Polymer manufacturing methods

Abstract

This invention provides a method for manufacturing a polymer with a uniform copolymer composition and a narrow molecular weight distribution. The method utilizes a microreactor equipped with a flow path capable of mixing multiple liquids, and performs free radical polymerization of a monomer component containing two or more monomers in the presence of a polymerization initiator. The microreactor is characterized by having a first inlet for introducing the monomer component and other inlets located downstream of the first inlet, through which the monomer component is introduced.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a polymer. Prior Technology

[0002] The most common method for manufacturing (meth)acrylate polymers is the one-step polymerization method, which involves dissolving raw monomers, polymerization initiators, and chain transfer agents (if desired) in a polymerization solvent and then heating them to polymerize them. However, the one-step polymerization method has the following drawbacks due to the difficulty in controlling the overall reaction temperature: subtle variations in reaction temperature lead to differences in the amount of free radicals generated, resulting in a wide molecular weight distribution of the obtained polymer (the polymer becomes non-uniform). Furthermore, the difficulty in controlling the reaction temperature also leads to batch-to-batch quality variations.

[0003] Furthermore, when two or more monomers with different reactivity are added as raw materials, the polymer formed in the early stages of the polymerization reaction contains a higher proportion of units derived from the more reactive monomer, while the polymer formed in the later stages of the polymerization reaction contains a higher proportion of units derived from the less reactive monomer. Because of its large reaction system, the single-stage polymerization method makes it difficult to control the monomer ratio, thus it is easily affected by the aforementioned factors, resulting in a non-uniform copolymer composition of the final polymer.

[0004] As a solution to the aforementioned problems, one method is to mix or separately supply the raw monomer, polymerization initiator, and chain transfer agent (if necessary) into a system maintained at a certain temperature for polymerization, which is called dropwise polymerization (semi-batch polymerization). Examples of dropwise polymerization methods include preheating the monomer before dropwise addition, or adding the monomer dropwise into a polymerization solvent maintained at a certain temperature (Patent Documents 1 and 2).

[0005] Compared to single-stage polymerization, dropwise polymerization has a smaller reaction system, so even if there are two or more monomers used as raw materials, the ratio of them in the reaction system can be easily controlled, which is effective in obtaining a uniform polymer. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2004-269855 [Patent Document 2] Japanese Patent Application Publication No. 2004-355023 Summary of the Invention

[0007] For photoresist resins, in addition to physical properties such as optical properties, chemical properties, coatability, and adhesion to the substrate or underlying film, a narrow molecular weight distribution is also required to improve solubility in developer. Especially in the manufacturing process of semiconductor materials requiring fine and precise shapes, a uniform copolymer composition and narrow molecular weight distribution of the polymer allow for precise control of solubility in developer, thus enabling ultra-fine processing. Furthermore, with the miniaturization of resist patterns, the quality requirements for photoresist resins are further increasing, seeking photoresist resins with small batch-to-batch molecular weight variations. Therefore, the drop polymerization method described above is commonly used as a manufacturing method for photoresist resins. However, the drop polymerization method is difficult to control the reaction temperature, and it is not sufficient as a manufacturing method for photoresist resins requiring even higher uniformity.

[0008] Furthermore, as one of the flow polymerization methods, there is a known polymerization method using a microreactor. Although this method has excellent control over the reaction temperature, its polymerization reaction is carried out in the same way as the usual batch method (such as the single polymerization method mentioned above). Therefore, it is not sufficient from the point of view of the uniformity of the copolymer composition of the photoresist resin.

[0009] Thus, despite the industry’s strong demand for polymers with uniform copolymer composition and narrow molecular weight distribution, their manufacturing methods have not yet been established.

[0010] Therefore, the object of the present invention is to provide a method for manufacturing a polymer to obtain a polymer with a uniform copolymer composition and a narrow molecular weight distribution.

[0011] The inventors conducted diligent research to achieve the aforementioned objectives and discovered that, in the presence of a polymerization initiator, free radical polymerization of monomer components containing two or more monomers under specific reaction conditions yields polymers with uniform copolymer composition and narrow molecular weight distribution. This invention is based on these insights.

[0012] That is, the present invention provides a method for manufacturing a polymer, which uses a microreactor equipped with a flow path capable of mixing multiple liquids to perform free radical polymerization of a monomer component containing two or more monomers in the presence of a polymerization initiator, characterized in that: The aforementioned microreactor has a first inlet for introducing monomer components, and other inlets located downstream of the first inlet. The monomeric components are introduced into the first inlet and the other inlets mentioned above.

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

[0014] The monomers introduced into the first inlet and the other inlets mentioned above preferably contain the same monomers, and the content of each monomer has an error of within ±5%.

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

[0016] In this invention, it is preferable that the chain transfer agent is a chain transfer agent containing sulfur carbonyl sulfide group but not cyanide group, and the polymerization initiator is a polymerization initiator that does not contain cyanide group.

[0017] In this invention, it is preferred that the chain transfer agent is a chain transfer agent containing cyano and thiocarbonyl groups.

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

[0019] According to the present invention, it is possible to manufacture polymers with uniform copolymer composition and narrow molecular weight distribution. Simple Explanation of the Diagram

[0020] [Figure 1] is a conceptual diagram of the microreactor used in the embodiment. Implementation

[0021] This invention relates to a method for manufacturing a polymer using a microreactor equipped with a flow path capable of mixing multiple liquids, in the presence of a polymerization initiator, to perform free radical polymerization of a monomer component containing two or more monomers. The method is characterized in that the microreactor has a first inlet for introducing the monomer component, and other inlets located downstream of the first inlet, through which the monomer component is introduced. Examples of these other inlets include a second inlet, a third inlet, a fourth inlet, and so on (N represents an integer of 2 or more). In this invention, free radical polymerization can also be carried out in the presence of a polymerization initiator and a chain transfer agent.

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

[0023] The reactants produced by the first reaction elongate their polymer chains through a polymer chain elongation reaction described later. That is, the reactants act as the nucleus of the polymer. Therefore, the first reaction can be rewritten as a "polymer nucleus formation reaction".

[0024] The Nth reaction (the reaction following the second reaction) is primarily a reaction that elongates the polymer chains of the reactants produced by the previous reaction. Therefore, the Nth reaction can be rewritten as a "polymer chain elongation reaction." However, the Nth reaction may include reactions that form new reactants that can become the polymer nucleus, thus acting as a reaction other than the reaction that elongates the polymer chains of the reactants produced by the previous reaction. That is, the monomer component introduced through the Nth inlet does not need to be used only in the aforementioned polymer chain elongation reaction; it can also form a new polymer (polymer nucleus) through free radical polymerization with unreacted monomer components.

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

[0026] The above situation also occurs in the first reaction, namely the polymer nucleation reaction, but it can be controlled by introducing monomer components into the polymer chain elongation reaction and adjusting the differences in the concentration of each monomer produced in the first reaction, so that polymers with the same composition can be continuously generated.

[0027] As polymerization initiators, known or conventional free radical polymerization initiators can be used, such as polymerization initiators containing cyano groups and polymerization initiators without cyano groups. Only one polymerization initiator can be used, or two or more can be used.

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

[0029] As a cyanide-free polymerization initiator, known or conventional polymerization initiators can be used, such as dimethyl 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dibutyl 2,2'-azobis(2-methylpropane), and other cyanide-free azo compounds. Furthermore, examples include: ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxy ketals 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 and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; diacyl peroxides such as isobutylperoxide and 3,5,5-trimethylhexylperoxide; peroxy esters such as 1,1,3,3-tetramethylbutyl peroxyneodecanoate and trihexyl peroxyneodecanoate; and peroxydicarbonates such as di-n-propyl peroxide and diisopropyl peroxide, which are peroxide compounds without cyano groups. Also, redox compounds without cyano groups such as hydrogen peroxide and ammonium persulfate can be listed.

[0030] As chain transfer agents, well-known or conventional chain transfer agents used in free radical polymerization can be used, such as chain transfer agents containing thiocarbonyl thio groups (chain transfer agents containing cyano and thiocarbonyl thio groups, chain transfer agents containing thiocarbonyl thio groups but not cyano groups), etc. Only one chain transfer agent can be used, or two or more can be used.

[0031] Examples of chain transfer agents containing cyano and thiocarbonyl thio groups include: 2-cyano-2-propane 4-cyanodithiobenzoic acid, 4-cyano-4-(phenylcarbonothioylthio))valeric acid, 2-cyano-2-propane dithiobenzoic acid, and N-succinimide 4-cyano-4-(phenylcarbonothioylthio))valeric acid, etc. Thiobenzoate chain transfer agents; 4-cyano-4-[(dodecyl thiosulfonyl)hydrothio]valeric acid, dodecyl trithiocarbonate 2-cyano-2-propyl ester, 4-cyano-4-[(dodecyl thiosulfonyl)hydrothio]pentanol, poly(ethylene glycol) methyl ether 4-cyano-4-[(dodecyl thiosulfonyl)hydrothio]valeric acid ester, poly(ethylene glycol) methyl ether (4-cyano-4-valeric acid ester) Chain transfer agents containing cyano groups, such as dodecyl trithiocarbonate and methyl dodecyl trithiocarbonate; chain transfer agents containing cyano groups, such as cyanomethymethyl(phenyl)carbamodithioate, diphenylaminomethyl dithiocyanate, 1-butadiene-imino-4-cyano-4-[N-methyl-N-(4-pyridyl)aminomethylthioylthio]valerate, N-methyl-N-(pyridin-4-yl)aminomethyl dithio-2-cyanopropane-2-yl ester, and methyl(4-pyridyl)aminomethyl dithiocyanate; and chain transfer agents containing cyano groups, such as xanthate esters. From the viewpoint of the molecular weight distribution of the obtained polymer, 4-cyano-4-(thiobenzoylthio)valerate, 2-cyano-2-propanedithiobenzoate, 4-cyano-4-[(dodecylhydrothiocarbonyl)hydrothio]valerate, and 2-cyano-2-propanedithiocarboxylate dodecyl trithiocarbonate are preferred.

[0032] Examples of chain transfer agents containing thiocarbonyl thio groups but without cyano groups include: 2-phenyl-2-propanoic acid dithiobenzoate, 1-(methoxycarbonyl)ethyl dithiobenzoate, benzyl dithiobenzoate, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, methyl 2-phenyl-2-(thiobenzoylthio)acetate, ethyl 2-(thiobenzoylthio)propionate, and bis(thiobenzoyl)propionate. Chain transfer agents of dithiobenzoic acid esters without cyano groups, such as dithioethers; 2-(dodecylthiothiocarbonylthio)propionic acid, 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, methyl 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, N-hydroxybutadiene ester of 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, poly(ethylene glycol) methyl ether (2-methyl-2-propionic acid) Dodecyl trithiocarbonate), poly(ethylene glycol) bis[2-(dodecylthiothoxycarbonylthio)-2-methylpropionate], 2-(dodecylthiothoxycarbonylthio)-2-methylpropionate 3-azido-1-propanol ester, 2-(dodecylthiothoxycarbonylthio)-2-methylpropionate pentafluorophenyl ester, poly(ethylene glycol) methyl ether 2-(dodecylthiothoxycarbonylthio)-2-methylpropionate, poly( Chain transfer agents such as ethylene glycol-based trithiocarbonate chain transfer agents (e.g., bis[2-(dodecylthiocarbonylthio)-2-methylpropionate], bis(dodecylhydrothiocarbonyl)disulfide), etc., which do not contain cyano groups; chain transfer agents such as benzyl 1H-pyrrole-1-dithiocarboxylic acid, methyl 2-propionate (4-pyridyl)aminomethyl dithiomethyl ester, N,N'-dimethyl N,N'-di(4-pyridyl)thiuram disulfide, etc., which do not contain cyano groups; and chain transfer agents such as xanthate chain transfer agents, which do not contain cyano groups. Of these, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate is preferred from the viewpoint of the molecular weight distribution of the obtained polymer.

[0033] In this invention, the polymer obtained when using a chain transfer agent containing cyano and thiocarbonyl groups as the chain transfer agent is a polymer with cyano groups at the ends (polymer ends). Since cyano groups exhibit poor solubility in solvents (e.g., solvents for photoresists), polymers with cyano groups at the ends tend to have poor solvent solubility. However, in the above-mentioned polymers, because the chain transfer agent has a high degree of polymerization control capability, there is a tendency to obtain polymers with uniform copolymer composition and narrow molecular weight distribution. As a result, the above-mentioned polymers tend to have high solvent solubility (e.g., solvents for photoresists).

[0034] On the other hand, when a chain transfer agent containing a thiocarbonyl group but not a cyano group is used as a chain transfer agent, and a polymerization initiator without a cyano group is used as a polymerization initiator, a polymer without a cyano group at the end can be obtained. Therefore, the above polymer tends to have high solvent solubility.

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

[0036] Examples of glycol 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 solvents include lactate esters such as ethyl lactate; propionate esters such as methyl 3-methoxypropionate; and acetate esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl pentanol, cyclopentanone, and cyclohexanone. Examples of ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, and dimethoxyethane (chain ethers); tetrahydrofuran, diethyl ether ... Alkane and other cyclic ethers, etc. Among amide solvents, N,N-dimethylformamide, etc., can be listed. Among sulfoxide solvents, dimethylsulfoxide, etc., can be listed. Among hydrocarbon solvents, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene, etc. Preferably, diol 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 pentyl ketone, cyclopentanone, and cyclohexanone; and mixtures thereof are preferred.

[0037] (Polymer nucleation reaction) The polymer nucleation reaction of this invention, namely the first reaction, is a reaction in which monomer components introduced into the microreactor through the first inlet undergo free radical polymerization. The monomer components introduced through the first inlet are free radical polymerized by a polymerization initiator present in the microreactor system to form reactants (free radical polymers). There is no particular limitation on the means of introducing monomer components into the microreactor; methods such as introducing them into the microreactor through an introduction path (hereinafter sometimes referred to as the "monomer introduction path") are acceptable.

[0038] There are no particular limitations on the means by which the polymerization initiator is introduced into the microreactor. For example, it can be introduced into the microreactor via an introduction path (hereinafter sometimes referred to as the "polymerization initiator introduction path"). There are no particular limitations on the introduction of the polymerization initiator into the microreactor. For example, it can be listed as: [1] before the monomer component is introduced into the microreactor; [2] at the same time as the monomer component is introduced into the microreactor; [3] after the monomer component is introduced into the microreactor. In particular, it is preferred to [2] in terms of being able to efficiently mix the monomer component with the polymerization initiator and to easily control the reaction time or reaction temperature.

[0039] When free radical polymerization is carried out in the presence of a polymerization initiator and a chain transfer agent, the method of introducing the chain transfer agent is the same as that described for introducing a polymerization initiator, such as introducing it into the microreactor via an introduction path (hereinafter sometimes referred to as the "chain transfer agent introduction path"). Furthermore, the aforementioned introduction path can be the same as the polymerization initiator introduction path. That is, a solution containing both the polymerization initiator and the chain transfer agent can be prepared in advance, and this solution can be introduced into the microreactor via an introduction path (hereinafter sometimes referred to as the "polymerization initiator, etc. introduction path"). By using a chain transfer agent, the polymerization reaction can be controlled, and polymers with a more uniform copolymer composition and a narrower molecular weight distribution can be obtained.

[0040] The reaction temperature of this reaction (polymer nucleation reaction), i.e. the temperature of the flow path between the first inlet and the second inlet, is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0-200°C, more preferably 20-180°C, even more preferably 40-160°C, especially preferably 60-140°C, and most preferably 80-120°C.

[0041] The molar concentration (total molar concentration of monomers) of the monomer components in this reaction is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0.01 to 5.0 mol / L, more preferably 0.05 to 3.0 mol / L, and even more preferably 0.1 to 2.0 mol / L. Within the above concentration range, there is a tendency for a better polymer yield per unit time. On the other hand, when the concentration is greater than 5.0 mol / L, there are problems such as increased viscosity of the reaction solution or insolubility of monomer components. Furthermore, when the concentration is less than 0.01 mol / L, there are problems such as decreased reaction rate and decreased polymer yield (incomplete reaction). Moreover, the above refers to the molar concentration of monomer components in the flow path immediately after being introduced into the microreactor.

[0042] The flow rate of the reaction solution in this reaction is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0.001 to 10 mL / min, more preferably 0.005 to 3 mL / min, and even more preferably 0.01 to 1 mL / min. Within the above flow rate range, there is a tendency to achieve rapid mixing of the monomer components and the polymerization initiator, thereby suppressing pressure loss. Furthermore, the above refers to the flow rate of the reaction solution in the flow path immediately after being introduced into the microreactor.

[0043] There are no particular limitations on the residence time in this reaction, and it can be appropriately selected according to the purpose. For example, it is preferred to be 1 to 180 min, more preferably 5 to 120 min, and even more preferably 8 to 90 min. By using a residence time within the above range, there is a tendency to narrow the molecular weight distribution of the obtained polymer.

[0044] The concentration of the polymerization initiator in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-3.0 mol / L, more preferably 0.0005-1.5 mol / L, further preferably 0.001-0.5 mol / L, and even more preferably 0.005-0.2 mol / L. By keeping the concentration within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the polymerization initiator in the flow path immediately after being introduced into the microreactor.

[0045] The concentration of the chain transfer agent in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-3.0 mol / L, more preferably 0.0005-1.5 mol / L, even more preferably 0.001-0.5 mol / L, and particularly preferably 0.005-0.2 mol / L. By keeping the concentration within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the chain transfer agent in the flow path immediately after being introduced into the microreactor.

[0046] The total concentration of the polymerization initiator and chain transfer agent in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-3.0 mol / L, more preferably 0.0005-1.5 mol / L, further preferably 0.001-0.5 mol / L, and even more preferably 0.005-0.2 mol / L. With the concentration within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration in the flow path immediately after being introduced into the microreactor.

[0047] The concentration ratio (polymerization initiator and chain transfer agent / monomer) of the polymerization initiator and chain transfer agent in this invention is not particularly limited, but is preferably 0.001 to 100.0 mol%, more preferably 0.01 to 50.0 mol%, further preferably 0.05 to 30.0 mol%, and even more preferably 0.1 to 20.0 mol%. By keeping the concentration ratio within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the polymerization initiator and chain transfer agent in the flow path immediately after being introduced into the microreactor.

[0048] (Polymer chain elongation reaction) The polymer chain elongation reaction, also known as the Nth reaction (where N is an integer greater than or equal to 2), is a free radical polymerization reaction in which reactants generated in a flow path located downstream of the Nth inlet, between the (N-1)th and Nth inlets, react with monomer components introduced through the Nth inlet. The means of introducing the monomer components into the microreactor is not particularly limited; methods such as introducing them through an inlet path can be used. For example, the second reaction is a free radical polymerization reaction in a flow path located downstream of the second inlet (or, in the case of a third inlet, between the second and third inlets), between reactants generated in a flow path located between the first and second inlets, reacting with monomer components introduced through the second inlet. Furthermore, methods of introducing monomer components into the microreactor can also include introducing them through an inlet path.

[0049] The monomeric components introduced into the first inlet and other inlets are preferably of the same monomer content, more preferably of the same monomer content with an error of ±5%, further preferably of the same monomer content with an error of ±1%, and even more preferably of the same monomer content and its content (substantially the same). Furthermore, the term "error in monomer content" refers to the error in the content (by weight %) of the same specific monomer contained in the monomeric component introduced into the first inlet, compared to the content (by weight %) of that specific monomer contained in the monomeric component introduced into the first inlet. For example, if the content of monomer A in the monomeric component introduced into the first inlet is 50% by weight and the content of monomer A in the monomeric components introduced into the other inlets is 51% by weight, the error (%) becomes (51 / 50-1)×100=2%. Furthermore, the phrase "the error in the content of each monomer is within ±5%" means that the error in the content of each monomer contained in the monomer component is within ±5%. For example, when the monomer component contains monomer A and monomer B, it 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 elongation reaction) is not particularly limited to the temperature of the flow path downstream of the Nth inlet (e.g., between the second and third inlets), and can be appropriately selected depending on the purpose. For example, it is preferably 0-200°C, more preferably 20-180°C, further preferably 40-160°C, especially preferably 60-140°C, and most preferably 80-120°C. Furthermore, the reaction temperature of this reaction can also be the same as that of the polymer nucleation reaction.

[0051] The molar concentration (total molar concentration of monomers) of the monomer components in this reaction is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0.01 to 5.0 mol / L, more preferably 0.05 to 3.0 mol / L, and even more preferably 0.1 to 2.0 mol / L. Within the above concentration range, there is a tendency for a better polymer yield per unit time. On the other hand, when the concentration is greater than 5.0 mol / L, problems such as increased viscosity of the reaction solution or insolubility of monomer components may occur. Furthermore, when the concentration is less than 0.01 mol / L, problems such as decreased reaction rate and decreased polymer yield (incomplete reaction) may occur. Moreover, the above refers to the molar concentration of monomer components in the flow path immediately after being introduced into the microreactor.

[0052] The flow rate of the reaction solution in this reaction is not particularly limited and can be appropriately selected according to the purpose. For example, it is preferably 0.001 to 10 mL / min, more preferably 0.005 to 3 mL / min, and even more preferably 0.01 to 1 mL / min. Within the above flow rate range, there is a tendency to achieve rapid mixing of the monomer components and the polymerization initiator, thereby suppressing pressure loss. Furthermore, the above refers to the flow rate of the reaction solution in the flow path immediately after being introduced into the microreactor.

[0053] There are no particular limitations on the residence time in this reaction, and it can be appropriately selected according to the purpose. For example, it is preferred to be 1 to 180 min, more preferably 5 to 120 min, and even more preferably 8 to 90 min. By using a residence time within the above range, there is a tendency to narrow the molecular weight distribution of the obtained polymer.

[0054] The concentration of the polymerization initiator in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-3.0 mol / L, more preferably 0.0005-1.5 mol / L, further preferably 0.001-0.5 mol / L, and even more preferably 0.005-0.2 mol / L. With the concentration within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the polymerization initiator in the flow path immediately after being introduced into the microreactor.

[0055] The concentration of the chain transfer agent in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-3.0 mol / L, more preferably 0.0005-1.5 mol / L, even more preferably 0.001-0.5 mol / L, and particularly preferably 0.005-0.2 mol / L. By keeping the concentration within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the chain transfer agent in the flow path immediately after being introduced into the microreactor.

[0056] The total concentration of the polymerization initiator and chain transfer agent in this reaction is not particularly limited and can be appropriately selected according to the composition and concentration of the monomer components. For example, it is preferably 0.0001-1.0 mol / L, more preferably 0.0003-0.5 mol / L, further preferably 0.0005-0.3 mol / L, and even more preferably 0.001-0.1 mol / L. With concentrations within the above ranges, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration of the polymerization initiator and chain transfer agent in the flow path immediately after being introduced 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 is preferably 0.001 to 100.0 mol%, more preferably 0.01 to 50.0 mol%, further preferably 0.05 to 30.0 mol%, and even more preferably 0.1 to 20.0 mol%. By keeping the concentration ratio within the above range, there is a tendency to suppress blockage of the flow path in the microreactor and to narrow the molecular weight distribution of the obtained polymer. Furthermore, the above refers to the concentration ratio of polymerization initiator and chain transfer agent to monomer in the flow path immediately after being introduced into the microreactor.

[0058] There are no particular limitations on the method for polymer recovery; for example, precipitation (including redeposition) can be used. For instance, the polymer can be precipitated by adding the reaction solution to a solvent (precipitation solvent), or the polymer can be redissolved in a suitable solvent and the solution added to a solvent (reprecipitation solvent) to redeposition, or the target polymer can be obtained by diluting the reaction solution with a solvent (reprecipitation solvent or polymerization solvent). The precipitation or redeposition solvent can be any organic solvent and water, or a mixture of solvents.

[0059] The solvent used for precipitation or reprecipitation is not particularly limited and can be the same as or different from the polymerization solvent. Examples of precipitating or reprecipitating solvents include: organic solvents (diol solvents, ester solvents, ketone solvents, ether solvents, amide solvents, sulfide solvents, hydrocarbon solvents) as examples of polymerization solvents; halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene); nitro compounds (nitromethane, nitrobenzene, etc.); nitriles (acetonitrile, benzonitrile, etc.); carbonates (dimethyl carbonate, diethyl carbonate, ethyl carbonate, propylene carbonate, etc.); carboxylic acids (acetic acid, etc.); and mixed solvents containing such solvents.

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

[0061] Furthermore, the preferred solvents for precipitation or reprecipitation are mixtures of alcohol (especially methanol) and water, or mixtures of glycol solvents (especially polyethylene glycol) and water. In such cases, the ratio of organic solvent (alcohol or glycol solvent) to water (volume ratio: 25°C) is, for example, 10 / 90 to 99 / 1, more preferably 30 / 70 to 98 / 2, and even more preferably 50 / 50 to 97 / 3.

[0062] Polymers obtained through precipitation (including reprecipitation) can be washed as needed, or cleaned by simultaneously dissolving and dispersing the polymer in a solvent while stirring (sometimes called "re-pulping"). Washing can also be performed after re-pulping. Using solvents to re-pulp or wash the polymer produced by polymerization can efficiently remove residual monomers or low-molecular-weight oligomers adhering to the polymer.

[0063] In this invention, the solvent used for repulping or rinsing is preferably a solvent containing at least hydrocarbons (especially aliphatic hydrocarbons such as hexane or heptane), alcohols (especially methanol, ethanol, propanol, isopropanol, butanol, etc.), or esters (especially ethyl acetate, etc.).

[0064] After precipitation (including reprecipitation), re-pulping, or rinsing, the solvent can be removed by methods such as decantation or filtration as needed, and then drying can be carried out.

[0065] (Microreactor) Microreactors can be microreactors equipped with flow paths capable of mixing multiple liquids. The microreactor has multiple inlets at different locations along the flow path, and at least one inlet (first inlet) for introducing monomer components into the microreactor, and another inlet (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. Furthermore, it may also have an introduction path that communicates with the flow path and passes through the first or other inlets to introduce liquids into the flow path, as needed. Examples of such introduction paths include polymerization initiator introduction paths, chain transfer agent introduction paths, polymerization initiator introduction paths, and monomer introduction paths. Furthermore, when the microreactor has an introduction path, the inlet (e.g., the first inlet, the second inlet) refers to the confluence of the introduction path and the flow path. Furthermore, it may also include components other than the flow path, inlets, and introduction paths, as needed.

[0066] There are no particular restrictions on the cross-sectional shape of the flow path; it can be selected appropriately depending on the purpose. Examples include circles, rectangles, semicircles, and triangles.

[0067] The microreactor may also have an inlet for introducing the polymerization initiator into the microreactor located 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). 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 the polymerization initiator into the microreactor located at the same position as the first inlet. Similarly, when using a chain transfer agent, an inlet for introducing the chain transfer agent into the microreactor may also be located upstream of the first inlet, at the same position as the first inlet, or downstream of the first inlet. It is preferable to have an inlet for introducing the chain transfer agent into the microreactor located at the same position as the first inlet.

[0068] The microreactor may or may not have an inlet for introducing the polymerization initiator at the same location as the Nth inlet (e.g., the second inlet) or downstream of the Nth inlet. When introducing the polymerization initiator into the microreactor, it is preferable to have an inlet at the same location as the Nth inlet to maintain 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 also be located at the same location as the Nth inlet or downstream of the Nth inlet; it is preferable to have an inlet at the same location as the Nth inlet.

[0069] As a microreactor, there are no particular limitations as long as it has a flow path capable of mixing multiple liquids. It can be appropriately selected according to the purpose. For example, micro mixers (substrate type micro mixers, pipe connector type micro mixers, etc.) and branch pipes can be listed.

[0070] Substrate-type micromixers are constructed from substrates with flow paths formed internally or on their surface, and are sometimes referred to as microchannels. There are no particular limitations on substrate-type micromixers as long as they do not impair the effectiveness of the invention, and appropriate selections can be made according to the purpose. Examples include: mixers with fine flow paths for mixing as described in International Publication No. 96 / 30113; and mixers 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 to have, in addition to the flow path, an introduction path that communicates with the flow path and is used to introduce multiple liquids into the flow path. That is, it is preferable that the upstream side of the flow path branches according to the number of introduction paths. There is no particular limitation on the number of introduction paths, which can be appropriately selected according to the purpose. It is preferable to introduce multiple liquids to be mixed from different introduction paths and then mix them by merging them in the flow path. Alternatively, it can be configured such that one liquid is added to the flow path in advance, and other liquids are introduced through the introduction path.

[0072] The pipe-connector type micromixer has an internal flow path and, as needed, a connection means for connecting the internal flow path to the pipe. There are no particular limitations on the connection method; any known pipe connection method can be appropriately selected according to the purpose. Examples include screw-in type, pipe sleeve type, butt welding type, insert welding type, socket welding type, flange type, embedded type, flared type, and mechanical type.

[0073] The interior of the pipe-type micromixer preferably includes, in addition to the aforementioned flow path, an inlet path that communicates with the flow path and introduces multiple liquids into it. That is, preferably, the upstream side of the flow path branches according to the number of inlet paths. When there are two inlet paths, a T-shaped or Y-shaped structure can be used as the pipe-type micromixer; when there are three inlet paths, a cross-shaped structure can be used. Alternatively, it can be configured such that one liquid is pre-added to the flow path, and other liquids are introduced through the inlet paths.

[0074] There are no particular restrictions on the material used for micro-mixers (such as flow paths). The appropriate material can be selected based on requirements such as heat resistance, pressure resistance, solvent resistance, and ease of processing. Examples include stainless steel, titanium, copper, nickel, aluminum, silicon, and fluoropolymers such as Teflon (registered trademark), PFA (perfluoroalkoxy resin), TFAA (trifluoroacetamide), and PTFE (polytetrafluoroethylene).

[0075] Micromixers, due to their precise control of the flow of reaction solutions through their microstructure, are preferably manufactured using microfabrication techniques. There are no particular limitations on microfabrication techniques; appropriate techniques can be 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 micromachining (micro-drilling, where drill bits with micrometer diameters rotate at high speeds); (d) high aspect ratio machining using Deep RIE silicon; (e) Hot Emboss machining; (f) photolithography; (g) laser machining; and (h) ion beam machining.

[0076] As micro mixers, commercially available products can be used, such as microreactors with interdigitated channel structures, single mixers and caterpillar mixers manufactured by Institut für Mikrotechnik Mainz (IMM); micro glass reactors manufactured by Micro Glass; SAITOS manufactured by CPC Systems; YM-1 and YM-2 mixers manufactured by Ayambu; Mixing Tee and Tee (T-connectors) manufactured by Shimadzu GLC; IMT chip reactors manufactured by the Institute of Microchemical Technology; Micro High Mixer developed by Toray Engineering; and Union T manufactured by Ironlock, etc.

[0077] As a microreactor, the micromixer can be used alone, or it can be configured to extend the flow path by connecting a tubular reactor downstream. By connecting the tubular 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 tubular reactor is a reactor used to precisely control (residence time control) the time required for subsequent reactions in a solution rapidly mixed by a micromixer. There are no particular limitations on the tubular reactor; for example, the inner diameter, outer diameter, length, and material of the tube can be appropriately selected according to the desired reaction. Commercially available tubular reactors can be used. There are no particular limitations on the material of the tubular reactor; the materials exemplified above for micromixers can be used more preferably.

[0079] The flow path has the function of mixing multiple liquids through diffusion and removing the heat of reaction. There are no particular restrictions on the mixing method of the liquids within the flow path; it can be appropriately selected according to the purpose. For example, laminar flow mixing and turbulent flow mixing can be listed. Among these, laminar flow mixing (static mixing) is preferred for more efficient reaction control or heat removal. Furthermore, due to the small size of the flow path in the microreactor, multiple liquids introduced from the inlet path easily and naturally become laminar-dominated in their flow direction and diffuse and mix in a direction orthogonal to the flow direction. In laminar flow mixing, the laminar flow profile of the flowing liquid can be divided by setting branch points and confluence points within the flow path, thereby increasing the mixing speed. Furthermore, when mixing via turbulent flow (dynamic mixing) is carried out in the flow path of a microreactor, the flow can be changed from laminar to turbulent by adjusting the flow rate or the shape of the flow path (such as the three-dimensional shape of the liquid-receiving part, the curvature of the flow path, and the roughness of the wall surface). Compared with the above-mentioned laminar flow mixing, the above-mentioned turbulent flow mixing has the advantages of better mixing efficiency and faster mixing speed.

[0080] Here, because the inner diameter of the flow path is smaller, the diffusion distance of molecules can be shortened, thus reducing the mixing time and improving mixing efficiency. Furthermore, the surface area to volume ratio 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 the liquid flows through increases, and the pump used for liquid delivery needs to be of particularly high pressure resistance, thus increasing manufacturing costs. Also, the tendency for flow path blockage due to reactants increases. Consequently, the limited liquid delivery flow rate restricts the design of the micromixer.

[0081] The inner diameter of the flow path is not particularly limited as long as it does not impair the effectiveness of the invention, and can be appropriately selected according to the purpose. For example, it is preferably 50 μm to 15 mm, more preferably 100 μm to 10 mm, further preferably 200 μm to 5 mm, and even more preferably 500 μm to 3 mm. If the inner diameter is less than 50 μm, the pressure loss will increase. If the inner diameter exceeds 15 mm, the surface area of ​​each unit volume will decrease, resulting in difficulty in rapid mixing or heat removal from the reaction. On the other hand, when the inner diameter is within the above range, the mixing of the monomer components introduced into the flow path with the polymerization initiator (and chain transfer agent) proceeds rapidly, and the heat of reaction can be removed efficiently, making it easier to control the heat of reaction.

[0082] There are no particular limitations on the cross-sectional area of ​​the flow path, and it can be appropriately selected according to the purpose. For example, it is preferably 5000 μm2 to 800 mm2, and more preferably 0.75 mm2 to 30 mm2. When the cross-sectional area is within the above range, the mixing of the monomer components introduced into the flow path with the polymerization initiator (and chain transfer agent) proceeds rapidly, and the heat of reaction can be efficiently removed, making it easier to control the heat of reaction.

[0083] The length (total length) of the flow path in the microreactor is not particularly limited and can be adjusted appropriately according to the optimal reaction time, for example, preferably 0.5 to 500 m, more preferably 1 to 400 m. The length of the flow path for the polymer nucleation reaction (reaction 1) is preferably 0.1 to 125 m, more preferably 0.3 to 100 m, and even more preferably 0.5 to 80 m. The length of the flow path for the polymer chain elongation reaction (e.g., reaction 2) is preferably 0.1 to 125 m, more preferably 0.3 to 100 m, and even more preferably 0.5 to 80 m.

[0084] The inlet path is connected to the flow path and has the function of introducing multiple liquids into the flow path. Furthermore, in the inlet path, the end that is different from the side connected to the flow path is usually connected to a container containing the liquids to be mixed.

[0085] The inner diameter of the inlet path is not particularly limited as long as it does not impair the effectiveness of the invention, and can be appropriately selected according to the purpose. For example, it is preferably 50 μm to 15 mm, more preferably 100 μm to 10 mm, further preferably 200 μm to 5 mm, and even more preferably 500 μm to 3 mm. Furthermore, when the microreactor has multiple inlet paths, the inner diameter of each inlet path can be the same or different.

[0086] There are no particular restrictions on the components other than the flow path and the inlet path. They can be selected appropriately according to the purpose. For example, pumps used for liquid delivery, temperature control means, reaction promotion means, sensors, tanks for storing the manufactured polymers, etc. can be listed.

[0087] There are no particular restrictions on the type of pump; it can be appropriately selected from industrially usable pumps. Preferably, it should not produce pulsation when delivering liquid, such as plunger pumps, gear pumps, rotary pumps, diaphragm pumps, etc.

[0088] There are no particular limitations on the means of temperature adjustment; they can be appropriately selected based on the reaction temperature. Examples include thermostatic baths, circulators, and heat exchangers. For instance, in the case of a reaction temperature of 80°C, an oil bath is preferable. Furthermore, in the case of cooling for the purpose of recovering the obtained polymer, a thermostatic bath filled with water or ice water is preferable.

[0089] As a reaction-promoting means, appropriate methods can be selected depending on the mixed liquid or the desired reaction. Examples include methods that impart vibrational energy, heating, light irradiation, and voltage application. For example, a microreactor equipped with a voltage application method could be the microfluidic electrochemical reactor disclosed in Japanese Patent Application Publication No. 2006-104538. There are no particular limitations on the aforementioned sensors; examples include temperature sensors, flow sensors, and pressure sensors for measuring pressure within the flow path.

[0090] (Monomer components) The monomer component of this invention is characterized by containing two or more monomers. Examples of monomers constituting the monomer component include (meth)acrylic acid monomers, aromatic vinyl monomers, vinyl carboxylate, conjugated diene monomers, olefin monomers, ethylene halides, and vinylidene halide, etc., with (meth)acrylic acid monomers being preferred from the viewpoint of reactivity. That is, the monomer component introduced into the first inlet and the other inlets described above preferably contains two or more (meth)acrylic acid monomers.

[0091] Examples of (meth)acrylic acid monomers include: (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, tributyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and other alkyl (meth)acrylates; 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, 1-propylcyclohexyl (meth)acrylate, and other cycloalkyl (meth)acrylates; γ-butyrolactone (meth)acrylates, etc., which are cyclic esters. (Meth)acrylates containing cyclic ether groups, such as 3,4-epoxycyclohexyl (meth)acrylate, glycidyl (meth)acrylate, β-methylglycidyl acrylate, and oxymethacrylate; (meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate; and 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 in the photoresist resins described later can also be used as examples.

[0092] Examples of aromatic vinyl monomers include: styrene, alkylstyrene (ortho-, meta-, and p-methylstyrene, etc., vinyltoluenes; 2,4-dimethylstyrene, etc., vinylxylenes; p-ethylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, etc.), α-alkylstyrene (α-methylstyrene, α-methylp-methylstyrene, etc.), alkoxystyrene (ortho-, meta-, and p-methoxystyrene, p-tert-butoxystyrene, etc.), halostyrene (ortho-, meta-, and p-chlorostyrene, p-bromostyrene, etc.), styrene sulfonic acid or its alkali metal salts, etc.

[0093] Examples of vinyl carboxylic acid esters include vinyl formate, vinyl acetate, vinyl propionate, trimethylvinyl acetate, and other C1-10 vinyl carboxylic acid esters.

[0094] Examples of conjugated diene monomers include butadiene, isoprene, chloroprene, chloroprene rubber, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, pentadiene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, and other C4-16 dienes.

[0095] Examples of olefin monomers include C2-10 olefins such as ethylene, propylene, and butene (isobutene, etc.).

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

[0097] This invention is particularly suitable for the manufacture of photoresist resins because it can produce polymers with uniform copolymer composition and narrow molecular weight distribution. Therefore, the monomer components are preferably monomers containing groups (sometimes called "acid-degradable groups") that can be detached from the polymer by acid to generate polar groups. This increases the polarity of the polymer (photoresist resin) due to acid action, thereby increasing its solubility in alkaline developing solutions.

[0098] Examples of the aforementioned polar groups include: phenolic hydroxyl, carboxyl, fluorool (preferably hexafluoroisopropanol), sulfonic acid, sulfonamide, sulfonimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene, tri(alkylsulfonyl)methylene, etc.; and alcoholic hydroxyl groups, etc. Among these, carboxyl, fluorool (preferably hexafluoroisopropanol), and sulfonic acid groups are preferred.

[0099] As the aforementioned acid-degradable group, it is preferable to obtain a group by replacing the hydrogen atom of the aforementioned polar group with a group that can be removed by acid. Examples of such acid-degradable groups include -C(RI)(RII)(RIII) and -C(RIV)(RV)(ORVI). In the above formulas, RI to RIII and RVI independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups, respectively. RIV and RV independently represent hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups, respectively. At least two groups among RI to RIII can be bonded to each other to form a ring. Furthermore, RIV and RV can also be bonded to each other to form a ring.

[0100] There is no particular limitation on the number of carbon atoms in the aforementioned acid-decomposing group, but it is preferably 4 or more, and more preferably 5 or more. There is no particular limitation on the upper limit of the number of carbon atoms, but it is preferably 20.

[0101] The alkyl groups of RI to RVI are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, n-butyl, dibutyl, tributyl, hexyl, octyl, etc.

[0102] The cycloalkyl groups RI to RVI mentioned above can be monocyclic or polycyclic (bridged) cycloalkyl groups. As monocyclic cycloalkyl groups, those with 3 to 8 carbon atoms are preferred, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As polycyclic cycloalkyl groups, those with 6 to 20 carbon atoms are preferred, such as adamantyl, northoalkyl, isocamphenyl, camphanyl group, dicyclopentyl, α-pinel, tricyclodecyl, tetracyclododecyl, and androstanyl group. Furthermore, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0103] The aryl groups of RI to RVI mentioned above are preferably aryl groups with 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracene, etc.

[0104] The aralkyl groups of RI to RVI mentioned above are preferably aralkyl groups with 7 to 12 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, etc.

[0105] The alkenyl groups of RI to RVI mentioned above are preferably alkenyl groups with 2 to 8 carbon atoms, such as vinyl, allyl, butenyl, cyclohexenyl, etc.

[0106] The ring formed by the mutual bonding of at least two groups among RI to RIII, and the ring formed by the bonding of RIV and RV, are preferably cycloalkane rings. The cycloalkane rings are preferably monocyclic cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane; or polycyclic cycloalkane rings such as norethane, tricyclic decane, tetracyclic dodecane, and adamantane.

[0107] Furthermore, the alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and cycloalkane rings in RI to RVI may also have substituents.

[0108] As the acid-decomposing group mentioned above, the preferred groups are tert-butyl, tert-pentyl, and the groups represented by formulas (I) to (IV) below.

[0109]

[0110] In the above equations (I) to (IV), R2 to R7, Ra, n, p, and ring Z1 respectively represent the same R2 to R7, Ra, n, p, and ring Z1 as in the following equations (a1) to (a4).

[0111] The aforementioned acid-degrading groups can also be provided via spacer groups. The aforementioned spacer group refers to the same as the linking group exemplified and explained later as A in formula (1).

[0112] As a monomer having the above-mentioned acid-decomposing group, for example, the monomer represented by the following formula (1) can be cited.

[0113]

[0114] In formula (1) above, R1 represents the acid-decomposing group. Also, in formula (1) above, R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. Examples of halogen atoms include chlorine, bromine, and iodine. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, isopentyl, dipentyl, tripentyl, and hexyl. Examples of alkyl groups having 1 to 6 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, etc., which are groups formed by replacing one or more hydrogen atoms of the alkyl group with halogen atoms (halo(C1-6)alkyl).

[0115] In formula (1) above, A represents a single bond or a linking group. Examples of such linking groups include carbonyl groups (-C(=O)-), ether bonds (-O-), ester bonds (-C(=O)-O-), amide bonds (-C(=O)-NH-), carbonate bonds (-OC(=O)-O-), and groups formed by multiple such links, as well as groups formed by alkyl groups and such links. Examples of such alkyl groups include linear or branched alkyl groups such as methylene, methylmethylene, dimethylmethylene, ethyl alkyl, propyl alkyl, and trimethylene; or divalent alicyclic hydrocarbon groups (especially divalent alkyl groups) such as 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl, 1,4-cyclohexyl, and cyclohexylene.

[0116] As the monomer represented by the above formula (1), it is preferably at least one monomer selected from the group of monomers represented by the following formulas (a1) to (a4). Furthermore, sometimes the above "at least one monomer selected from the group of monomers represented by formulas (a1) to (a4)" is referred to as "monomer a".

[0117]

[0118] In the monomers represented by formulas (a1) to (a4) above, R is the same as R in formula (1) above, representing a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have a halogen atom, and A represents a single bond or a linking group. As A in formulas (a1) to (a4) above, it is preferably a group formed by a single bond, an alkyl group bonded to a carbonyl group (alkyl-carbonyl group). R2 to R4 may be the same or different, representing an alkyl group with 1 to 6 carbon atoms that may have substituents. Furthermore, R2 and R3 may be bonded to each other to form a ring. R5 and R6 may be the same or different, representing a hydrogen atom or an alkyl group with 1 to 6 carbon atoms that may have substituents. R7 represents a -COORc group, where Rc represents a tertiary hydrocarbon group, tetrahydrofuranyl, tetrahydropyranyl, or oxeheptyl group that may have substituents. n represents an integer from 1 to 3. When n is 2 or 3, the two or three R7s may be the same or different. Ra is a substituent bonded to the Z1 ring. These substituents can be the same or different, representing a side oxygen group, alkyl group, a hydroxyl group that can be protected by a protecting group, a hydroxyalkyl group that can be protected by a protecting group, or a carboxyl group that can be protected by a protecting group. p represents an integer from 0 to 3. The Z1 ring represents an alicyclic hydrocarbon ring with 3 to 20 carbon atoms. When p is 2 or 3, the two or three Ra groups can be the same or different.

[0119] Examples of alkyl groups of the aforementioned Ra include methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, tributyl, pentyl, isopentyl, dipentyl, tripentyl, n-hexyl, and other alkyl groups having 1 to 6 carbon atoms.

[0120] Examples of hydroxyalkyl groups such as Ra include hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, and other hydroxyC1-6 alkyl groups.

[0121] Protecting groups that can be present in the hydroxyl group of Ra and hydroxyalkyl groups include, for example, C1-4 alkyl groups such as methyl, ethyl, and tributyl; groups that form an acetal bond together with the oxygen atom constituting the hydroxyl group (e.g., C1-4 alkyl-O-C1-4 alkyl such as methoxymethyl); and groups that form an ester bond together with the oxygen atom constituting the hydroxyl group (e.g., acetyl, benzoyl, etc.).

[0122] Examples of protecting groups for the carboxyl group of the aforementioned Ra include: methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, tributyl, pentyl, isopentyl, dipentyl, tripentyl, hexyl, and other C1-6 alkyl groups; 2-tetrahydrofuranyl, 2-tetrahydropyranyl, 2-oxetaneheptyl, etc.

[0123] Examples of alkyl groups having 1 to 6 carbon atoms among R2 to R6 include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, pentyl, isopentyl, dipentyl, tripentyl, and hexyl. In this invention, C1-4 alkyl groups are preferred, C1-3 alkyl groups are more preferred, and C1-2 alkyl groups are even more preferred.

[0124] Substituents that may be present in the alkyl groups having 1 to 6 carbon atoms (R2 to R6) include, for example, halogen atoms, hydroxyl groups, substituted hydroxyl groups (e.g., methoxy, ethoxy, propoxy, etc., C1-4 alkoxy groups), cyano groups, etc. Examples of alkyl groups having substituents that have 1 to 6 carbon atoms include: trifluoromethyl, 2,2,2-trifluoroethyl, etc., which are halo(C1-6)alkyl groups formed by replacing one or more hydrogen atoms of the alkyl group with halogen atoms; hydroxymethyl, 2-hydroxyethyl, methoxymethyl, 2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, cyanomethyl, 2-cyanoethyl, etc.

[0125] When R2 and R3 are bonded together to form a ring, the ring can be, for example, an alicyclic hydrocarbon ring with 3 to 12 carbon atoms that may have substituents.

[0126] Examples of tertiary hydrocarbon groups of the aforementioned Rc include tertiary butyl and tertiary pentyl.

[0127] Substituents that can be present in the tertiary hydrocarbon group of the aforementioned Rc include, for example, halogen atoms, hydroxyl groups, substituted hydroxyl groups (such as methoxy, ethoxy, propoxy, and other C1-4 alkoxy groups), cyano groups, etc.

[0128] Examples of alicyclic hydrocarbon rings with 3 to 20 carbon atoms in the aforementioned ring Z1 include: cycloalkanes with approximately 3 to 20 members (preferably 3 to 15 members, especially 5 to 12 members), such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cyclooctane rings; monocyclic alicyclic hydrocarbon rings with approximately 3 to 20 members (preferably 3 to 15 members, especially 5 to 10 members), such as cyclopropene, cyclobutene, cyclopentene, and cyclohexene rings; adamantane rings; norethane rings, norethene rings, ethane rings, isoethane rings, and tricyclic [5.2.1.02,6]decane. Rings containing norethane or norethene rings, such as tetracyclic [4.4.0.12,5.17,10]dodecane ring; rings formed by hydrogenation of polycyclic aromatic condensation rings such as perhydroindene ring, decahydronaphthalene ring (perhydronaphthalene ring), perhydrofuran ring (tricyclic [7.4.0.03,8]tridecane ring), perhydroanthracene ring, etc. (preferably rings formed by complete hydrogenation); bridging hydrocarbon rings of 2-ring, 3-ring, 4-ring systems such as tricyclic [4.2.2.12,5]undecane ring, etc. (e.g. bridging hydrocarbon rings with approximately 6 to 20 carbon atoms), etc.

[0129] Furthermore, the aforementioned monomer components preferably contain monomers having at least an alicyclic backbone of [-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-OC(=O)-]. Using monomers with the aforementioned alicyclic backbone can impart higher substrate adhesion and etching resistance to the polymer (photoresist resin). Moreover, the monomer having at least an alicyclic backbone of [-C(=O)-O-], [-S(=O)2-O-], or [-C(=O)-OC(=O)-] is sometimes referred to as "monomer b".

[0130] Regarding the aforementioned monomer b, it is preferred to select at least one monomer 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 that may have a halogen atom; A represents a single bond or a linking group; X represents a non-bonded, methylene, ethyl, oxygen atom, or sulfur atom; Y represents a methylene or carbonyl group; Z represents a divalent organic group (for example, an alkyl group exemplified and described as an alkyl group that may be contained in A of the monomers represented by formulas (a1) to (a4) (especially a straight-chain alkyl group having 1 to 3 carbon atoms)). V1 to V3 may be the same or different, representing -CH2-, [-C(=O)-], or [-C(=O)-O-]. However, at least one of V1 to V3 is [-C(=O)-O-]. R8 to R14 may be the same or different, representing hydrogen atom, fluorine atom, alkyl group that may have fluorine atom, hydroxyl group that may be protected by a protecting group, hydroxyalkyl group that may be protected by a protecting group, carboxyl group that may be protected by a protecting group, or cyano group.

[0131]

[0132] Examples of R and A in the monomers represented by formulas (b1) to (b5) that are the same as those in the monomers represented by formulas (a1) to (a4) can be given. Furthermore, examples of alkyl groups in R8 to R14, hydroxyl groups that can be protected by a protecting group, hydroxyalkyl groups that can be protected by a protecting group, and carboxyl groups that can be protected by a protecting group in the monomers represented by formulas (b1) to (a4) that are the same as those in the monomers represented by formulas (a1) to (a4) can be given.

[0133] Examples of alkyl groups among R8 to R14 include trifluoromethyl, 2,2,2-trifluoroethyl, etc., which are alkyl groups formed by replacing one or more hydrogen atoms of the alkyl group with fluorine atoms [fluoro(C1-6)alkyl].

[0134] In the monomers represented by formulas (b1) to (b4) above, there may be one or more of R8 to R11, preferably one to three. Furthermore, in the case where there are two or more of the aforementioned R8 to R11 in the monomers represented by formulas (b1) to (b4) above, the two or more of the aforementioned R8 to R11 may be the same or different.

[0135] Among monomers b, those that can impart excellent substrate adhesion and etching resistance to polymers (photoresist resins), and have excellent solubility in alkaline developing solutions, and can form fine patterns with high precision, are preferably: monomers represented by formula (b1) where R8 is a cyano group, a amide group, an imine group, or an electron-withdrawing group such as a fluorine (C1-6) alkyl group; monomers represented by formula (b2); monomers represented by formula (b3) where Y is a carbonyl group; monomers represented by formula (b4); and monomers represented by formula (b5).

[0136] In the above formula (b1), when R8 is an electron-withdrawing group such as a cyano group, a amide group, an imine group, or a fluorine (C1-6) alkyl group, the above R8 is preferably bonded to at least the carbon atom of the appended carbon atom in formula (b1).

[0137] The aforementioned monomer components may further contain monomer c. Monomer c is the monomer represented by the following formula (c1). When the aforementioned monomer components contain monomer c, the polymer (resin for photoresist) can be endowed with higher transparency and etching resistance. In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. A represents a single bond or a linking group. Rb represents a hydroxyl group protected by a protecting group, a hydroxyalkyl group protected by a protecting group, a carboxyl group protected by a protecting group, or a cyano group, preferably hydroxyl or cyano. q represents an integer from 1 to 5. Ring Z2 represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. When q is an integer from 2 to 5, the 2 to 5 Rb may be the same or different.

[0138]

[0139] Examples of R and A in the monomers represented by formula (c1) that are the same as those of R and A in the monomers represented by formulas (a1) to (a4) can be given. Furthermore, examples of the hydroxyl group, hydroxyalkyl group, and carboxyl group that can be protected by a protecting group in Rb in the monomers represented by formula (c1) that are the same as those of Ra in the monomers represented by formulas (a1) to (a4) can be given.

[0140] In formula (c1), ring Z2 in the monomer represents an alicyclic hydrocarbon ring with 6 to 20 carbon atoms. Examples include: cyclohexane rings, cyclooctane rings, and other cycloalkanes with approximately 6 to 20 members (preferably 6 to 15 members, especially 6 to 12 members); cyclohexene rings, and other monocyclic alicyclic hydrocarbon rings with approximately 6 to 20 members (preferably 6 to 15 members, especially 6 to 10 members); adamantane rings; norethane rings, norethene rings, ethane rings, isoethane rings, tricyclic [5.2.1.02,6]decane rings, tetracyclic [4.4.0.12,5.17,6]decane rings, and tetracyclic [4.4.0.12,5.17,6]decane rings.

[10] Rings containing noralkyl or norethene rings, such as dodecane rings; rings formed by hydrogenation of polycyclic aromatic condensation rings such as perhydroindene rings, decahydronaphthalene rings (perhydronaphthalene rings), perhydrofuran rings (tricyclic [7.4.0.03,8]tridecane rings), and perhydroanthracene rings (preferably rings formed by complete hydrogenation); bridging hydrocarbon rings of about 2 to 6 rings, such as tricyclic [4.2.2.12,5]undecane rings, 2-cyclic, 3-cyclic, and 4-cyclic systems (e.g., bridging hydrocarbon rings with about 6 to 20 carbon atoms). Among the above-mentioned rings Z2, rings containing noralkyl or norethene rings, or adamantane rings, are preferred.

[0141] (polymer) The polymer obtained in this invention has the characteristics of uniform copolymer composition and narrow molecular weight distribution, and therefore exhibits, for example, extremely high solubility in solvents. Therefore, the above-mentioned polymer can be used as a photoresist resin, etc.

[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 using the polymer obtained in this invention as a photoresist resin, the excellent solubility in alkaline developing solutions due to the molecular weight distribution (Mw / Mn) of 1.45 or less allows for the formation of fine patterns with high precision, which is preferable in this respect. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification can be determined, for example, by using polystyrene as a standard substance using GPC.

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

[0144] As radiation-sensitive acid generators, commonly used or known compounds that efficiently produce acids upon exposure to radiation such as visible light, ultraviolet light, far-ultraviolet light, electron beams, and X-rays can be used. These compounds consist of a parent nucleus and the generated acid. Examples of parent nuclei include: monium salts, strontium salts (containing tetrahydrothiophene onium salts), phosphonium salts, diazonium salts, pyridinium salts, and other onium salt compounds; sulfonylimine compounds, sulfonium compounds, sulfonate compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, etc. Furthermore, examples of acids generated by exposure include alkyl or fluorinated alkyl sulfonic acids, alkyl or fluorinated alkyl carboxylic acids, and alkyl or fluorinated alkyl sulfonylimine acids. Only one type of these can be used, or two or more types can be used.

[0145] The amount of radiation-sensitive acid generator used can be appropriately selected based on the intensity of the acid generated by radiation irradiation or 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, more preferably 1 to 25 parts by weight, and even more preferably 2 to 20 parts by weight relative to 100 parts by weight of the photoresist resin.

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

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

[0148] (Pattern Formation Method) The above-mentioned photoresist resin composition is coated onto a substrate or base plate and dried. Then, the coating (resist film) is exposed through a specific mask (or further exposed and then baked) to form a latent pattern. Subsequently, alkaline dissolution is performed, thereby enabling the formation of fine patterns with high precision.

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

[0150] During exposure, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays can be used.

[0151] By exposing the photoresist to a radiation-sensitive acid-generating agent, an acid is generated. Through this acid, the protective groups (acid-decomposing groups) of the photoresist resin components, which are alkali-soluble polymer units (repeating units with acid-decomposing groups), rapidly detach, generating carboxyl groups and other groups that aid in solubility. Therefore, by developing with an alkaline developer, specific patterns can be formed with high precision. [Example]

[0152] The present invention will be further described in detail below based on examples, but the invention is not limited to these examples. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin were determined by GPC (gel permeation chromatography) using tetrahydrofuran solvent. Polystyrene was used as the standard sample, and a refractometer (Refractive Index Detector; RI detector) was used as the detector. The GPC determination was performed using a column (trade name "KF-806L") manufactured by Showa Denko Co., Ltd., connected in series, at a column temperature of 40°C, an RI temperature of 40°C, and a tetrahydrofuran flow rate of 0.8 mL / min. The molecular weight distribution (Mw / Mn) was calculated from the above-mentioned measured values.

[0153] The microreactor used in this embodiment is the microreactor shown in Figure 1, which includes a micromixer composed of a T-shaped pipe joint and a tubular reactor connected downstream of the micromixer. Specifically, the microreactor includes a polymerization initiator, or a polymerization initiator and chain transfer agent introduction path (polymerization initiator introduction path 1), a first monomer introduction path 2, a confluence (mixing section) of these introduction paths (micromixer 3), a flow path connected downstream of the micromixer 3 (tubular reactor 5), a second monomer introduction path 4, a confluence (mixing section) of the tubular reactor 5 and the second monomer introduction path 4 (micromixer 6), and a flow path connected downstream of the micromixer 6 (tubular reactor 7). Furthermore, the microreactor used in this embodiment is equipped with a pump for liquid delivery upstream of the polymerization initiator introduction path 1, the first monomer introduction path 2, and the second monomer introduction path 4, but this is omitted in Figure 1. Furthermore, a reaction solution collection section is provided at the junction of tubular reactor 5 and micro mixer 6, and at the downstream end of tubular reactor 7, but these are omitted in Figure 1.

[0154] The aforementioned micromixer was a custom-made product manufactured by Sanko Seiki Industrial Co., Ltd. (a similar product can be obtained by commissioning manufacturing based on the description in this embodiment). Furthermore, the mixer is made of stainless steel, T-shaped, and has an inner diameter of 400 μm. Tubular reactors 5 and 7 use stainless steel tubing manufactured by GL Science Co., Ltd. The pump used for liquid delivery is a Model 11 Plus syringe pump manufactured by HARVARD Corporation. The reaction temperature is adjusted by embedding the entire microreactor within a thermostatic bath.

[0155] [Examples 1 and 2] (Phase 1 Response) A mixture of AIBN (azobisisobutyronitrile) as the polymerization initiator, and an equal molar amount of GBLMA (γ-butyrolactone methacrylate) and MCPMA (1-methylcyclopentyl methacrylate) as the first monomer component was introduced into the microreactor via the polymerization initiator introduction path and the first monomer introduction path, respectively. Subsequently, the amount of residual monomer or the weight-average molecular weight of the reactants (polymer) was measured. Furthermore, the monomer conversion rate, the weight-average molecular weight and molecular weight distribution of the polymer, and the flow rate of the microreactor during the first stage of the reaction are described in Table 1.

[0156] (Phase 2 response) Following the first stage reaction, an equal molar amount of a mixture of GBLMA and MCPMA, serving as the second monomer component, is introduced into the microreactor via the second monomer introduction pathway. Subsequently, the reaction solution is collected to determine the amount of residual monomer or the weight-average molecular weight of the reactants (polymers). Furthermore, the monomer conversion rate, polymer weight-average molecular weight and molecular weight distribution, and microreactor flow rate conditions during the second stage reaction are described in Table 2.

[0157] [Example 3] (Phase 1 Response) A mixture of AIBN (azobisisobutyronitrile) as a polymerization initiator and RAFT-A (2-cyano-2-propyl 4-cyanodithiobenzoate) as a chain transfer agent, and an equal molar mixture of GBLMA (γ-butyrolactone methacrylate) and MCPMA (1-methylcyclopentyl methacrylate) as the first monomer components were introduced into the microreactor via the polymerization initiator introduction path and the first monomer introduction path, respectively. Subsequently, the amount of residual monomer or the weight-average molecular weight of the reactants (polymer) was measured. Furthermore, the monomer conversion rate, polymer weight-average molecular weight and molecular weight distribution, and microreactor flow rate conditions in the first stage of the reaction are described in Table 1.

[0158] (Phase 2 response) Following the first stage reaction, an equal molar amount of a mixture of GBLMA and MCPMA, serving as the second monomer component, is introduced into the microreactor via the second monomer introduction pathway. Subsequently, the reaction solution is collected to determine the amount of residual monomer or the weight-average molecular weight of the reactants (polymers). Furthermore, the monomer conversion rate, polymer weight-average molecular weight and molecular weight distribution, and microreactor flow rate conditions during the second stage reaction are described in Table 2.

[0159] [Examples 4-24] The polymerization initiator, chain transfer agent, and reaction conditions were changed to those described in Tables 1 and 2. Otherwise, the weight-average molecular weight and other parameters of the polymers obtained in the first and second stages of the reaction were measured in the same manner as in Example 3, and are recorded in Tables 1 and 2 respectively.

[0160] [Table 1] Example First monomer component Polymerization initiator Chain transfer agent Phase 1 Response Flow rate (mL / min) monomer concentration (mol / L) Concentration of polymerization initiator and chain transfer agent (mol / L) Polymerization initiators and chain transfer agents / monomers (mol%) temperature (°C) Long flow path (m) Flow path inner diameter (mm) flow path volume (mL) Detention time (min) GBLMA conversion rate (%) MCPMA conversion rate (%) average Conversion rate (%) GBLMA ratio (%) in the system MCPMA ratio (%) in the system Weight average molecular weight of polymer (Mw) polymers Molecular weight distribution (Mw / Mn) Example 1 GBLMA / MCPMA AIBN - 0.06 0.81 0.06 8.0 80 4.5 0.5 0.88 14.7 60.8 35.1 48.0 63.4 36.6 13,860 1.77 Example 2 GBLMA / MCPMA AIBN - 0.06 0.81 0.06 7.2 80 1.2 1.0 0.94 15.7 65.7 31.8 48.7 67.5 32.5 11,437 1.75 Example 3 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.06 8.0 80 4.5 0.5 0.88 14.7 25.1 17.7 21.4 58.6 41.4 757 1.25 Example 4 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.03 4.0 80 4.5 0.5 0.88 14.7 23.7 9.5 16.6 71.4 28.6 1,009 1.10 Example 5 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.03 4.0 90 4.5 0.5 0.88 14.7 47.6 31.9 39.8 59.8 40.2 956 1.32 Example 6 GBLMA / MCPMA AIBN RAFT-A 0.03 0.81 0.06 7.4 80 4.5 0.5 0.88 29.4 74.5 38.3 56.4 66.1 33.9 909 1.10 Example 7 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.06 7.1 80 1.2 1.0 0.94 15.7 52.1 19.6 35.9 72.7 27.3 747 1.09 Example 8 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 0.7 80 1.2 1.0 0.94 15.7 36.1 0.9 18.5 97.6 2.4 1,539 1.17 Example 9 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 80 2.3 1.0 1.81 30.1 26.9 19.5 23.2 58.0 42.0 1,348 1.20 Example 10 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 0.9 80 2.3 1.0 1.81 30.1 16.3 16.2 16.3 50.2 49.8 1,337 1.15 Example 11 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 80 4.6 1.0 3.61 60.2 52.9 39.2 46.1 57.4 42.6 1,870 1.18 Example 12 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 90 4.6 1.0 3.61 60.2 81.4 68.1 74.7 54.5 45.5 2,149 1.19 Example 13 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 80 1.2 1.0 0.94 15.7 9.8 3.9 6.9 71.5 28.5 1,106 1.12 Example 14 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 90 1.2 1.0 0.94 15.7 27.0 20.5 23.8 56.8 43.2 1,956 1.17 Example 15 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 100 1.2 1.0 0.94 15.7 41.6 32.1 36.9 56.4 43.6 2,113 1.18 Example 16 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 110 1.2 1.0 0.94 15.7 43.2 33.0 38.1 56.7 43.3 1,965 1.19 Example 17 GBLMA / MCPMA AIBN RAFT-A 0.06 0.81 0.01 1.8 120 1.2 1.0 0.94 15.7 27.5 18.8 23.1 59.4 40.6 1,534 1.17 Example 18 GBLMA / MCPMA AIBN RAFT-B 0.06 0.81 0.01 1.8 80 4.6 1.0 3.61 60.2 70.8 55.5 63.2 56.1 43.9 5,134 1.45 Example 19 GBLMA / MCPMA V-601 RAFT-A 0.06 0.81 0.01 1.8 80 4.6 1.0 3.61 60.2 49.5 42.0 45.8 54.1 45.9 1,836 1.17 Example 20 GBLMA / MCPMA V-601 RAFT-B 0.06 0.81 0.01 1.8 80 4.6 1.0 3.61 60.2 65.6 50.9 58.2 56.3 43.7 3,815 1.34 Example 21 GBLMA / MCPMA V-601 RAFT-B 0.06 0.81 0.03 3.6 80 4.6 1.0 3.61 60.2 76.7 63.9 70.3 54.6 45.4 2,953 1.28 Example 22 GBLMA / MCPMA V-601 RAFT-B 0.06 0.81 0.03 3.6 80 4.6 1.0 3.61 60.2 76.6 62.7 69.7 55.0 45.0 2,811 1.28 Example 23 GBLMA / MCPMA V-601 RAFT-B 0.06 0.81 0.03 3.6 80 4.6 1.0 3.61 60.2 72.2 60.6 66.4 54.4 45.6 2,974 1.29 Example 24 GBLMA / MCPMA V-601 RAFT-B 0.06 0.81 0.03 3.6 80 4.6 1.0 3.61 60.2 75.9 78.4 77.2 49.2 50.8 2,804 1.29

[0161] [Table 2] Example Second monomer component Import flow rate (mL / min) Phase 2 Response Flow rate (mL / min) Monomer concentration (mol / L) Concentration of polymerization initiator and chain transfer agent (mol / L) Polymerization initiators and chain transfer agents / monomers (mol%) temperature (°C) Long flow path (m) Flow path inner diameter (mm) Flow path volume (mL) Detention time (min) GBLMA conversion rate (%) MCPMA conversion rate (%) average Conversion rate (%) GBLMA ratio (%) in the system MCPMA ratio (%) in the system Weight-average molecular weight (Mw) of polymers Molecular weight distribution of polymers (Mw / Mn) Example 1 GBLMA / MCPMA 0.04 0.10 0.72 0.034 4.7 80 7.7 0.5 1.51 14.9 67.7 47.0 57.4 59.0 41.0 16,043 1.82 Example 2 GBLMA / MCPMA 0.04 0.10 0.72 0.031 4.3 80 2.0 1.0 1.57 15.4 78.0 43.6 60.8 64.1 35.9 14,741 1.91 Example 3 GBLMA / MCPMA 0.04 0.10 0.85 0.034 4.0 80 7.7 0.5 1.51 14.9 36.1 26.2 31.2 57.9 42.1 1,184 1.27 Example 4 GBLMA / MCPMA 0.04 0.10 0.87 0.017 1.9 80 7.7 0.5 1.51 14.9 35.2 20.1 27.7 63.7 36.3 1,437 1.14 Example 5 GBLMA / MCPMA 0.04 0.10 0.76 0.017 2.2 90 7.7 0.5 1.51 14.9 56.9 41.2 49.1 58.0 42.0 1,487 1.16 Example 6 GBLMA / MCPMA 0.02 0.05 0.68 0.031 4.6 80 7.7 0.5 1.51 29.6 85.2 47.8 66.5 64.1 35.9 1,195 1.18 Example 7 GBLMA / MCPMA 0.04 0.10 0.78 0.030 3.8 80 2.0 1.0 1.57 15.4 58.8 29.7 44.3 66.4 33.6 1,069 1.16 Example 8 GBLMA / MCPMA 0.04 0.10 0.87 0.003 0.3 80 2.0 1.0 1.57 15.4 42.4 12.0 27.2 77.9 22.1 2,368 1.22 Example 9 GBLMA / MCPMA 0.04 0.10 0.84 0.008 0.9 80 4.0 1.0 3.14 30.8 38.4 28.3 33.4 57.6 42.4 1,986 1.22 Example 10 GBLMA / MCPMA 0.04 0.10 0.88 0.004 0.4 80 4.0 1.0 3.14 30.8 22.0 19.7 20.9 52.8 47.2 1,915 1.18 Example 11 GBLMA / MCPMA 0.04 0.10 0.73 0.008 1.0 80 8.0 1.0 6.28 61.6 63.3 49.1 56.2 56.3 43.7 2,824 1.20 Example 12 GBLMA / MCPMA 0.04 0.10 0.60 0.008 1.3 90 8.0 1.0 6.28 61.6 69.9 57.3 63.6 54.9 45.1 2,436 1.20 Example 13 GBLMA / MCPMA 0.04 0.10 0.92 0.008 0.8 80 2.0 1.0 1.57 15.4 29.9 22.0 26.0 57.6 42.4 1,707 1.17 Example 14 GBLMA / MCPMA 0.04 0.10 0.84 0.008 0.9 90 2.0 1.0 1.57 15.4 44.0 33.6 38.8 56.7 43.3 3,191 1.19 Example 15 GBLMA / MCPMA 0.04 0.10 0.78 0.008 1.0 100 2.0 1.0 1.57 15.4 48.7 37.1 42.9 56.8 43.2 3,155 1.18 Example 16 GBLMA / MCPMA 0.04 0.10 0.77 0.008 1.0 110 2.0 1.0 1.57 15.4 26.5 18.2 22.3 59.2 40.8 2,179 1.20 Example 17 GBLMA / MCPMA 0.04 0.10 0.84 0.008 0.9 120 2.0 1.0 1.57 15.4 15.9 10.5 13.2 60.3 39.7 1,546 1.16 Example 18 GBLMA / MCPMA 0.04 0.10 0.65 0.008 1.2 80 8.0 1.0 6.28 61.6 71.1 58.1 64.6 55.0 45.0 6,240 1.45 Example 19 GBLMA / MCPMA 0.04 0.10 0.74 0.008 1.0 80 8.0 1.0 6.28 61.6 54.9 46.9 50.9 53.9 46.1 2,672 1.19 Example 20 GBLMA / MCPMA 0.04 0.10 0.68 0.008 1.1 80 8.0 1.0 6.28 61.6 66.8 53.2 60.0 55.7 44.3 4,953 1.31 Example 21 GBLMA / MCPMA 0.04 0.10 0.62 0.015 2.5 80 8.0 1.0 6.28 61.6 77.4 65.7 71.6 54.1 45.9 3,673 1.31 Example 22 GBLMA / MCPMA 0.04 0.10 0.62 0.015 2.5 80 8.0 1.0 6.28 61.6 85.3 73.5 79.4 53.7 46.3 3,700 1.32 Example 23 GBLMA / MCPMA 0.04 0.10 0.64 0.015 2.4 80 8.0 1.0 6.28 61.6 85.4 76.6 81.0 52.7 47.3 4,006 1.34 Example 24 GBLMA / MCPMA 0.04 0.10 0.59 0.015 2.6 80 8.0 1.0 6.28 61.6 89.6 93.7 91.6 48.9 51.1 3,851 1.35

[0162] 1: Import path for polymerization initiators, etc. 2: Import path for the first unit 3: Micro mixer 4: Import path for the second unit 5: Tubular reactor 6: Micro mixer 7: Tubular reactor

Claims

1. A method for manufacturing a polymer, comprising using a microreactor having a flow path capable of mixing a plurality of liquids, wherein a monomer component containing two or more monomers is subjected to free radical polymerization in the presence of a polymerization initiator, the microreactor having a first inlet for introducing the monomer component and other inlets located downstream of the first inlet, the monomer component being introduced into the first inlet and the other inlets, the monomer component introduced into the first inlet and the other inlets containing two or more (meth)acrylic acid monomers, and the molecular weight distribution (Mw / Mn) of the polymer being 1.45 or less.

2. A method for manufacturing a polymer, comprising using a microreactor having a flow path capable of mixing a plurality of liquids, wherein a monomer component containing two or more monomers is subjected to free radical polymerization in the presence of a polymerization initiator, the microreactor having a first inlet for introducing the monomer component and other inlets located downstream of the first inlet, the monomer component being introduced into the first inlet and the other inlets, the monomer component introduced into the first inlet and the other inlets containing the same monomers, the content error of each monomer being within ±5%, and the molecular weight distribution (Mw / Mn) of the polymer being 1.45 or less.

3. A method for manufacturing the polymer as described in claim 1 or 2, wherein free radical polymerization is carried out in the presence of a polymerization initiator and a chain transfer agent.

4. A method for manufacturing the polymer as described in claim 3, wherein, The chain transfer agent is a chain transfer agent containing sulfur carbonyl sulfide groups but not cyanide groups, and the polymerization initiator is a polymerization initiator that does not contain cyanide groups.

5. A method for manufacturing the polymer as described in claim 3, wherein, Chain transfer agents are chain transfer agents containing cyano and thiocarbonyl groups.

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