Note that R ２ and R ３ may be bonded to each other to form a ring. R ５ , R ６ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. R ７ represents a -COOR ｃ group, and the above-mentioned R ｃ represents a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group. n represents an integer of 1 to 3. When n is 2 or 3, the two or three R ７ may be the same or different from each other. R ａ is a substituent bonded to ring Z １ and is the same or different and represents an oxo group, an alkyl group, a hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a carboxy group which may be protected by a protecting group. p represents an integer of 0 to 3. Ring Z １ represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms.) At least one selected from the group consisting of monomers represented by, Said [-C(=O)-O-], [-S(=O) ２ A monomer having an alicyclic skeleton containing at least [-O-] or [-C(=O)-O-C(=O)-] is defined by the following formulas (b1) to (b5) 【Chemistry 2】 (In the formula, R represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom; A represents a single bond or a linking group; X represents an unbonded atom, a methylene group, an ethylene group, an oxygen atom, or a sulfur atom; Y represents a methylene group or a carbonyl group; Z represents a divalent organic group. V) １ ~V ３ They are the same or different, -CH ２ - indicates [-C(=O)-] or [-C(=O)-O-]. However, V １ ~V ３ At least one of them is [-C(=O)-O-]. ８ ~R １４ (These represent, either identically or differently, a hydrogen atom, a fluorine atom, an alkyl group which may have a fluorine atom, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a carboxyl group which may be protected by a protecting group, or a cyano group.) At least one selected from the group consisting of monomers represented by, The microreactor comprises a first inlet for introducing monomer components and another inlet located downstream of the first inlet. A method for producing a polymer, characterized by introducing monomer components into the first inlet and the other inlet (excluding a method for producing a polymer in which monomer components are radically polymerized in the presence of a polymerization initiator and a chain transfer agent).

2. The method for producing a polymer according to claim 1, wherein the microreactor is a substrate-type micromixer.

3. A method for producing a polymer according to claim 1 or 2, wherein the monomer components introduced into the first inlet and the other inlet include two or more (meth)acrylic monomers.

4. A method for producing a polymer according to any one of claims 1 to 3, wherein the monomers contained in the monomer component introduced into the first inlet and the other inlet are the same, and the error in the content ratio of each monomer is within ±5%.

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