Methods for producing salt, methods for producing photosensitive or radiation-sensitive resin compositions, methods for forming patterns, and methods for producing electronic devices

Abstract

The present invention provides a method for producing a salt (P) of an organic cation and an organic anion, the method comprising: (1) a step for obtaining a product which contains the salt (P) by subjecting a salt (I) of the organic cation and a halide ion to anion exchange; (2) a step for obtaining the molar ratio X of the salt (I) to the salt (P) by applying a potentiometric titration method using an aqueous solution of silver nitrate to the product; and (3) a step for determining whether or not the purity of the salt (P) meets a specific standard on the basis of the molar ratio X.

Description

[Technical Field]

[0001] The present invention relates to a method for producing salt, a method for producing a photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device. [Background technology]

[0002] In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large-Scale Integrated Circuits), microfabrication is performed using lithography with photosensitive compositions. One lithography method involves forming a resist film using a photosensitive composition, exposing the resulting film to light, and then developing it. In particular, in recent years, studies have been conducted on using EB (Electron Beam) and EUV (Extreme Ultraviolet) light in addition to ArF excimer lasers during exposure, and the development of photosensitive or radiation-sensitive resin compositions suitable for EUV exposure has been undertaken.

[0003] In the formation of resist patterns using EUV (wavelength 13.5 nm) or electron beams for the purpose of creating fine patterns, the requirements for various performance aspects have become stricter than when using conventional ArF (wavelength 193 nm) light, etc. (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2020 / 261885 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, with the miniaturization of patterns formed using EUV light or electron beams, there is a growing demand for further improvements in various performance aspects of the photosensitive or radiation-sensitive resin compositions that form these patterns. In order to improve the various performance aspects of the above-mentioned composition, the present inventors conducted research and found that even compositions with the same components manufactured under the same conditions can exhibit differences in resolution and other properties during pattern formation depending on the product lot of the composition. It was also found that such performance differences (hereinafter referred to as "performance variations between product lots") tend to become more apparent and unavoidable as the pattern becomes finer. In one preferred embodiment, a photosensitive or radiation-sensitive resin composition contains components such as a resin, a compound that generates acid upon irradiation with active light or radiation, an acid diffusion control agent, and a solvent. In order to suppress performance variations between product lots of the composition, the inventors focused on a salt consisting of an organic cation and an organic anion, which is used as the compound that generates acid upon irradiation with active light or radiation among the above components, and investigated the effect of any differences between product lots of this salt (for example, differences in the amount of impurities in the salt between product lots) on performance variations between product lots of the composition using the conventional method of NMR (nuclear magnetic resonance). However, analysis of the amount of impurities in the above salt by NMR, and the method of manufacturing the composition based on the analysis results, revealed that it is difficult to suppress performance variations between product lots of the composition. Based on these results, the inventors conducted further investigations and found that by performing analysis using potentiometric titration with an aqueous silver nitrate solution and controlling the purity of the salt based on the analysis results in the above salt manufacturing method, performance variations between product lots of the composition can be significantly suppressed, thus completing the present invention.

[0006] Therefore, the object of the present invention is to provide a method for producing salt that can suppress variations in sensitivity due to differences in product lots of photosensitive or radiation-sensitive resin compositions. Furthermore, the present invention aims to provide a method for producing the above-mentioned photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device. [Means for solving the problem]

[0007] The inventors have found that the above problems can be solved by the following configuration. <1> A method for producing a photosensitive or radiation-sensitive resin composition, A method for producing a salt (P) of an organic cation and an organic anion, comprising the following steps. Includes, (1) Salt (I) of the above organic cation and halide ion Then, through ion exchange with the metal salt (M) of the above organic anion, the above salt (I) The process involves performing anion exchange on the above salt (P) to obtain a product containing the above salt (P). (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the above product. (3) The above molar ratio X Whether or not it is 0.5 mol% or less determination process (4) If the molar ratio X in step (3) exceeds 0.5 mol%, a step to obtain a product containing salt (P) with a molar ratio X of 0.5 mol% or less by applying a method to improve the purity of salt (P) to the product containing salt (P). (5) The above molar ratio X is 0.5 mol% The following steps involve determining the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) by high-performance liquid chromatography. (6) A step to obtain the concentration Z of the residual acid contained in the product containing the salt (P) by ultraviolet-visible absorption spectroscopy. 、 ( 7) The concentration Z of the residual acid is Is it 100 ppm or less? determination process , and, (8) A step in which, if the concentration Z of the residual acid exceeds 100 ppm in step (7) above, measures are taken to reduce the concentration Z of the residual acid. The measure to improve the purity of the salt (P) in step (4) above is purification by removing the salt (I) from the product containing the salt (P). The measures to reduce the concentration Z of the residual acid in step (8) above are: The product containing the above salt (P) is purified and extracted by adding a basic compound. The product containing the above salt (P) is then treated with an organic solvent, and the organic layer is washed with water or water containing a basic compound. Crystallization of the product containing the above salt (P), or Apply chromatography to the product containing the above salt (P). And, The cation in the above salt (P) is a cation represented by the following formula (ZaI), The above salt (P) is contained as a compound that generates acid upon irradiation with active light or radiation, The amount of the product containing the salt (P) in the above composition is defined as the planned amount of the salt (P) × (100 / Y) (where Y represents the concentration Y of the salt (P) determined in step (5) above). A method for producing a photosensitive or radiation-sensitive resin composition. [ka] In equation (ZaI), R 201 , R 202 , and R 203 Each of these independently represents an organic group. <2> A method for producing a photosensitive or radiation-sensitive resin composition, The method for producing a salt (P) of an organic cation and an organic anion comprises the following steps: (1) A step to obtain a product containing the salt (P) by performing anion exchange with the salt (I) of the organic cation and halide ion and the metal salt (M) of the organic anion. (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the above product. (3) A step to determine whether the above molar ratio X is 0.5 mol% or less. (4) If the molar ratio X in step (3) exceeds 0.5 mol%, a step to obtain a product containing salt (P) with a molar ratio X of 0.5 mol% or less by applying a method to improve the purity of salt (P) to the product containing salt (P). (5) A step to determine the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) with a molar ratio X of 0.5 mol% or less, by high-performance liquid chromatography. (6) A step of obtaining the concentration Z of the residual acid contained in the product containing the salt (P) by ultraviolet-visible absorption spectroscopy. (7) A step of determining whether the concentration Z of the residual acid is 100 ppm or less, and (8) A step in which, if the concentration Z of the residual acid exceeds 100 ppm in step (7) above, measures are taken to reduce the concentration Z of the residual acid. The measure to improve the purity of the salt (P) in step (4) above is to add the metal salt (M) of the organic anion to the product and perform the anion exchange. The measures to reduce the concentration Z of the residual acid in step (8) above are: The product containing the above salt (P) is purified and extracted by adding a basic compound. The product containing the above salt (P) is then treated with an organic solvent, and the organic layer is washed with water or water containing a basic compound. Crystallization of the product containing the above salt (P), or Apply chromatography to the product containing the above salt (P). And, The cation in the above salt (P) is a cation represented by the following formula (ZaI), The above salt (P) is contained as a compound that generates acid upon irradiation with active light or radiation, The amount of the product containing the salt (P) in the above composition is defined as the planned amount of the salt (P) × (100 / Y) (where Y represents the concentration Y of the salt (P) determined in step (5) above). A method for producing a photosensitive or radiation-sensitive resin composition. [ka] In equation (ZaI), R 201 , R 202 , and R 203 Each of these independently represents an organic group. <3> In the above formula (ZaI), R 201 ~R 203 At least one of them is an aryl group. <1> or <2> As described A method for producing a photosensitive or radiation-sensitive resin composition. <4> <1> or <2> A step of forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition produced by the method for producing the active photosensitive or radiation-sensitive resin composition described above, The process of exposing the above-mentioned photosensitive or radiation-sensitive film, and The process of developing the exposed light-sensitive or radiation-sensitive film using a developer. A pattern forming method having the following characteristics. <5> <4> A method for manufacturing an electronic device, including the pattern formation method described above. The present invention, the above <1> ~ <5> The invention relates to the above, but other matters (for example, [1] to

[13] below) are also described below.

[0008] [1] A method for producing a salt (P) of an organic cation and an organic anion, comprising the following steps. (1) A step to obtain a product containing the above-mentioned salt (P) by performing anion exchange with the above-mentioned organic cation and halide ion salt (I). (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the above product. (3) A step of determining whether the purity of the salt (P) meets a predetermined standard based on the above molar ratio X. [2] Furthermore, the method for producing salt (P) according to [1], further comprising the step of (4) if the molar ratio X in step (3) exceeds a predetermined value, applying a purity improvement measure to the product containing the salt (P) to obtain a product containing salt (P) in which the molar ratio X is less than or equal to the predetermined value.

[0009] [3] A method for producing salt (P) according to [2], wherein the measure for improving the purity of the product containing salt (P) in step (4) above is purification by removing salt (I) from the product containing salt (P). [4] The anion exchange in step (1) above is due to ion exchange between the salt (I) and the metal salt (M) of the organic anion. The measure to improve the purity of the product containing the salt (P) in step (4) above is to add the metal salt (M) of the organic anion to the product and perform the anion exchange. The method for producing salt (P) as described in [2].

[0010] [5] Furthermore, the method for producing salt (P) according to any one of [1] to [4], comprising the step of (5) determining the concentration Y of salt (P) based on the total amount of product containing salt (P) in molar ratio X less than or equal to the predetermined value by high-performance liquid chromatography. [6] Furthermore, the method for producing the salt (P) according to any one of [1] to [5], comprising: (6) obtaining the concentration Z of residual acid contained in the product containing the salt (P) by ultraviolet-visible absorption spectroscopy; and (7) determining whether the concentration Z of residual acid satisfies a predetermined standard.

[0011] [7] A method for producing a salt (P) according to [6], further comprising the step (7) above, wherein if the concentration Z of the residual acid exceeds a predetermined value, (8) a step of implementing measures to reduce the concentration Z of the residual acid. [8] A method for producing the salt (P) according to any one of [1] to [7], wherein the salt (P) is a compound that generates acid upon irradiation with active light or radiation for an active light-sensitive or radiation-sensitive resin composition.

[0012] [9] A method for producing the salt (P) according to any one of [1] to [8], wherein the cation in the salt (P) is represented by the following formula (ZaI).

[0013] [ka]

[0014] In formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group.

[10] <^ R in the above formula (ZaI) 201 ~R 203 The method for producing the salt (P) according to [9], wherein at least one of them is an aryl group.

[0015]

[11] <^ A method for producing a photosensitive or radiation-sensitive resin composition containing the salt (P) as a compound that generates an acid upon irradiation with actinic rays or radiation, the method comprising the method for producing the salt (P) according to any one of [1] to

[10] .

[12] A step of forming a photosensitive or radiation-sensitive film on a substrate with the photosensitive or radiation-sensitive resin composition produced by the method for producing the photosensitive or radiation-sensitive resin composition according to

[11] , A step of exposing the photosensitive or radiation-sensitive film, and A step of developing the exposed photosensitive or radiation-sensitive film with a developer A patterning method having.

[13] A method for producing an electronic device, the method comprising the patterning method according to

[12] . [Advantages of the Invention] <^ <^

[0016] <^ According to the present invention, a method for producing a salt capable of suppressing fluctuations in sensitivity due to differences in product lots of a photosensitive or radiation-sensitive resin composition can be provided. Further, according to the present invention, a method for producing the photosensitive or radiation-sensitive resin composition, a patterning method, and a method for producing an electronic device can be provided. [Embodiments for Carrying Out the Invention]

[0017] Hereinafter, the present invention will be described in detail. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred.

[0018] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, and X-rays, but also drawing using particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0019] In this specification, the bonding direction of the divalent linking group is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. The above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0020] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0021] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0022] pKa can also be determined by molecular orbital calculations. Specifically, based on the thermodynamic cycle, H in aqueous solution + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0023] In this specification, pKa refers to a value calculated using software package 1, based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used. "Solid content" refers to components that form photosensitive or radiation-sensitive films, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered solid content, even if its state is liquid.

[0024] (Method for producing salt (P)) The method for producing the salt (P) of the present invention will be described in detail below. The method for producing salt (P) is a method for producing salt (P) of an organic cation and an organic anion, comprising the following steps (1) to (3). (1) A step to obtain a product containing the above-mentioned salt (P) by performing anion exchange with the above-mentioned organic cation and halide ion salt (I). (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the above product. (3) A step of determining whether the purity of the salt (P) meets a predetermined standard based on the above molar ratio X.

[0025] Thus, the method for producing salt (P) first involves a step of obtaining a product containing salt (P) by performing anion exchange with salt (I) of an organic cation and a halide ion. In this invention, the molar ratio X of salt (I) to salt (P) is obtained by applying a potentiometric titration method using an aqueous silver nitrate solution. Based on this method, the purity of salt (I) in the product is determined, and if necessary, salt (I) is produced through purity improvement measures. When a photosensitive or radiation-sensitive resin composition is made using the obtained salt (I), it becomes possible to suppress the variation in sensitivity due to differences in product lots of the photosensitive or radiation-sensitive resin composition. The reason for this is not fully clear, but it is thought that, for example, compared to using typical analytical methods such as NMR, the potentiometric titration method using an aqueous silver nitrate solution allows for more accurate analysis of halide ions, and therefore the purity of salt (P) in the product can be analyzed with extremely high accuracy. Furthermore, while slight lot-to-lot linewidth variations were acceptable in conventional ArF resists, they cannot be ignored in EUV resists intended for ultrafine patterns. Therefore, potentiometric titration, which can detect lot-to-lot differences that cannot be detected by conventional NMR, became necessary. As a result, it is possible to accurately apply necessary purity improvement measures based on these analytical results, making it easier to produce high-purity salts (P) in any manufacturing lot. Consequently, it is presumed that this suppresses compositional variations that affect sensitivity caused by differences between product lots of photosensitive or radiation-sensitive resin compositions.

[0026] [Method for producing salt (P)] The method for producing salt (P) is a method for producing salt (P) of an organic cation and an organic anion, comprising the above steps (1) to (3).

[0027] (Process (1)) Step (1) is a step in which anion exchange is performed on the salt (I) of the organic cation and the halide ion to obtain a product containing the salt (P). Salts (P) are compounds composed of an organic cation and an organic anion. The salt (P) is not particularly limited, but the "M" in the "photoacid generator" described later is also used. + X - Examples include compounds represented by " (onium salt), or at least one selected from the group consisting of compounds (I) to (II) in the "photoacid generators" described later. The organic cation is not particularly limited, but is an organic cation M in the "photoacid generator" described later. + The following can be listed, and the cation represented by formula (ZaI) described below is preferred. The organic anion is not particularly limited, but X in the "photoacid generator" described later. - Alternatively, one could refer to the "anion portion" of at least one compound selected from the group consisting of compounds (I) to (II) in the "photoacid generator" described later. The "anionic part" in compound (I) refers to the cationic part M1 in compound (I). + cation site M2 + Represents structures other than those mentioned above. The "anionic part" in compound (II) refers to the cationic part M1 in compound (II). + Represents structures other than those mentioned above.

[0028] The product containing salt (P) can be obtained by anion exchange with the salt (I) of the above organic cation and halide ion. Salt (I) is a compound consisting of the above-mentioned organic cation and halide ions. Examples of halide ions, though not particularly limited, include chloride ions, bromide ions, and iodide ions. Anion exchange can be carried out by conventional methods. A preferred embodiment is the synthesis example described in the Examples. The method of anion exchange is not particularly limited, but it is preferable to carry out the reaction in a two-phase system containing water and a solvent immiscible with water. Examples of solvents that can be used include halogenated solvents such as methylene chloride and chloroform, ester solvents such as ethyl acetate, ketone solvents such as methyl isobutyl ketone, and ether solvents such as cyclopentyl methyl ether and tert-butyl methyl ether. These may be combined with water-soluble solvents such as acetone, THF, and methanol as appropriate. Anion exchange typically occurs through ion exchange between the salt (I) and the metal salt (M) of the organic anion. The metal ion in the metal salt (M) of the above-mentioned organic anion is not particularly limited, but examples include potassium ions and sodium ions. Furthermore, the metal salt of the above-mentioned organic anion may be generated in the reaction system by mixing the proton form of the organic anion with an inorganic salt such as sodium bicarbonate, along with the salt (I) and solvent during the reaction.

[0029] (Process (2)) Step (2) is a step in which the molar ratio X of salt (I) to salt (P) is obtained by applying a potentiometric titration method using an aqueous silver nitrate solution to the above product. The following describes an example of a preferred embodiment of a potentiometric titration method using an aqueous silver nitrate solution.

[0030] (potentiometric titration method) The product containing the salt (P) is weighed out in wg and dissolved in a solvent such as THF (tetrahydrofuran) to prepare the sample solution. Using an aqueous solution of silver nitrate (A(N)), the titration volume is measured for a blank solution of only the solvent and the sample solution using an automatic titrator (AT-510 Kyoto Electronics Manufacturing Co., Ltd.). From the obtained titration volumes, the halogen amount Q (ppm) is calculated using the following formula (1). Q(ppm)=(V1-V2)×A×f×MQ×1000 / W (1)

[0031] In equation (1), V1 is the titration volume of the sample solution (ml), V2 is the titration volume of the blank solution (ml), f is the titer of the titrator (silver nitrate aqueous solution), MQ is the molar mass of the halogen atom to be determined (g / mol), and W is the weighed value of the product containing the salt (P). Assuming that the Q obtained above is entirely due to the residual salt (I) (raw material), the molar ratio X (mol%) of salt (I) to salt (P) is calculated using the following formula (2). X = Q × MB / MQ / 10000 (2)

[0032] In equation (2), MB (g / mol) represents the molecular weight of the salt (P). For example, regarding methods for measuring titer, see "JIS K 8001:2017 General Rules for Test Reagent Methods". The method described in "Appendix JA.6 Titration Solutions - JA.6.4n" is one example. The above molar ratio X represents the percentage (mol%) of salt (I) remaining relative to 1 mol of salt (P).

[0033] The concentration of the silver nitrate aqueous solution used is not particularly limited, but is preferably 0.01 N (mol / L) or less. The amount of the product containing the salt (P) used is not particularly limited, but is preferably 50 mg or more. The solvent used to dissolve the product containing the salt (P) is not particularly limited as long as it is a water-soluble polar solvent that does not react with silver nitrate, but is preferably an ether-based solvent such as THF or an ester-based solvent such as γ-butyrolactone.

[0034] (Step (3)) Step (3) is a step in which, based on the above molar ratio X, it is determined whether or not the purity of the above salt (P) meets a predetermined standard. The purity of the salt (P) is determined based on the above molar ratio X. If the molar ratio X is high, the purity of the salt (P) decreases, and if the molar ratio X is low, the purity of the salt (P) increases. Therefore, the determination of whether the purity of the salt (P) meets a predetermined standard is preferably made by determining whether the molar ratio X is below a predetermined value. The above-mentioned predetermined standards (for example, the above-mentioned predetermined values) can be set as appropriate in the method for producing salt (P). Since salt (I) can function as an acid diffusion control agent, it has a significant effect on sensitivity (linewidth variation), and it is preferable to make X as small as possible. In one preferred embodiment, X is preferably 0.5 mol% or less, more preferably 0.4 mol% or less, and even more preferably 0.3 mol% or less.

[0035] The present invention's method for producing salt (P) further preferably includes a step of (4) if the molar ratio X exceeds a predetermined value in step (3) above, applying a purity improvement measure to the product containing salt (P) to obtain a product containing salt (P) where the molar ratio X is less than or equal to the predetermined value.

[0036] (Step (4)) Step (4) is a step in which, if the molar ratio X in step (3) exceeds a predetermined value, a purity improvement measure is applied to the product containing the salt (P) to obtain a product containing the salt (P) with a molar ratio X of less than or equal to the predetermined value. Step (4) is a step in which a process is applied to reduce the molar ratio X when the above molar ratio X exceeds a predetermined value. The above predetermined value can be set as appropriate, but it is preferably 0.5 mol%, more preferably 0.4 mol%, and even more preferably 0.3 mol%.

[0037] In a preferred embodiment, the measure to improve the purity of the product containing salt (P) in step (4) is purification by removing salt (I) from the product containing salt (P). As a method for removing the salt (I) mentioned above, one example is to perform crystallization on the product. The solvents that can be used for crystallization are not particularly limited, but examples include water, alcohol-based solvents (preferably methanol), nitrile-based solvents (preferably acetonitrile), ketone-based solvents (preferably acetone), ester-based solvents (preferably ethyl acetate), halogen-based solvents (preferably chloroform), ether-based solvents (preferably diisopropyl ether), and hydrocarbon-based solvents (preferably hexane). It is preferable to select and combine two or more of these. Furthermore, to remove the salt (I) mentioned above, for example, if the water solubility of salt (I) is relatively high, it can be removed by increasing the number of liquid-liquid extraction operations. Examples of organic solvents include halogenated solvents such as methylene chloride and chloroform, ester solvents such as ethyl acetate, ketone solvents such as methyl isobutyl ketone, and ether solvents such as cyclopentyl methyl ether and tert-butyl methyl ether. These may be combined with water-soluble solvents such as acetone, THF, and methanol as appropriate. Three or more liquid-liquid extraction operations are preferred, and five or more are more preferred. Furthermore, various chromatographic methods, such as silica gel column chromatography, can be used to remove the above-mentioned salt (I).

[0038] In another preferred embodiment, the anion exchange in step (1) is performed by ion exchange between the salt (I) and the metal salt (M) of the organic anion. One way to improve the purity of the product containing the salt (P) in step (4) above is to add the metal salt (M) of the organic anion to the product and perform the anion exchange. The amount of the metal salt (M) of the organic anion added can be appropriately set according to the molar ratio X determined in step (3). Since the amount of salt (I) remaining in the product can be calculated from the above molar ratio X, the amount of the metal salt (M) of the organic anion that reacts with the remaining salt (I) can be appropriately set.

[0039] In another preferred embodiment, the anion exchange in step (1) is performed by ion exchange between the salt (I) and the metal salt (M) of the organic anion. One way to improve the purity of the product containing the salt (P) in step (4) above is to change the molar ratio of the salt (I) to the metal salt (M) of the organic anion and then carry out step (1) above.

[0040] Based on the above purity improvement measures, the product containing the obtained salt (P) is subjected to step (2) above to obtain the molar ratio X of salt (I) to salt (P). Then, step (3) is performed to determine whether the purity of salt (P) meets a predetermined standard. The reaction is terminated when the purity of the above salt (P) meets the specified standard (specifically, the molar ratio X is less than or equal to the specified value). If the purity of the salt (P) does not meet the prescribed standard, the purity improvement measures for the product containing the salt (P) in step (4) will be carried out again. Step (4) yields a product containing salt (P) in which the molar ratio X is less than or equal to the predetermined value. In this way, salt (P) is produced.

[0041] The present invention's method for producing salt (P) further preferably includes the step of determining the concentration Y of salt (P) based on the total amount of product containing salt (P) with a molar ratio X of less than or equal to the predetermined value, by high-performance liquid chromatography (HPLC).

[0042] (Step (5)) Step (5) is a step in which the concentration Y of the salt (P) is determined by high-performance liquid chromatography (HPLC) based on the total amount of the product containing the salt (P) in molar ratio X of the salt (P) which is less than or equal to the predetermined value. The above salt (P) concentration Y (mass%) can be obtained by step (5). The following describes an example of a preferred embodiment of a method for measuring the concentration Y of the above salt (P) by high-performance liquid chromatography (HPLC).

[0043] (Method for Measuring Concentration Y) An example of the measurement method by HPLC is shown below, but the present invention is not limited thereto. (A) Preparation of Calibration Curve Prepare a solution A by dissolving an internal standard substance in a solvent. Mix the reference lot W1 g of salt (P), solution A, and the solvent to prepare solution B1. Change the amounts of salt (P) to W2 g and W3 g respectively, and similarly prepare solutions B2 and B3. Perform HPLC measurement on solutions B1 to B3 under the following conditions, and for each, calculate the peak area values S1 to S3 of the cation (or anion) of salt (P) with respect to the peak area value of the internal standard substance. Repeat the same measurement several times, and calculate the average values S 1AVE ~S 3AVE Calculate. Prepare a calibration curve from the sample concentration (g / ml) of each solution and S 1AVE ~S 3AVE <HPLC Measurement Conditions> Measuring device: Waters HPLC system 2695 (manufactured by Waters) Column: Shim-pack CLC-ODS (inner diameter 6.0 mm × 150 mm) Eluent: Acetonitrile / 0.05 M ammonium acetate aqueous solution Column temperature: 40 °C Flow rate: 1 ml / min Sample injection volume: 5 μl Detection wavelength: 254 nm

[0044] The internal standard substance is not particularly limited as long as its peak does not overlap with the cations and anions constituting salt (P) and it has absorption at the detection wavelength, but it is preferably an aromatic compound, and examples include alkoxy group-substituted benzenes (such as 1,3,5-trimethoxybenzene), ester group-substituted benzenes (such as propyl benzoate), alkyl group-substituted benzenes (such as dibenzyl), etc. The solvent is not particularly limited, and acetonitrile, THF, methanol, etc. are preferably used. ​There are no particular restrictions on the eluent, but acetonitrile, THF, methanol, etc., are preferably used. Ammonium acetate, phosphoric acid / triethylamine, etc., are preferably used as buffer solutions. The optimal ratio of organic solvent to buffer solution varies depending on the structure of the salt (P) and the type of solvent used, but it is preferable to measure it within the range of organic solvent / buffer solution = 40 / 60 to 80 / 20 (volume ratio). When creating a calibration curve, it is preferable to measure three or more solutions with different sample concentrations to improve the accuracy of the calibration curve. Furthermore, to suppress the influence of variations in HPLC peak area values, it is preferable to measure each solution three or more times and use the average value.

[0045] (B) Concentration Y measurement Prepare solution A of the internal standard. Mix the target lot Wg of product containing salt (P), solution A, and solvent to prepare LC ml of solution C1. Perform HPLC measurement of solution C1 under the same conditions as above, and calculate the peak area value SC of the salt (P) cation (or anion) relative to the peak area value of the internal standard. Repeat the measurement of the same sample solution several times and calculate the average value SC. AVE Calculate the above SC. AVE From the calibration curve above, the corresponding sample concentration KC (g / ml) is calculated. The concentration Y (mass%) of salt (P) in the product containing salt (P) is calculated from the following formula (3). Y = (KC × LC / W) × 100 (3) In equation (3), LC represents the solvent volume (ml) of solution C1. Concentration Y represents the concentration of salt (P) in the product containing salt (P).

[0046] <Regarding the reference lot of salt (P) in calibration curve creation> The standard lot of salt (P) is preferably one in which the raw material cations and anions have been sufficiently removed as much as possible, and impurities that affect the cation / anion ratio have been reduced. For purification to sufficiently remove the raw material cation or raw material anion, purification by recrystallization or purification by various types of chromatography is preferred. As a means of confirming that the raw material cation has been sufficiently removed from the reference lot, a method of detecting residual halogen by silver nitrate titration is preferred. If the raw material cation is a salt of an organic anion, it is preferable to convert it to a halogen salt using an ion exchange resin before using it in the synthesis of salt (P) and then use the silver nitrate titration method described above. As a means of confirming that the raw material anion has been completely removed from the reference lot, if the raw material anion is a metal salt, it is preferable to detect the metal element by means of ICP-OES or ICP-MS. In the case of a non-metallic salt, if there is an element that only exists in the pair salt between the raw material anion and its pair salt, it can be detected by elemental analysis, but otherwise, it is preferable to synthesize the raw material anion as a metal salt only in the reference lot. It is preferable to have fewer impurities other than the raw material cations and anions, as well as less residual solvent. Purification methods to reduce impurities include purification by recrystallization and purification by various chromatography methods, as described above. It is preferable to confirm that organic impurities have been sufficiently removed by HPLC or LCMS measurement. It is also preferable to detect metal elements by means such as ICP-OES or ICP-MS to confirm that there are no inorganic salts or similar impurities. Methods for reducing residual solvent include making a solution with a low boiling point solvent such as methylene chloride and drying under reduced pressure while heating. If it is difficult to reduce the residual solvent, the residual solvent may be quantified by NMR or gas chromatography and used as a reference lot. In this case, the accuracy of the concentration (solid content value) of the reference lot itself is low, but it is possible to control the lot as a relative value using the method of the present invention, and in some cases the solid content value may exceed 100%, but this is not a problem.

[0047] In step (5), the concentration Y (mass%) of the salt (P) can be obtained. In the method for producing salt (P) of the present invention, the reaction is terminated when the purity of the salt (P) meets a predetermined standard (specifically, the molar ratio X is less than or equal to a predetermined value). Salt (P) is obtained by this reaction, and variations in resolution due to differences in product lots of the photosensitive or radiation-sensitive resin composition can be suppressed. In step (5), the concentration Y (mass%) of salt (P) can be obtained from a perspective different from that of the molar ratio X. The concentration Y is determined based on the product containing salt (P), focusing on impurities other than salt (I) (e.g., solvents). This step is preferable because it allows for more detailed determination of the salt (P) concentration, thereby better suppressing variations in resolution due to differences in product lots of the photosensitive or radiation-sensitive resin composition.

[0048] After obtaining concentration Y, the product containing salt (P) may or may not be purified. Known methods can be used for purification. If purification is not performed, and a concentration Y can be obtained, then in the production of the resist composition (typically a preparation), the salt (P) Products containing By setting the amount of salt (P) to be added as the planned amount of salt (P) × (100 / Y), the planned amount of salt (P) can be more reliably incorporated into the resist composition, which tends to further suppress variations in resolution due to differences between product lots, and is therefore preferable.

[0049] The present invention's method for producing salt (P) further preferably includes (6) a step of obtaining the concentration Z of residual acid contained in the product containing salt (P) by ultraviolet-visible absorption spectroscopy, and (7) a step of determining whether the concentration Z of residual acid satisfies a predetermined standard. (Process (6)) Step (6) is a step in which the concentration Z of the residual acid contained in the product containing the salt (P) is obtained by ultraviolet-visible absorption spectroscopy. In the manufacturing process of salt (P), residual acid may remain due to the persistence of protonated forms of the raw material anions, residual acid used during liquid-liquid separation, or decomposition of the raw materials or salt (P) itself. However, by removing the residual acid that does not meet the predetermined standards obtained in step (7), the purity of salt (P) can be further increased, which is preferable.

[0050] The following describes an example of a preferred embodiment of a method for measuring the concentration Z of residual acid contained in a product containing the above-mentioned salt (P) by ultraviolet-visible absorption spectroscopy.

[0051] (Method for measuring concentration Z) An example of a method for measuring concentration Z using ultraviolet-visible absorption spectroscopy is shown below, but the present invention is not limited thereto.

[0052] (A) Calibration curve creation Solution A is prepared by dissolving compound C (hereinafter also referred to as compound C), which develops color when exposed to acid, in a solvent. Solution B is prepared by dissolving an existing acidic compound D (hereinafter also referred to as compound D) in a solvent. Solution D1 is prepared by mixing solution A and solution B and diluting them with a solvent. The ultraviolet-visible absorption spectrum of solution D1 is measured using "UV-1800 (manufactured by Shimadzu Corporation), solvent: acetonitrile," and the absorbance Abs of compound C at its maximum absorption wavelength is measured. D1 Obtain solution D1. Prepare solutions D2, D3, and D4 by changing the dilution of solution D1. Measure the ultraviolet-visible absorption spectra of the obtained D2, D3, and D4 in the same manner, and Abs D2 , Abs D3 , Abs D4 To obtain the result, prepare solution E by diluting only solution A as a blank. Similarly, measure the ultraviolet-visible absorption spectrum of solution E and obtain the absorbance Abbs at the maximum absorption wavelength. E Obtain the Abs obtained above. D1 ~Abs D4 Regarding Abs E The difference is calculated, and the obtained results are analyzed using Abs. DE1 ~Abs DE4 The molar concentrations of compound D in D1, D2, D3, and D4, and the resulting Abs DE1 ~Abs DE4 From this, a calibration curve is created between the molar concentration of compound D and the absorbance of compound C.

[0053] Compound C, which develops color in response to acid, is not particularly limited as long as it is a compound that reacts quantitatively with even trace amounts of acid and produces a chromogen that has strong absorption at a specific wavelength. For example, rhodamine derivatives (e.g., rhodamine base (manufactured by Sigma-Aldrich)) can be cited. Acidic compound D is not particularly limited as long as it is an acidic compound that can produce color in compound C, but examples include tosylic acid (p-toluenesulfonic acid), methanesulfonic acid, and hydrochloric acid. To improve the accuracy of the calibration curve, it is preferable to prepare at least three solutions, D1 to D3, with varying concentrations of acidic compound D, and perform measurements. Furthermore, to further improve the accuracy of the calibration curve, multiple UV-Vis absorption spectra measurements should be taken for each solution D, and the average value should be used as the Abs curve. D It can also be used as such. The solvent used is not particularly limited as long as it is neutral or basic and does not absorb at the absorption wavelength of the acid chromogen. Preferred solvents include aprotic polar solvents such as acetonitrile and THF, protic polar solvents such as methanol, and halogenated solvents such as methylene chloride.

[0054] (B) Measurement of concentration Z Solution A is prepared by dissolving compound C, which develops color when exposed to acid, in a solvent. A quantity of product Wg containing the salt (P) is measured, solution A is added, and solution F is prepared by diluting with the solvent. Solution E is prepared as a blank by diluting only solution A. The ultraviolet-visible absorption spectra of solutions F and E are measured in the same manner as when creating the calibration curve, and the absorbance Abbs at the maximum absorption wavelength of compound C is measured. F and Abs E To obtain. These differences Abs FE =Abs F -Abs E Using the above, calculate the molar concentration T (mol / l) of the corresponding compound D from the calibration curve created above. Using the following formula (4), calculate the concentration Z (ppm) of the residual acid contained in the product containing the salt (P), in terms of compound D. Z = T × MT × LB × 1000 / W (4) In equation (4), MT (g / mol) represents the molecular weight of compound D. LB represents the total solvent volume (l) of solution F. The concentration Z of the residual acid contained in the product containing the above salt (P) is the concentration in terms of compound D.

[0055] (Process (7)) Step (7) is a step in which it is determined whether the concentration Z of the residual acid meets a predetermined standard. The prescribed standards can be set as appropriate in the method for producing salt (P). In one preferred embodiment, Z is preferably 100 ppm or less, and more preferably 50 ppm or less.

[0056] (Process (8)) In step (7) above, if the concentration Z of the residual acid exceeds a predetermined value, it is preferable to have a step (8) in which measures are taken to reduce the concentration Z of the residual acid. In one preferred embodiment, a method for reducing the concentration Z is to appropriately add a basic compound and then purify and extract the solution. Known methods can be used for purification and extraction. In one preferred embodiment, a measure to reduce the concentration Z is to add an organic solvent (e.g., methylene chloride) and wash the organic layer with water or water containing a basic compound (e.g., ammonia). The number of washes is preferably three or more, and more preferably five or more. In one preferred embodiment, a method for reducing the concentration Z is to perform crystallization in the product. The solvent that can be used for crystallization is not particularly limited, but examples include the same solvent as in step (4). In one preferred embodiment, various chromatographic methods such as silica gel column chromatography can be used to reduce the concentration Z.

[0057] Preferably, the salt (P) is a compound that generates acid upon irradiation with active light or radiation for active light-sensitive or radiation-sensitive resin compositions. Examples of compounds that generate acid upon irradiation with active light or radiation include the photoacid generator (B) described later, or the acid diffusion control agent.

[0058] (Method for producing a photosensitive or radiation-sensitive resin composition) The method for producing a photosensitive or radiation-sensitive resin composition according to the present invention (hereinafter also referred to as "the method for producing the composition of the present invention" or "the method for producing the composition") is, The present invention relates to a method for producing the above-mentioned salt (P), and includes a method for producing the above-mentioned salt (P), wherein the salt (P) is a compound that generates acid upon irradiation with active light or radiation, and is contained in the above-mentioned salt (P). The photosensitive or radiation-sensitive resin compositions obtained by the method for producing the compositions of the present invention are described below.

[0059] The photosensitive or radiation-sensitive resin composition is preferably a resist composition, and may be either a positive-type or negative-type resist composition. The resist composition may be an alkaline-developable resist composition or an organic solvent-developable resist composition. The resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition. Typically, the resist composition is a chemically amplified resist composition.

[0060] The following describes in detail the various components that the photosensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition of the present invention") may have in the method for producing the photosensitive or radiation-sensitive resin composition of the present invention.

[0061] <Acid decomposable resin> The composition of the present invention may also contain an acid-degradable resin (hereinafter also referred to as "resin (A)"). Resin (A) typically contains groups that decompose and increase in polarity due to the action of acid (hereinafter also referred to as "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. When resin (A) has acid-degradable groups, in the pattern forming method described herein, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic developer is used as the developer, a negative-type pattern is suitably formed. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are preferred as repeating units having acid-degradable groups.

[0062] (Repeating unit with acid-degradable group) An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group (a group that is released upon the action of an acid). In other words, resin (A) has repeating units that decompose upon the action of an acid to produce a polar group. Resins having these repeating units become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents. Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0063] Examples of groups that are eliminated by the action of an acid include those represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0064] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In cycloalkyl groups formed by the bonding of two Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. If the composition of the present invention is, for example, a resist composition for EUV lithography, it is preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0065] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the composition of the present invention is, for example, a resist composition for EUV lithography, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0066] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0067] [ka]

[0068] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0069] If the composition of the present invention is, for example, a resist composition for EUV lithography, then the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by L1 and L2 may further preferably have a fluorine atom or an iodine atom as a substituent. In addition to fluorine atoms and iodine atoms, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may also preferably contain heteroatoms such as oxygen atoms. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. If the resist composition is, for example, an EUV lithography resist composition, then in alkyl groups which may contain a heteroatom represented by Q, cycloalkyl groups which may contain a heteroatom, aryl groups which may contain a heteroatom, amino groups which may contain a heteroatom, ammonium groups which may contain a heteroatom, mercapto groups which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and groups which may contain a heteroatom, the heteroatom is preferably a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom which may contain a heteroatom.

[0070] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. If the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0071] From the standpoint of excellent acid decomposition properties of repeating units, in the case of a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0072] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0073] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0074] [ka]

[0075] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. Examples of divalent linking groups represented by L1, which may have a fluorine atom or an iodine atom, include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. Among these, L1 is preferably -CO-, an arylene group, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO-, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0076] The alkyl group represented by R1 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms in the alkyl group having a fluorine atom or an iodine atom, represented by R1, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by R1 may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0077] Examples of leaving groups represented by R2 that may have a fluorine atom or an iodine atom include the leaving groups represented by the above formulas (Y1) to (Y4) and that have a fluorine atom or an iodine atom.

[0078] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0079] [ka]

[0080] In formula (AI), Xa1 represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may bond together to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0081] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. 11 Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. For Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0082] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0083] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The repeating unit represented by formula (AI) preferably has, for example, Rx1 being a methyl group or an ethyl group, and Rx2 and Rx3 being bonded to form the cycloalkyl group described above.

[0084] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0085] The repeating unit represented by formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0086] Specific examples of repeating units having acid-degradable groups are shown below, but are not limited to these. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Resin (A) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0093] [ka]

[0094] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0095] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0096] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0097] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. An ethynyl group is preferred as the alkynyl group for Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Ry3 are bonded together to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0098] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0099] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0100] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0101] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but are not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''', R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, or monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof, and n, m, and l represent integers of 0 or more.

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0107] The resin (A) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of the following repeating units (20) to (25). (20) Repeating units having an acid group, as described later (21) Repeating units that do not have either an acid-degradable group or an acid group, as described later, and have a fluorine atom, a bromine atom, or an iodine atom. (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having photoacid generators, as described later (24) Repeating units represented by formula (V-1) or formula (V-2), as described later. (25) Repeating units for reducing the mobility of the main chain Furthermore, the repeating units represented by formulas (A) to (E) described in International Publication No. 2020 / 004306

[0120] to

[0151] , as described later, correspond to (25) repeating units for reducing the mobility of the main chain. Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0108] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from the photoacid generator is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0109] The resin (A) may have at least one repeating unit selected from the group consisting of A above. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of A above. Resin (A) may contain at least one of fluorine atoms and iodine atoms. When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (A) contains at least one of fluorine atoms and iodine atoms. If resin (A) contains both fluorine atoms and iodine atoms, resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may contain two types of repeating units: repeating units containing fluorine atoms and repeating units containing iodine atoms. The resin (A) may have repeating units having aromatic groups. When the composition of the present invention is used as a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the resin (A) has repeating units having aromatic groups. Resin (A) may have at least one repeating unit selected from the group consisting of group B. When the resist composition is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) has at least one repeating unit selected from the group consisting of group B. Furthermore, when the resist composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not have aromatic groups.

[0110] (Repeating units containing acidic groups) The resin (A) may have repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. The hexafluoroisopropanol group described above may have one or more fluorine atoms (preferably one to two) substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which the polar group is protected by a group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0111] Examples of repeating units having an acidic group include the following:

[0112] [ka]

[0113] As a repeating unit having an acid group, the repeating unit represented by the following formula (1) is preferred.

[0114] [ka]

[0115] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. If there are multiple Rs, they may cooperate to form a ring. A hydrogen atom is preferred as R. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0116] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] Of the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0122] [ka]

[0123] [ka]

[0124] The content of repeating units having acid groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0125] (A repeating unit that does not possess either an acid-degradable group or an acidic group, but has a fluorine atom, a bromine atom, or an iodine atom.) Resin (A) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. It is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0126] The repeating unit X is preferably represented by formula (C).

[0127] [ka]

[0128] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom. 10 This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof.

[0129] Examples of repeating units having fluorine or iodine atoms are shown below.

[0130] [ka]

[0131] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A).

[0132] The total content of repeating units in resin (A) that contain at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of resin (A). There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0133] (Repeating units having a lactone group, sultone group, or carbonate group) The resin (A) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0134] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferable. The resin (A) preferably has repeating units having lactone groups or sultone groups obtained by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), and the lactone groups or sultone groups may be directly bonded to the main chain. For example, the ring member atoms of the lactone groups or sultone groups may constitute the main chain of the resin (A).

[0135] [ka]

[0136] The above lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0137] Examples of repeating units having a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3), include the repeating unit represented by the following formula (AI).

[0138] [ka]

[0139] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these. Among these, a single bond or a linking group represented as -Ab1-CO2- is preferred for Ab. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

[0140] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0141] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by the following formula (A-1) is preferred.

[0142] [ka]

[0143] In formula (A-1), R A 1 R represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent linking groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0144] The unit Y is exemplified below. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0145] [ka]

[0146] [ka]

[0147] [ka]

[0148] The content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0149] (Repeating unit with photoacid-generating group) The resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (hereinafter also referred to as a "photoacid generating group"). Examples of repeating units having photoacid-generating groups are those described in paragraphs

[0109] to

[0115] of International Publication No. 2020 / 004306.

[0150] (Repeating units represented by formula (V-1) or formula (V-2)) The resin (A) may have repeating units represented by formula (V-1) or formula (V-2). Examples of repeating units represented by formula (V-1) or formula (V-2) are those described in paragraphs

[0116] to

[0119] of International Publication No. 2020 / 004306.

[0151] (A repeating unit that reduces the mobility of the main chain) Examples of repeating units for reducing the mobility of the main chain include those described in paragraphs

[0120] to

[0151] of International Publication No. 2020 / 004306.

[0152] (A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0153] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating units having a hydroxyl group or a cyano group do not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0154] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups are those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921.

[0155] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have an alicyclic hydrocarbon structure and repeating units that do not exhibit acid decomposition. Examples of such repeating units include those described in paragraph

[0164] of International Publication No. 2020 / 004306.

[0156] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group are those described in paragraphs

[0165] to

[0173] of International Publication No. 2020 / 004306.

[0157] (Other repeating units) Furthermore, resin (A) may have other repeating units besides those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. The following are examples of other repeating units besides those mentioned above.

[0158] [ka]

[0159] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0160] As for resin (A), in particular when the composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are a combination of methacrylate and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0161] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0162] In the composition of the present invention, the content of resin (A) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition. Resin (A) may be used alone or in combination of multiple types.

[0163] <Photoacid Generator> The composition of the present invention may contain a compound that generates acid upon irradiation with active light or radiation (hereinafter also referred to as "photoacid generator (B)"). The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer (for example, resin (A) described later). Alternatively, both the form of a low molecular weight compound and the form incorporated into a polymer (for example, resin (A) described later) may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0164] For example, the photoacid generator (B) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0165] "M + X - In the compound represented by ", M+ This represents an organic cation. The organic cation is not particularly limited. The valency of the organic cation may be 1 or 2 or more. In particular, among the above organic cations, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0166] [ka]

[0167] In the above equation (ZaI), R 201 , R 202 , and R 203 Each of these independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. 201 ~R 203 Two of these may bond together to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0168] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0169] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group. R in the above formula (ZaI) 201 ~R 203 It is preferable that at least one of them is an aryl group. In the arylsulfonium cation, all of R 201 ~R 203 may be aryl groups, or a part of R 201 ~R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group. One of R 201 ~R 203 is an aryl group, and the remaining two of R 201 ~R 203 may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. As the group formed by combining two of R 201 ~R 203 for example, an alkylene group (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group can be mentioned. Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0170] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0171] R 201 ~R 203 Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent, forming a halogenated alkyl group such as a trifluoromethyl group. The above substituents may also preferably form an acid-degradable group in any combination. Furthermore, an acid-degradable group is defined as a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a group that is eliminated by the action of an acid. The polar group and leaving group are as described above. R in the above formula (ZaI) 201 ~R 203 It is preferable that at least one aryl group has a substituent.

[0172] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 However, each of these independently represents a cation that is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0173] R 201 ~R 203 Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 This may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0174] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0175] [ka]

[0176] In formula (ZaI-3b), R 1c ~R 5cEach of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R 1c ~R 7c , and R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0177] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These elements may bond to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0178] R 1c ~R 5c Two or more of the following, R 6c and R 7c, and R x and R y Examples of groups formed by the bonding of these atoms include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0179] R 1c ~R 5c , R 6c , R 7c , R x , R y , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The rings formed by the bonding of these elements to each other may have substituents.

[0180] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0181] [ka]

[0182] In equation (ZaI-4b), l represents an integer between 0 and 2, and r represents an integer between 0 and 8. R 13This represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. R 14 R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. 14 If multiple instances exist, each independently represents one of the above-mentioned groups, such as a hydroxyl group. R 15 Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R 15 It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R 15 The ring formed by the bonding of these elements may have substituents.

[0183] In equation (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. R 13 ~R 15 , and R x and R yIt is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0184] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0185] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 and R 205 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0186] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] "M + X - In the compound represented by ", X - This represents an organic anion. The organic anion is not particularly limited and can be any organic anion with one or more valents. As for the organic anion, anion with a remarkably low ability to undergo nucleophilic reactions is preferred, and non-nucleophilic anions are more preferred.

[0191] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0192] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group described above may be, for example, a fluoroalkyl group (which may have substituents other than a fluorine atom; it may also be a perfluoroalkyl group).

[0193] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0194] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0195] In aralkyl carboxylic acid anions, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0196] An example of a sulfonylimid anion is the saccharin anion.

[0197] For bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure. This increases the acid strength.

[0198] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4 - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0199] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably with 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0200] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0201] [ka]

[0202] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. The non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0203] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0204] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0205] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0206] In formula (AN1-1), * a R in equation (AN1) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) 1 )(R 2)- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. However, X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) 2a and R 2b If all of them are hydrogen atoms, then Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. * A R in equation (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0207] In formula (AN1), R 3 This represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0208] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0209] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0210] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0211] [ka]

[0212] In equation (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0213] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0214] R 4 and R 5 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred for R4 and R5.

[0215] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0216] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0217] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0218] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0219] The anion represented by formula (AN2) is SO3. - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q, and W are the same as in equation (AN2). q' represents an integer from 0 to 10.

[0220] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0221] [ka]

[0222] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0223] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations of these.

[0224] B represents a hydrocarbon group. For B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group) is more preferred.

[0225] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, R q R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. q They may be joined to each other to form a ring. Two R q The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0226] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0227] [ka]

[0228] [ka]

[0229] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have substituents (for example, a hydroxyl group).

[0230] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). Z 2c The hydrocarbon group in the above may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group, which may have substituents. The carbon atoms forming the norbornyl group may also be carbonyl carbons. In equation (d1-2), "Z 2c -SO3 - It is preferable that the anion is different from the anion represented by the above formulas (AN1) to (AN3). For example, Z 2c The group other than an aryl group is preferable. For example, Z 2c -SO3 - For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z 2c is, -SO3 - Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0231] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0232] In formula (d1-4), R 53 and R 54 Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom).53 and R 54 They may be joined to each other to form a ring.

[0233] Organic anions may be used individually or in combination of two or more.

[0234] The photoacid generator is preferably at least one selected from the group consisting of compounds (I) to (II).

[0235] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural part X: Anion part A1 - and cation site M1 + It consists of the above, and upon irradiation with active light or radiation, it forms a structural site that forms a first acidic site represented by HA1. Structural site Y: Anionic site A2 - and cation site M2 + It consists of the above, and upon irradiation with active light or radiation, a structural site which forms a second acidic site represented by HA2. The above compound (I) satisfies the following condition I.

[0236] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation portion M2 in the structural portion Y + to H + The compound PI obtained by replacing the above structural site X is the above cation site M1 + to H + The acid dissociation constant a1 derived from the acidic site represented by HA1, which is replaced by the above-mentioned cation site M2 in the above-mentioned structural site Y + to H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, which is replaced by the above acid dissociation constant a1, and the above acid dissociation constant a2 is greater than the above acid dissociation constant a1.

[0237] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having HA1 and HA2". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of the compound having the above characteristics is the acid dissociation constant a2.

[0238] If compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having two HA1 and one HA2". When the acid dissociation constant of compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the acid dissociation constant when a compound having one A1 - A compound having one HA1 and one HA2 is "two A1 - The acid dissociation constant when forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation site M1 corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the acid dissociation constant when a compound has the above-mentioned cation site M1 in the above-mentioned structural site X corresponds to the acid dissociation constant a2. + to H +When there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 which is replaced, the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. Note that when the compound PI is "one A1 - and a compound having one HA1 and one HA2", the acid dissociation constant is aa, and "one A1 - and a compound having one HA1 and one HA2" becomes "two A1 - and a compound having one HA2", when the acid dissociation constant is ab, the relationship between aa and ab satisfies aa < ab.

[0239] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 <000032 >and two or more of the above M1 + may be the same or different from each other. In the compound (I), the above A1 - and the above A2 - and the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0240] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. Note that the upper limit value of the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less.

[0241] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0242] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0243] Anion part A1 - and anion part A2 - This refers to a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion part A1 - Preferably, the acidic site can form an acidic site with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion part A2 - For example, Anion part A1 - It is preferable that the material can form an acidic site with a larger acid dissociation constant than the other material, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), R A R represents a monovalent organic group. A The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0244] [ka]

[0245] [ka]

[0246] Cation site M1 + and cation site M2 + This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. + Examples of organic cations represented by the following are given.

[0247] The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later.

[0248] - Compound represented by formula (Ia-1) - In the following, we will first discuss the compound represented by formula (Ia-1).

[0249] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0250] The compound represented by formula (Ia-1) is HA when irradiated with active light or radiation. 11 -L1-A 12 It produces an acid represented by H.

[0251] In formula (Ia-1), M 11 + and M 12 + Each of these independently represents an organic cation. A 11 - and A 12 - Each of these independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12+ These may be the same or different. A 11 - and A 12 - These may be the same or different, but it is preferable that they are different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + The compound PIa(HA) is formed by replacing it with PIa(HA) 11 -L1-A 12 In H), A 12 The acid dissociation constant a2, which originates from the acidic site represented by H, is HA 11 It is greater than the acid dissociation constant a1 derived from the acidic site represented by (Ia-1). The preferred values ​​for the acid dissociation constants a1 and a2 are as described above. The acid generated from compound PIa and the compound represented by formula (Ia-1) upon irradiation with active light or radiation is the same. Also, M 11 + M 12 + , A 11 - , A 12 - , and at least one of L1 may have an acid-degradable group as a substituent.

[0252] In formula (Ia-1), M 11 + and M 12 + The organic cations represented by the above M are as follows: + Examples of organic cations represented by the following are given.

[0253] A 11 - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group including A. 12 - The monovalent anionic functional group represented by is the anionic moiety A2 mentioned above.- This refers to a monovalent group that includes [the specified element]. A 11 - and A 12 - The monovalent anionic functional group represented by is preferably a monovalent anionic functional group containing any of the anionic moieties of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) described above, and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). 11 - Among the monovalent anionic functional groups represented by (AX-1) to (AX-3), it is preferable that the monovalent anionic functional group is represented by any of the formulas (AX-1) to (AX-3). 12 - Among the monovalent anionic functional groups represented by (BX-1) to (BX-7), a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is preferred, and a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is more preferred.

[0254] [ka]

[0255] In formulas (AX-1) to (AX-3), R A1 and R A2 Each of these independently represents a monovalent organic group. * represents a bond position. R A1 The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0256] R A2 The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0257] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, or perfluoroalkyl groups being more preferred.

[0258] In equations (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. While the substituents are not particularly limited, fluorine atoms or cyano groups are preferred, with fluorine atoms being more preferred. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Furthermore, if the carbon atom at the bonding position in the alkyl group has a substituent, it is also preferable that the substituent is not a fluorine atom or a cyano group. Here, the carbon atom at the bonding position in the alkyl group is, for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to the -CO- explicitly stated in the formula of the alkyl group; in the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to the -SO2- explicitly stated in the formula of the alkyl group; and in the case of formula (BX-6), the carbon atom directly bonded to the N explicitly stated in the formula of the alkyl group. - This refers to carbon atoms that are directly bonded to it. The alkyl group described above may have a carbon atom substituted with a carbonyl carbon.

[0259] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents include fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), cyano groups, alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), and fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups are more preferred.

[0260] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited and may include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), and divalent aliphatic heterocyclic group (having at least one N, O, S, or Se atom in the ring structure, which may be 5 to 15 carbon atoms). Examples include 10-membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic heterocyclic groups (5-10 membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic hydrocarbon ring groups (6-10 membered rings, and even more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms) are preferred. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0261] In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1).

[0262] [ka]

[0263] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111 The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -NH-, -O-, -SO-, -SO2-, optionally substituted alkylene groups (preferably having 1 to 6 carbon atoms, and may be linear or branched), optionally substituted cycloalkylene groups (preferably having 3 to 15 carbon atoms), optionally substituted aryl groups (preferably having 6 to 10 carbon atoms), and divalent linking groups formed by combining several of these. The substituent is not particularly limited and includes, for example, halogen atoms. p represents an integer between 0 and 3, preferably an integer between 1 and 3. v represents an integer, either 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. In particular, Xf1 and Xf2 are preferably independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. It is especially preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the connection position. L in equation (Ia-1) 11 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 The side joint (*) is A in equation (Ia-1). 12 - It is preferable that it be bonded with.

[0264] - Compounds represented by formulas (Ia-2) to (Ia-4) - Next, we will explain the compounds represented by formulas (Ia-2) to (Ia-4).

[0265] [ka]

[0266] In equation (Ia-2), A 21a - and A 21b - Each of these independently represents a monovalent anionic functional group. Here, A 21a - and A 21b - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 21a - and A 21b -The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. Here, A 22 - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent linking group containing A. 22 - Examples of divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below include the divalent anionic functional groups represented by the formulas (BX-8) to (BX-11).

[0267] [ka]

[0268] M 21a + M 21b + , and M 22 + Each of these independently represents an organic cation. 21a + M 21b + , and M 22 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 21 and L 22 Each of these independently represents a divalent organic group.

[0269] In the above equation (Ia-2), M 21a + M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, which is obtained by substituting A, 22 The acid dissociation constant a2, which originates from the acidic site represented by H, is A21a Acid dissociation constants a1-1 and A derived from H 21b It is greater than the acid dissociation constant a1-2, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 mentioned above. Note A 21a - and A 21b - They may be the same or different from each other. 21a + M 21b + , and M 22 + They may be the same or different from one another. M 21a + M 21b + M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of these may have an acid-degradable group as a substituent.

[0270] In equation (Ia-3), A 31a - and A 32 - Each of these independently represents a monovalent anionic functional group. 31a - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - This is synonymous with the same thing, and the preferred embodiment is also the same. A 32 - The monovalent anionic functional group represented by is the anionic moiety A2 described above. - This refers to a monovalent group containing A. 32 -The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - represents a divalent anionic functional group. Here, A 31b - The divalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a divalent linking group containing A. 31b - Examples of divalent anionic functional groups represented by the formula (AX-4) shown below include the divalent anionic functional group represented by the formula (AX-4).

[0271] [ka]

[0272] M 31a + M 31b + , and M 32 + Each of these independently represents a monovalent organic cation. 31a + M 31b + , and M 32 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 31 and L 32 Each of these independently represents a divalent organic group.

[0273] In the above equation (Ia-3), M 31a + M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, which is obtained by substituting A, 32 The acid dissociation constant a2, which originates from the acidic site represented by H, is A31a Acid dissociation constants a1-3 and A, derived from the acidic site represented by H. 31b It is larger than the acid dissociation constant a1-4, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 mentioned above. Note A 31a - and A 32 - They may be the same or different from each other. Also, M 31a + M 31b + , and M 32 + They may be the same or different from one another. M 31a + M 31b + M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of these may have an acid-degradable group as a substituent.

[0274] In equation (Ia-4), A 41a - , A 41b - , and A 42 - Each of these independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - It is synonymous with A. 42 - The definition of a monovalent anionic functional group represented by is A in formula (Ia-3) above. 32 - This is synonymous with the same thing, and the preferred embodiment is also the same. M 41a+ M 41b + , and M 42 + Each of these independently represents an organic cation. 41a + M 41b + , and M 42 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 41 This represents a trivalent organic group.

[0275] In the above equation (Ia-4), M 41a + M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, which is obtained by substituting A, 42 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 41a Acid dissociation constants a1-5 and A, derived from the acidic site represented by H. 41b It is larger than the acid dissociation constant a1-6, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-5 and a1-6 correspond to the acid dissociation constant a1 mentioned above. Note A 41a - , A 41b - , and A 42 - They may be the same or different from each other. Also, M 41a + M 41b + , and M 42 + They may be the same or different from one another. M 41a + M 41b + M 42 + , A 41a - , A 41b- , A 42 - , and L 41 At least one of these may have an acid-degradable group as a substituent.

[0276] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is not particularly limited and includes, for example, -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent organic groups formed by combining several of these. In the above -NR-, R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0277] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is preferably, for example, the divalent organic group represented by the following formula (L2).

[0278] [ka]

[0279] In equation (L2), q represents an integer between 1 and 3. * indicates the joining position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0280] L A This represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6 to 10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0281] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Herein, Ph is a phenylene group which may have substituents, and is preferably a 1,4-phenylene group. The substituent is not particularly limited, but alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), or alkoxycarbonyl groups (for example, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are preferred). L in equation (Ia-2) 21 and L 22 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-2). 21a - and A 21b - It is preferable that it be bonded with. L in equation (Ia-3) 31 and L 32 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-3). 31a - and A 32 - It is preferable that it be bonded with.

[0282] - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5).

[0283] [ka]

[0284] In equation (Ia-5), A 51a - , A 51b -, and A 51c - Each of these independently represents a monovalent anionic functional group. Here, A 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent linking group containing A. 22 - Examples of divalent anionic functional groups represented by the above formulas (BX-8) to (BX-11) include divalent anionic functional groups selected from the group.

[0285] M 51a + M 51b + M 51c + M 52a + , and M 52b + Each of these independently represents an organic cation. 51a + M 51b + M 51c + M 52a + , and M 52b+ The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 51 and L 53 Each of these independently represents a divalent organic group. 51 and L 53 As a divalent organic group represented by the above formula (Ia-2), L 21 and L 22 This is synonymous with the same thing, and the preferred embodiment is also the same. L 52 L represents a trivalent organic group. 52 As a trivalent organic group represented by the above formula (Ia-4), L 41 This is synonymous with the same thing, and the preferred embodiment is also the same.

[0286] In the above equation (Ia-5), M 51a + M 51b + M 51c + M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, which is obtained by substituting A, 52a Acid dissociation constants a2-1 and A, which originate from the acidic site represented by H. 52b The acid dissociation constant a2-2, which originates from the acidic site represented by H, is A 51a Acid dissociation constants a1-1 and A derived from H. 51b Acid dissociation constants a1-2 and A originate from the acidic site represented by H. 51c This is greater than the acid dissociation constant a1-3 derived from the acidic site represented by H. Note that acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 mentioned above, and acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 mentioned above. Note A 51a - , A 51b - , and A 51c - They may be the same or different from each other. Also, A52a - and A 52b - They may be the same or different from each other. 51a + M 51b + M 51c + M 52a + , and M 52b + They may be the same or different from one another. M 51b + M 51c + M 52a + M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of these may have an acid-degradable group as a substituent.

[0287] (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids.

[0288] Definition of structural site X in compound (II), and A1 - and M1 + The definition is the definition of structural site X in compound (I) described above, and A1 - and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0289] In the above compound (II), the above cation moiety M1 in the above structural moiety X + to H+ In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic site represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII corresponds to "one A1 - The acid dissociation constant when a compound having "one HA1" is formed, and "one A1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0290] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. - , and two or more of the above M1 + These may be the same or different.

[0291] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably, for example, a site that can electrostatically interact with a proton or a site that contains an electron-containing functional group. Examples of functional groups that can electrostatically interact with protons, or that have electrons, include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0292] [ka]

[0293] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0294] Compound (II) is not particularly limited, but examples include compounds represented by the following formulas (IIa-1) and (IIa-2).

[0295] [ka]

[0296] In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) mentioned above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 61a + and M 61b + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-1), L 61 and L 62 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0297] In formula (IIa-1), R 2X R represents a monovalent organic group. 2X The monovalent organic group represented by is not particularly limited and includes alkyl groups (preferably having 1 to 10 carbon atoms, which may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms).2X The -CH2- contained in the alkyl, cycloalkyl, and alkenyl groups in the monovalent organic group represented by may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. The alkylene group, the cycloalkylene group, and the alkenylene group may have substituents. The substituents are not particularly limited, but examples include halogen atoms (preferably fluorine atoms).

[0298] In the above equation (IIa-1), M 61a + and M 61b + The organic cation represented by H + In compound PIIa-1, which is obtained by substituting A, 61a Acid dissociation constants a1-7 and A, derived from the acidic site represented by H. 61b The acid dissociation constants a1-8, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 61a + and M 61b + to H + Compound PIIa-1, which is obtained by replacing HA, 61a -L 61 -N(R 2X )-L 62 -A 61b H is the corresponding element. Furthermore, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with active light or radiation are the same. M 61a + M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R 2X At least one of these may have an acid-degradable group as a substituent.

[0299] In the above equation (IIa-2), A 71a - , A 71b - , and A 71c - These are A in equation (Ia-1) mentioned above. 11 - This is synonymous with the same thing, and the preferred embodiment is also the same. 71a + M 71b + , and M 71c + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-2), L 71 , L 72 , and L 73 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0300] In the above equation (IIa-2), M 71a + M 71b + , and M 71c + The organic cation represented by H + In compound PIIa-2, which is obtained by substituting A, 71a Acid dissociation constants a1-9 and A, derived from the acidic site represented by H. 71b Acid dissociation constants a1-10 and A originate from the acidic site represented by H. 71c The acid dissociation constants a1-11, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 71a + M 71b + , and M 71c + to H + Compound PIIa-2, which is obtained by replacing HA, 71a -L 71 -N(L 73 -A 71c H)-L72 -A 71b H is the corresponding element. Furthermore, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with active light or radiation are the same. M 71a + M 71b + M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 , and L 73 At least one of these may have an acid-degradable group as a substituent.

[0301] Examples of non-cationic sites that compound (I) and compound (II) may possess are given below.

[0302] [ka]

[0303] [ka]

[0304] The following are specific examples of photoacid generators, but are not limited to these. Me represents a methyl group.

[0305] [ka]

[0306] [ka]

[0307] [ka]

[0308] [ka]

[0309] [ka]

[0310] When the composition of the present invention contains a photoacid generator (B), its content is not particularly limited, but it is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the composition, in that the cross-sectional shape of the formed pattern becomes more rectangular. The above content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition. The photoacid generator (B) may be used alone or in combination of two or more types.

[0311] <Acid diffusion control agent (C)> The composition of the present invention may contain an acid diffusion control agent. The acid diffusion control agent traps the acid generated from photoacid generators during exposure and acts as a quencher to suppress the reaction of acid-degradable resins in unexposed areas due to excess generated acid. The type of acid diffusion control agent is not particularly limited and includes, for example, basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation. Specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824; and specific examples of basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation include those described in paragraph

[0164] of International Publication No. 2020 / 066824. Specific examples of onium salt compounds (CDs) that are relatively weak acids with respect to photoacid generators include, for example, those described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337.

[0312] In addition to the above, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents.

[0313] If the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (total if there are multiple types) is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass, relative to the total solid content of the resist composition. In the resist composition, one acid diffusion control agent may be used alone, or two or more may be used in combination.

[0314] <Hydrophobic resin (D)> The composition of the present invention may further contain a hydrophobic resin different from resin (A). Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0315] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. The hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0316] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition.

[0317] <Surfactant (E)> The composition of the present invention may contain a surfactant. The inclusion of a surfactant results in superior adhesion and the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0318] These surfactants may be used individually or in combination of two or more types.

[0319] If the composition of the present invention contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition.

[0320] <Solvent (F)> The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0321] Combining the solvent and resin described above is preferable in terms of improving the coatability of the resist composition and reducing the number of development defects in the pattern. The solvent described above has a good balance of solubility, boiling point, and viscosity with the resin described above, which can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein by reference.

[0322] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0323] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the coatability of the resist composition.

[0324] Furthermore, "solid content" refers to all components other than the solvent, and as mentioned above, it refers to the components that form a photosensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the mass of the components other than the solvent, relative to the total mass of the composition of the present invention. "Total solids" refers to the total mass of the components of the composition of the present invention, excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent, as described above, and may be solid or liquid at 25°C, for example.

[0325] <Other additives> The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0326] The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developing solutions.

[0327] The compositions described herein are suitably used as photosensitive compositions for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0328] The present invention provides a method for producing a photosensitive or radiation-sensitive resin composition (hereinafter also referred to as "the method for producing the composition of the present invention" or "the method for producing the composition"), as described above, and includes a method for producing the salt (P), and is a method for producing a photosensitive or radiation-sensitive resin composition containing the salt (P) as a compound that generates acid upon irradiation with active light or radiation. The composition can be manufactured, for example, by mixing a compound that generates acid upon irradiation with active light or radiation in the photosensitive or radiation-sensitive resin composition, which is manufactured by the above-mentioned method for manufacturing salt (P), with each component that the photosensitive or radiation-sensitive resin composition may contain.

[0329] A high A value, calculated using the following formula (1), indicates that the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition is high, which is effective in reducing photon shot noise. The A value represents the EUV light and electron beam absorption efficiency of the mass percentage of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value of 0.120 or higher is preferred. There is no particular upper limit, but if the A value is too high, the EUV light and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result it becomes difficult to obtain a good pattern shape. Therefore, 0.240 or lower is preferred, and 0.220 or lower is more preferred.

[0330] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from the total solids in the photosensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition. For example, if the resist composition contains an acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-degradable resin, the photoacid generator, and the acid diffusion control agent constitute the solid content. In other words, the total atoms of the total solid content refer to the sum of the total atoms derived from the resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the total hydrogen atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent to the sum of the total atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent.

[0331] The A value can be calculated by determining the atomic ratio of the constituent components if the structure and content of the total solid components in the resist composition are known. Even if the constituent components are unknown, the atomic ratio can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.

[0332] <Method for forming patterns on photosensitive or radiation-sensitive films> The procedure for a pattern formation method using the above composition is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition produced by the method for producing an active photosensitive or radiation-sensitive resin composition. Step 2: Exposing the above-mentioned photosensitive or radiation-sensitive film. Step 3: Developing the exposed photosensitive or radiation-sensitive film using a developer. The following details the steps for each of the above processes.

[0333] (Step 1: Actinic ray-sensitive or radiation-sensitive film formation step) Step 1 is a step of forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition produced by the method for producing the active photosensitive or radiation-sensitive resin composition.

[0334] A method for forming an active photosensitive or radiation-sensitive film (preferably a resist film) on a substrate using an active photosensitive or radiation-sensitive resin composition produced by a method for producing an active photosensitive or radiation-sensitive resin composition includes, for example, a method of coating the composition of the present invention onto a substrate. Furthermore, it is preferable to filter the composition of the present invention before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0335] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred as the coating method. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the composition of the present invention, the substrate may be dried to form a photosensitive or radiation-sensitive film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed beneath the photosensitive or radiation-sensitive film.

[0336] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0337] The thickness of the photosensitive or radiation-sensitive film is not particularly limited, but 10 to 120 nm is preferred in order to form finer patterns with higher precision. In particular, when using EUV exposure, 10 to 65 nm is more preferred for the thickness of the photosensitive or radiation-sensitive film, and 15 to 50 nm is even more preferred. When using ArF immersion exposure, 10 to 120 nm is more preferred for the thickness of the photosensitive or radiation-sensitive film, and 15 to 90 nm is even more preferred.

[0338] Furthermore, a topcoat may be formed on the upper layer of the photosensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition is not mixed with the photosensitive or radiation-sensitive film and can be uniformly applied to the upper layer of the photosensitive or radiation-sensitive film. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods, for example, a topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Publication No. 2013-61648, on a photosensitive or radiation-sensitive film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be included in the resist composition. The top coat may also preferably contain a compound comprising at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0339] (Step 2: Exposure process) Step 2 is the step of exposing a photosensitive or radiation-sensitive film. One method of exposure is to irradiate the formed photosensitive or radiation-sensitive film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, with wavelengths of 250 nm or less being preferred, more preferably 220 nm or less, and far ultraviolet light with wavelengths of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams being particularly preferred.

[0340] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also called post-exposure baking.

[0341] (Process 3: Development process) Step 3 is the process of developing the exposed photosensitive or radiation-sensitive film using a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0342] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and letting it stand for a certain period of time (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0343] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0344] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0345] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, based on the total amount of the developer.

[0346] (Other processes) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0347] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse solution.

[0348] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0349] The rinsing process is not particularly limited and can be performed in any way, for example, by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), by immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or by spraying rinsing solution onto the surface of the substrate (spray method). Furthermore, the pattern formation method may include a heating step (Post Bake) after the rinsing step. This step removes any developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0350] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask. Dry etching is preferably performed using oxygen plasma etching.

[0351] The compositions of the present invention and the various materials used in the pattern-forming methods of this specification (e.g., solvents, developers, rinses, anti-reflective film-forming compositions, topcoat-forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0352] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0353] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the constituent materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0354] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred.

[0355] In organic processing solutions such as rinsing solutions, a conductive compound may be added to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. For chemical piping, various types of piping can be used, such as SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating can be used.

[0356] <Method of manufacturing electronic devices> This specification also relates to a method for manufacturing an electronic device, including the pattern forming method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic devices described herein include those mounted in electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0357] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0358] For the salt (P) synthesized in the following synthesis example, X was measured as follows.

[0359] (potentiometric titration method) Prepare a 0.001 N silver nitrate aqueous solution by diluting a commercially available 0.01 N silver nitrate aqueous solution 10-fold with ion-exchanged water. Weigh 100 mg of the product containing salt (P), dissolve it in 60 ml of a mixed solvent of THF and water (THF / water = 54 / 6 volume ratio) to obtain a sample solution. Using the 0.001 N silver nitrate aqueous solution prepared above, measure the titration volumes of only the above mixed solvent and the above sample solution with an automatic titrator (AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). From the obtained titration volume results, the molar ratio X (mol%) of salt (I) to salt (P) was calculated using the above formula (1) and formula (2). The above molar ratio X indicates the residual ratio (mol%) of salt (I) to 1 mol of salt (P). The predetermined standard (predetermined amount) of X was set to 0.5 mol%. As the titer of the above silver nitrate aqueous solution, 1 obtained by measuring by the above method was used.

[0360] For the salt (P) synthesized in the following synthesis examples, the concentration Y was measured as follows.

[0361] (Method for measuring concentration Y) (A) Preparation of calibration curve Prepare solution A by dissolving 1.6 g of the internal standard substance 1,3,5-trimethoxybenzene in 100 ml of acetonitrile. Add 10 ml of solution A to 0.07 g of the reference lot of salt (P), and dilute to 20 ml with acetonitrile to prepare solution B1. Change the amount of salt (P) to 0.08 g and 0.09 g respectively, and prepare solution B2 and B_{3} in the same manner. Perform HPLC measurement on solutions B1 to B_{3} under the following conditions, and for each, calculate the peak area values S1 to S3 of the cations of salt (P) with respect to the peak area value of the internal standard substance. Repeat the same measurement 3 times, and calculate the average value S 1AVE ~S 3AVE Calculate. Prepare a calibration curve from the sample concentration (g / ml) of each solution and S 1AVE ~S 3AVE (B) Measurement of sample solution <HPLC measurement conditions> Measuring device: Waters HPLC system 2695 (manufactured by Waters) Column: Shim-pack CLC-ODS (6.0×150 mm) Eluent: Acetonitrile / 0.05M ammonium acetate aqueous solution Column temperature: 40℃ Flow rate: 1ml / min Sample injection volume: 5 μl Detection wavelength: 254nm

[0362] For each of the salts (P) in the following synthesis examples 1 to 20, a reference lot was prepared as described below.

[0363] (B) Concentration Y measurement Prepare solution A by dissolving 1.6 g of the internal standard substance 1,3,5-trimethoxybenzene in 100 ml of acetonitrile. Add 10 ml of solution A to 0.08 g of the product lot to be measured, which contains salt (P), and dilute with acetonitrile to 20 ml to prepare solution C1. Perform HPLC measurement of solution C1 under the same conditions as above and calculate the peak area value SC of the salt (P) cation relative to the peak area value of the internal standard substance. Repeat the measurement of the same sample solution two more times and calculate the average value SC. AVE Calculate the above SC. AVE From the calibration curve described above, the corresponding sample concentration KC (g / ml) was calculated. The concentration Y (mass%) of salt (P) in the product containing salt (P) in the target lot was calculated from formula (3) above.

[0364] For the salt (P) synthesized in the following synthesis example, the concentration Z was measured as follows.

[0365] (Method for measuring concentration Z) (A) Calibration curve creation Prepare solution A by dissolving 12 mg of rhodamine base (Sigma-Aldrich) (compound C) in 200 ml of acetonitrile. Prepare solution B by dissolving 50 mg of tosylic acid (compound D) in 200 ml of acetonitrile. Prepare solution C by diluting 5 ml of solution B 40 times with acetonitrile. Prepare solution D1 by placing 2 ml of solution A and 2 ml of solution C into a 10 ml volumetric flask and diluting them to 10 ml with acetonitrile. Measure the ultraviolet-visible absorption spectrum of solution D1 using a "UV-1800" (Shimadzu Corporation) and measure the absorbance Abbs at the maximum absorption wavelength of 556 nm.D1 Obtain solution A. Similarly, prepare solutions D2, D3, and D4 by varying the amount of solution C mixed with solution A. The obtained UV-Vis absorption spectra of D2, D3, and D4 were similarly measured, and Abs D2 , Abs D3 , Abs D4 To obtain the desired result, as a blank, take 2 ml of solution A into a 10 ml volumetric flask and dilute it with acetonitrile to prepare solution E. Similarly, measure the ultraviolet-visible absorption spectrum of solution E and measure the absorbance Abbs at a wavelength of 556 nm. E To obtain. Abs obtained above D1 ~Abs D4 Regarding Abs E The difference is calculated, and the obtained results are analyzed using Abs. DE1 ~Abs DE4 The molar concentrations of tosylic acid in D1, D2, D3, and D4, and the resulting Abs DE1 ~Abs DE4 A calibration curve is created between the molar concentration of tosylic acid and its absorbance at a wavelength of 556 nm.

[0366] (B) Measurement of concentration Z Prepare solution A by dissolving 12 mg of rhodamine base (Sigma-Aldrich) (compound C) in 200 ml of acetonitrile. Measure out 0.05 g of the product containing salt (P), add 2 ml of solution A, and then add acetonitrile to dilute to 10 ml to prepare solution F. As a blank, take 2 ml of solution A into a 10 ml volumetric flask and dilute with acetonitrile to prepare solution E. Measure the ultraviolet-visible absorption spectra of solutions F and E in the same manner as when creating the calibration curve, and measure the absorbance at a wavelength of 556 nm (Abs). F and Abs E Obtain these differences Abs FE =Abs F -Abs E Using the above formula (4), the molar concentration T (mol / l) of tosylic acid corresponding to the calibration curve created above was calculated. Using the above formula (4), the concentration Z (ppm) of residual acid in terms of tosylic acid contained in the product containing salt (P) was calculated. In equation (4), MT (g / mol) was calculated using the molecular weight of tosylic acid, which is 172.20, and LB was calculated using the solvent volume of solution F, which is 0.01 liters. The concentration Z of the residual acid contained in the product containing the above salt (P) is the concentration in terms of tosylic acid (compound D).

[0367] The prescribed standard (specified amount) for Z was set at 100 ppm.

[0368] [Example of combination] In each of the synthesis examples below, for each type of salt (P), three series lots were prepared: a-1 to a-3 in which all of X, Y, and Z were evaluated; a-1 to b-3 in which only X and Z were evaluated; a-1 to c-3 in which only X and Y were evaluated; and, as a comparative example, a-1 to R-3 in which none of X, Y, and Z were evaluated. Note that the three series lots (b-1 to b-3) that evaluate only X and Z, and the three series lots (c-1 to c-3) that evaluate only X and Y, should be interpreted as reference examples.

[0369] <Synthesis Example 1: Synthesis of Salt (P) (Salt B1)>

[0370] [ka]

[0371] <Preparation of a reference lot (concentration Y measurement)> Salt C1 (5.9g), methylene chloride (100g), and water (100g) were mixed, then salt A1 (6.5g) was added and the mixture was stirred at room temperature (25°C) for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100g of 0.1N hydrochloric acid and five times with 100g of water, and the organic layer was concentrated under reduced pressure. X was calculated from the obtained crude product using the above method and was found to be 0.32 mol%. 105g of methanol was added to the crude product to dissolve it, and 35g of water was added while stirring. The precipitated solid was filtered and collected. 30g of tert-butyl methyl ether and 30g of hexane were added to the obtained solid and stirred, then filtered. The obtained solid was dried under reduced pressure for 8 hours. A portion of the obtained solid was dissolved in biacetone. 1H NMR measurement was performed, and since no hexane peak was observed, the solid content value was determined from the integration ratio with residual tert-butyl methyl ether to be 99.4%. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 6 ppm. The obtained solid was designated as Lot 1-a-0. The concentration of the reference lot was set to 99.4% as described above.

[0372] <Synthesis of a-1 (Lot 1-a-1)> Salt C1 (5.9 g), 100 g of methylene chloride, and 100 g of water were mixed, then salt A1 (6.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, 1 When H NMR measurement was performed, the cation / anion ratio was 1.02 / 1.00. When X was calculated for the obtained crude product by the above method, it was 1.8 mol%. As a purity improvement measure, 105 g of methanol was added to the crude product and dissolved, and 35 g of water was added while stirring, and crystals precipitated. The crystals were collected by filtration and dried under reduced pressure for 5 hours. A part of the obtained crystals was dissolved in deuterated acetone, 1 When H NMR measurement was performed, the solid content value was determined from the integration ratio with residual methanol to be 99.8%. When X, Y, and Z were measured for the dried crystals, X was 0.18 mol%, Y was 98.0%, and Z was 9 ppm. The obtained crystals were designated as Lot 1-a-1. In Table 1 described later, in Synthesis Example 1, Salt B1, and the item of "a", the above values (X is 0.18 mol%, Y is 98.0%, and Z is 9 ppm) were respectively described in the columns of X, Y, and Z for Lot 1.

[0373] <Synthesis of a-2 (Lot 1-a-2)> Salt C(5.9 g), 100 g of methylene chloride, and 100 g of water were mixed, then salt A1 (6.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 0. N hydrochloric acid and three times with water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, 1When performing \(^1H\) NMR measurement, the cation / anion ratio was 1.02 / 1.00. When calculating X for the obtained crude product by the above method, it was 0.28 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 97.5%. When measuring X, Y, and Z for the dried solid, X was 0.28 mol%, Y was 96.4%, and Z was 10 ppm. The obtained solid was designated as Lot 1-a-2. In Table 1 described later, in Synthesis Example 1, Salt B1, item “a”, the above values (X is 0.28 mol%, Y is 96.4%, Z is 10 ppm) are respectively described in the columns of X, Y, and Z for Lot 2.

[0374] <Synthesis of a-3 (Lot 1-a-3)> Lot 1-a-3 was synthesized by the same method as Lot 1-a-1. When measuring X, Y, and Z for Lot 1-a-3, X was 0.20 mol%, Y was 98.2%, and Z was 12 ppm. In Table 1 described later, in Synthesis Example 1, Salt B1, item “a”, the above values (X is 0.20 mol%, Y is 98.2%, Z is 12 ppm) are respectively described in the columns of X, Y, and Z for Lot 3. Similarly for Synthesis Examples 2 to 20, X, Y, and Z are respectively described in Table 1.

[0375] <Synthesis of b-1 (Lot 1-b-1)> Lot 1-b-1 was synthesized by the same method as above. X of the dried solid (Lot 1-b-1) was 0.23 mol% and Z was 12 ppm. Y was not calculated, and 1 99.7% calculated from \(^1H\) NMR measurement was taken as the solid content. In Table 1 described later, in Synthesis Example 1, Salt B1, item “b”, the above values (X is 0.23 mol%, Z is 12 ppm) are respectively described in the columns of X and Z for Lot 1.

[0376] <Synthesis of b-2 (Lot 1-b-2) and synthesis of b-3 (Lot 1-b-3)> Lot 1-b-2 and Lot 1-b-3 were synthesized by the same method as described above, respectively. For Lot 1-b-2, X was 0.15 mol% and Z was 21 ppm. In Table 1 described later, in Synthesis Example 1, Salt B1, under the item of "b", the above values (X is 0.15 mol%, Z is 21 ppm) are respectively described in the columns of X and Z for Lot 2. For Lot 1-b-3, X was 0.29 mol% and Z was 16 ppm. In Table 1 described later, in Synthesis Example 1, Salt B1, under the item of "b", the above values (X is 0.29 mol%, Z is 16 ppm) are respectively described in the columns of X and Z for Lot 3. Similarly for Synthesis Examples 2 to 20, X and Z are respectively described in Table 1. Lot 1-b-2 1 [[ID=十七]]<Regarding the solid content calculated from 1H NMR measurement, 99.1% was used as the solid content, and similarly for Lot 1-b-3, 98.2% was used as the solid content.

[0377] <Synthesis of c-1 (Lot 1-c-1)> Lot 1-c-1 was synthesized by the same method as described above. For the solid (Lot 1-c-1) after drying, X was 0.24 mol% and Y was 98.4%. Z was not calculated. In Table 1 described later, in Synthesis Example 1, Salt B1, under the item of "c", the above values (X is 0.24 mol%, Y is 98.4%) are respectively described in the columns of X and Y for Lot 1.

[0378] <Synthesis of c-2 (Lot 1-c-2) and synthesis of c-3 (Lot 1-c-3)> Lot 1-c-2 and Lot 1-c-3 were synthesized by the same method as described above, respectively. For Lot 1-c-2, X was 0.16 mol% and Y was 99.0%. In Table 1 described later, in Synthesis Example 1, Salt B1, under the item of "c", the above values (X is 0.16 mol%, Y is 99.0%) are respectively described in the columns of X and Y for Lot 2. For Lot 1-c-3, X was 0.12 mol% and Y was 98.5%. In Table 1 described below, in Synthesis Example 1, Salt B1, and the item "c", enter the above values (X is 0.12 mol% and Y is 98.5%) in the columns for X and Y of Lot 3 respectively. Similarly, for Synthesis Examples 2 to 20, enter X and Y in Table 1 respectively.

[0379] <Synthesis of R-1 (Lot 1-R-1), Synthesis of R-2 (Lot 1-R-2), and Synthesis of R-3 (Lot 1-R-3)> Mix 5.9 g of Salt C1, 100 g of methylene chloride, and 100 g of water, then add 6.5 g of Salt A1 and stir at room temperature for 30 minutes. After removing the aqueous layer, wash the organic layer once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and concentrate the organic layer under reduced pressure. Dissolve a part of the obtained crude product in heavy acetone, <​​​​​​​​​​​​​​​​​​​​​​​​​​Salt C2 (4.9 g), 100 g of methylene chloride, and 100 g of water were mixed, and then Salt A2 (4.8 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.10 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. The solid obtained by repeating this three times was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.3%. When X and Z were measured for the solid after drying, X was 0.09 mol% and Z was 10 ppm. The obtained solid was designated as Lot 2-a-0. The concentration of the reference lot was 99.3% as described above.

[0383] <Synthesis of a-1 (Lot 2-a-1)> Salt C2 (4.5 g), 100 g of methylene chloride, and 100 g of water were mixed, and then Salt A2 (4.8 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. When a part of the obtained crude product was dissolved in deuterated acetone and 1 1H NMR measurement was performed, and the cation / anion ratio was 1.01 / 1.00. When X was calculated for the obtained crude product by the above method, it was 1.0 mol%. As a purity improvement measure, the crude product was mixed with Salt C2 (0.045 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1 N hydrochloric acid and five times with 80 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.18 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and 11H NMR measurement was carried out, and the solid content value was determined from the integration ratio with residual diisopropyl ether to be 98.5%. When measurements of X, Y, and Z were performed on the dried solid, X was 0.18 mol%, Y was 99.2%, and Z was 20 ppm. The obtained solid was designated as Lot 2-a-1.

[0384] <Synthesis of a-2 (Lot 2-a-2)> Salt C2 (4.5 g), 100 g of methylene chloride, and 100 g of water were mixed, then Salt A2 (4.8 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 and 1H NMR measurement was carried out. The cation / anion ratio was 1.01 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.13 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When measurements of X, Y, and Z were performed on the dried solid, X was 0.12 mol%, Y was 98.8%, and Z was 650 ppm. The solid was dissolved in 80 g of methylene chloride, the organic layer was washed five times with 80 g of water, and the organic layer was concentrated under reduced pressure. 80 g of diisopropyl ether was added to the residue, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When measurements of X, Y, and Z were performed on the dried solid, X was 0.11 mol%, Y was 98.5%, and Z was 14 ppm. The obtained solid was designated as Lot 2-a-2.

[0385] <Synthesis of a-3 (Lot 2-a-3)> Lot 2-a-3 was synthesized by the same method as Lot 2-a-1. When measurements of X, Y, and Z were performed on Lot 2-a-3, X was 0.24 mol%, Y was 98.2%, and Z was 31 ppm.

[0386] <Synthesis of b-1 (Lot 2-b-1)> Lot 2-b-1 was synthesized by the same method as above. For the dried solid (Lot 2-b-1), X was 0.23 mol% and Z was 24 ppm. Y was not calculated.1 98.6% of the solid content was calculated from the 1H NMR measurement.

[0387] <Synthesis of b-2 (Lot 2-b-2) and synthesis of b-3 (Lot 2-b-3)> Lot 2-b-2 and Lot 2-b-3 were synthesized by the same method as described above. For Lot 2-b-2, X was 0.14 mol% and Z was 44 ppm. For Lot 2-b-3, X was 0.28 mol% and Z was 11 ppm. Lot 2-b-2 1 had a solid content of 97.5% calculated from the 1H NMR measurement. Similarly, Lot 2-b-3 had a solid content of 98.8%.

[0388] <Synthesis of c-1 (Lot 2-c-1)> Lot 2-c-1 was synthesized by the same method as described above. For the solid (Lot 2-c-1) after drying, X was 0.13 mol%, Y was 99.1%. Z was not calculated.

[0389] <Synthesis of c-2 (Lot 2-c-`2) and synthesis of c-3 (Lot 2-c-3)> Lot 2-c-2 and Lot 2-c-3 were synthesized by the same method as described above. For Lot 2-c-2, X was 0.18 mol% and Y was 98.5%. For Lot 2-c-3, X was 0.21 mol% and Y was 99.0%.

[0390] <Synthesis of R-1 (Lot 2-R-1), synthesis of R-2 (Lot 2-R-2), and synthesis of R-3 (Lot 2-R-3)> 4.5 g of Salt C2, 100 g of methylene chloride, and 100 g of water were mixed, and then 4.8 g of Salt A2 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and then the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1When \(^1H\) NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. 100 g of diisopropyl ether was added in bold and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 98.1%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 2-R-1. Lot 2-R-2 and Lot 2-R-3 were synthesized respectively by the same method as above. Lot 2-R-2 1 had a solid content of 99.3% calculated from \(^1H\) NMR measurement. Similarly, Lot 2-R-3 had a solid content of 98.0%.

[0391] <Synthesis of Salt (P) (Salt B3)>

[0392]

Chemical formula

[0393] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C3 (5.6 g), 120 g of methylene chloride, and 120 g of water were mixed, then Salt A3 (8.1 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 120 g of 0.1 N hydrochloric acid and five times with 120 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.14 mol%. 120 g of isopropyl alcohol was added to the crude product and stirred, and then filtered. This was repeated twice, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 99.1%. When X and Z were measured for the dried solid, X was 0.08 mol% and Z was 4 ppm. The obtained solid was designated as Lot 3-a-0. The concentration of the reference lot was set to 99.1% as above.

[0394] [[ID=三十二]]<Synthesis of a-1 (Lot 3-a-1)> 3 (5.6 g) of salt, 120 g of methylene chloride, and 120 g of water were mixed, and then 3 (8.1 g) of salt A was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 120 g of 0.1 N hydrochloric acid and three times with 120 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, and 1 When 1H NMR measurement was performed, the cation / anion ratio was 2.05 / 1.00. When X was calculated for the obtained crude product by the above method, it was 2.1 mol%. As a purity improvement measure, the crude product was mixed with 3 (0.11 g) of salt C, 100 g of methylene chloride, and 100 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.22 mol%. 120 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 When 1H NMR measurement was performed and the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 95.4%. When X, Y, and Z were measured for the dried solid, X was 0.22 mol%, Y was 96.8%, and Z was 10 ppm. The obtained solid was designated as Lot 3-a-1.

[0395] <Synthesis of a-2 (Lot 3-a-2)> 3 (5.6 g) of salt, 120 g of methylene chloride, and 120 g of water were mixed, and then 3 (8.1 g) of salt A was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 120 g of 0.1 N hydrochloric acid and three times with 120 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, and 1 When 1H NMR measurement was performed, the cation / anion ratio was 2.04 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.16 mol%. Since X was sufficiently low, 120 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1When performing \(^{1}H\) NMR measurement and determining the solid content value from the integration ratio with residual diisopropyl ether, it was 97.7%. When measuring X, Y, and Z for the solid after drying, X was 0.16 mol%, Y was 95.2%, and Z was 11 ppm. The obtained solid is designated as Lot 3-a-2.

[0396] <Synthesis of a-3 (Lot 3-a-3)> Lot 3-a-3 was synthesized by the same method as Lot 3-a-2. When measuring X, Y, and Z for Lot 3-a-3, X was 0.19 mol%, Y was 95.7%, and Z was 19 ppm.

[0397] <Synthesis of b-1 (Lot 3-b-1)> Lot 3-b-1 was synthesized by the same method as above. For the solid after drying (Lot 3-b-1), X was 0.15 mol% and Z was 11 ppm. Y was not calculated, 1 The solid content was taken as 96.1% calculated from \(^{1}H\) NMR measurement.

[0398] <Synthesis of b-2 (Lot 3-b-2) and Synthesis of b-3 (Lot 3-b-3)> Lot 3-b-2 and Lot 3-b-3 were each synthesized by the same method as above. For Lot 3-b-2, X was 0.11 mol% and Z was 10 ppm. For Lot 3-b-3, X was 0.20 mol% and Z was 16 ppm. Lot 3-b-2 1 had a solid content of 97.5% calculated from \(^{1}H\) NMR measurement, and similarly, Lot 3-b-3 had a solid content of 99.0%.

[0399] <Synthesis of c-1 (Lot 3-c-1)> Lot 3-c-1 was synthesized by the same method as above. For the solid after drying (Lot 3-c-1), X was 0.20 mol% and Y was 97.4%. Z was not calculated.

[0400] <Synthesis of c-2 (Lot 3-c-2) and Synthesis of c-3 (Lot 3-c-3)> Lots 3-c-2 and 3-c-3 were synthesized by the same method as described above, respectively. For Lot 3-c-2, X was 0.17 mol% and Y was 95.8%. For Lot 3-c-3, X was 0.12 mol% and Y was 96.9%.

[0401] <Synthesis of R-1 (Lot 3-R-1), Synthesis of R-2 (Lot 3-R-2), and Synthesis of R-3 (Lot 3-R-3)> 5.6 g of Salt C3, 120 g of methylene chloride, and 120 g of water were mixed, and then 8.1 g of Salt A3 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 120 g of 0.1 N hydrochloric acid and three times with 120 g of water, and then concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 and when 1H NMR measurement was carried out, the cation / anion ratio was 2.05 / 1.00. 120 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was performed. When the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 97.5%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 3-R-1. Lots 3-R-2 and 3-R-3 were synthesized by the same method as described above, respectively. Lot 3-R-2 1 had a solid content of 98.7% calculated from 1H NMR measurement, and similarly, Lot 3-R-3 had a solid content of 96.8%.

[0402] <Synthesis Example 4 Synthesis of Salt (P) (Salt B4)>

[0403]

Chemical Formula

[0404] [[ID=##]] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C4 (8.0 g), 200 g of methylene chloride, and 200 g of water were mixed, and then Salt A4 (20.0 g) was added. The mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and ten times with 200 g of water, and then the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.11 mol%. 120 g of diisopropyl ether was added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.2%. When X and Z were measured for the dried solid, X was 0.10 mol% and Z was 5 ppm. The obtained solid was designated as Lot 4-a-0. The concentration of the reference lot was 99.2% as described above.

[0405] <Synthesis of a-1 (Lot 4-a-1)> Salt C4 (7.4 g), 200 g of methylene chloride, and 200 g of water were mixed, and then Salt A4 (20.0 g) was added. The mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and three times with 200 g of water, and then the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone and 1 1H NMR measurement was carried out, and the cation / anion ratio was 2.96 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.14 mol%. Since X was sufficiently low, 200 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 97.3%. When X, Y, and Z were measured for the dried solid, X was 0.12 mol%, Y was 96.9%, and Z was 18 ppm. The obtained solid was designated as Lot 4-a-1.

[0406] <Synthesis of a-2 (Lot 4-a-2)> Salt C4 (7.4 g), 200 g of methylene chloride, and 200 g of water were mixed, and then Salt A4 (20.0 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and three times with 200 g of water, and then the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 3.10 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.93 mol%. As a measure to improve purity, the crude product was mixed with Salt C4 (0.070 g), 160 g of methylene chloride, and 160 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 160 g of 0.1 N hydrochloric acid and five times with 160 g of water, and then the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.10 mol%. 200 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was carried out. When the solid content value was determined from the integral ratio with residual diisopropyl ether, it was 97.6%. When X, Y, and Z were measured for the dried solid, X was 0.10 mol%, Y was 97.2%, and Z was 10 ppm. The obtained solid was designated as Lot 4-a-2.

[0407] <Synthesis of a-3 (Lot 4-a-3)> Lot 4-a-3 was synthesized by the same method as Lot 4-a-1. When X, Y, and Z were measured for Lot 4-a-3, X was 0.24 mol%, Y was 96.6%, and Z was 9 ppm.

[0408] <Synthesis of b-1 (Lot 4-b-1)> Lot 4-b-1 was synthesized by the same method as above. X of the dried solid (Lot 4-b-1) was 0.13 mol% and Z was 18 ppm. Y was not calculated, 1 and 97.7% calculated from 1H NMR measurement was taken as the solid content.

[0409] <Synthesis of b-2 (Lot 4-b-2) and synthesis of b-3 (Lot 4-b-3)> Lots 4-b-2 and 4-b-3 were synthesized by the same method as described above. For Lot 4-b-2, X was 0.17 mol% and Z was 35 ppm. For Lot 4-b-3, X was 0.14 mol% and Z was 10 ppm. Lot 4-b-2 1 had a solid content of 97.5% calculated from 1H NMR measurement. Similarly, Lot 4-b-3 had a solid content of 98.1%.

[0410] [[ID=​​​​​​​​​​​​​​​​​​​​​1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 97.6%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 4-R-1. Lot 4-R-2 and Lot 4-R-3 were each synthesized by the same method as above. Lot 4-R-2 1 had a solid content of 98.5% calculated from 1H NMR measurement, and similarly, Lot 4-R-3 had a solid content of 97.1%.

[0413] <Synthesis Example 5 Synthesis of Salt (P) (Salt B5)>

[0414]

Chemical Formula

[0415] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C5 (5.0 g), 100 g of methylene chloride, and 100 g of water were mixed, then Salt A5 (6.9 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.11 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was carried out. When the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.0%. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 4 ppm. The obtained solid was designated as Lot 5-a-0. The concentration of the reference lot was set to 99.0% as above.

[0416] <Synthesis of a-1 (Lot 5-a-1)> Salt C5 (5.0 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A5 (6.9 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.99 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.12 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was performed. When the solid content value was determined from the integration ratio with the residual diisopropyl ether, it was 96.6%. When X, Y, and Z were measured for the dried solid, X was 0.11 mol%, Y was 97.8%, and Z was 13 ppm. The obtained solid was designated as Lot 5-a-1.

[0417] <Synthesis of a-2 (Lot 5-a-2)> Salt C5 (5.0 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A5 (6.9 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and three times with 200 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 2.05 / 1.00. When X was calculated for the obtained crude product by the above method, it was 1.02 mol%. As a purity improvement measure, the crude product was mixed with salt C5 (0.050 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1 N hydrochloric acid and five times with 80 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.25 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1When performing \(^1H\) NMR measurement and determining the solid content value from the integration ratio with residual diisopropyl ether, it was 96.8%. When measuring X, Y, and Z for the solid after drying, X was 0.23 mol%, Y was 96.4%, and Z was 10 ppm. The obtained solid is designated as Lot 5-a-2.

[0418] <Synthesis of a-3 (Lot 5-a-3)> Lot 5-a-3 was synthesized by the same method as Lot 5-a-1. When measuring X, Y, and Z for Lot 5-a-3, X was 0.13 mol%, Y was 96.0%, and Z was 21 ppm.

[0419] <Synthesis of b-1 (Lot 5-b-1)> Lot 5-b-1 was synthesized by the same method as above. For the solid after drying (Lot 5-b-1), X was 0.27 mol% and Z was 10 ppm. Y was not calculated. 1 Based on \(^1H\) NMR measurement, 97.3% was taken as the solid content.

[0420] <Synthesis of b-2 (Lot 5-b-2) and Synthesis of b-3 (Lot 5-b-3)> Lot 5-b-2 and Lot 5-b-3 were each synthesized by the same method as above. For Lot 5-b-2, X was 0.13 mol% and Z was 18 ppm. For Lot 5-b-3, X was 0.15 mol% and Z was 33 ppm. Lot 5-b-2 1 Based on \(^1H\) NMR measurement, 96.6% was taken as the solid content, and similarly for Lot 5-b-; 96.7% was taken as the solid content.

[0421] <Synthesis of c-1 (Lot 5-c-1)> Lot 5-c-1 was synthesized by the same method as above. For the solid after drying (Lot 5-c-1), X was 0.19 mol% and Y was 96.6%. Z was not calculated.

[0422] <Synthesis of c-2 (Lot 5-c-2) and Synthesis of c-3 (Lot 5-c-3)> Lots 5-c-2 and 5-c-3 were synthesized by the same method as described above, respectively. For Lot 5-c-2, X was 0.18 mol% and Y was 97.3%. For Lot 5-c-3, X was 0.22 mol% and Y was 97.4%.

[0423] <Synthesis of R-1 (Lot 5-R-1), Synthesis of R-2 (Lot 5-R-2), and Synthesis of R-3 (Lot 5-R-3)> 5.0 g of Salt C5, 100 g of methylene chloride, and 100 g of water were mixed, then 6.9 g of Salt A5 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 2.04 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for five hours. A part of the obtained solid was dissolved in heavy acetone 1 1H NMR measurement was performed, and the solid content value was determined to be 96.2% from the integration ratio with the remaining diisopropyl ether. X, Y, and Z were not calculated. The obtained solid was designated as Lot 5-R-1. Lots 5-R-2 and 5-R-3 were synthesized by the same method as described above, respectively. Lot 5-R-2 1 had a solid content of 97.4% calculated from 1H NMR measurement, and similarly, Lot 5-R-3 had a solid content of 95.4%.

[0424] <Synthesis Example 6 Synthesis of Salt (P) (Salt B6)>

[0425]

Chemical formula

[0426] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C6 (4.0 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A6 (4.3 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.10 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. The solid obtained by repeating this three times was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.5%. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 6 ppm. The obtained solid was designated as lot 6-a-0. The concentration of the reference lot was 99.5% as described above.

[0427] <Synthesis of a-1 (Lot 6-a-1)> C6 (4.0 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A6 (4.3 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, and 1 1H NMR measurement was performed, and the cation / anion ratio was 0.99 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.11 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 98.8%. When X, Y, and Z were measured for the dried solid, X was​​​​​Lots 6-a-2 and 6-a-3 were each synthesized by the same method as Lot 6-a-1. For Lot 6-a-2, X was 0.09 mol%, Y was 98.9%, and Z was 13 ppm. For Lot 6-a-3, X was 0.14 mol%, Y was 99.4%, and Z was 22 ppm.

[0429] <Synthesis of <b-1 (Lot 6-b-1)>> Lot 6-b-1 was synthesized by the same method as above. For the solid after drying (Lot 6-b-1), X was 0.13 mol% and Z was 8 ppm. Y was not calculated, 1 99.0% calculated from 1H NMR measurement was taken as the solid content.

[0430] <Synthesis of <b-2 (Lot 6-b-2)>, and synthesis of <b-3 (Lot 6-b-3)>> Lot 6-b-2 and Lot 6-b-3 were each synthesized by the same method as above. For Lot 6-b-2, X was 0.13 mol% and Z was 14 ppm. For Lot 6-b-3, X was 0.10 mol% and Z was 10 ppm. Lot 6-b-2 1 98.8% calculated from 1H NMR measurement was taken as the solid content, and for Lot 6-b-3 as well, 96.8% was taken as the solid content.

[0431] <Synthesis of <c-1 (Lot 6-c-1)>> Lot 6-c-1 was synthesized by the same method as above. For the solid after drying (Lot 6-c-1), X was​​​​​​​​​​

[0433] <Synthesis of R-1 (Lot 6-R-1), Synthesis of R-2 (Lot 6-R-2), and Synthesis of R-3 (Lot 6-R-3)> 4.0 g of Salt C6, 100 g of methylene chloride, and 100 g of water were mixed, and then 4.3 g of Salt A6 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and then concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, and 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone, and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.5%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 6-R-1. Lot 6-R-2 and Lot 6-R-3 were each synthesized by the same method as described above. Lot 6-R-2 1 [[ID=十五]]had a solid content of 99.9% calculated from 1H NMR measurement, and similarly, Lot 6-R-3 had a solid content of 98.5%.

[0434] <Synthesis Example 7 Synthesis of Salt (P) (Salt B7)>

[0435]

Chemical formula

[0436] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C7 (3.6 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A7 (5.2 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and then the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.35 mol%. 100 g of isopropyl alcohol and 20 g of diisopropyl ether were added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was carried out. Since the peak of diisopropyl ether was not observed, when the solid content value was determined from the integration ratio with residual isopropyl alcohol, it was 99.7%. When X and Z were measured for the dried solid, X was 0.10 mol% and Z was 5 ppm. The obtained solid was designated as lot 7-a-0. The concentration of the reference lot was 99.7% as described above.

[0437] <Synthesis of a-1 (Lot 7-a-1)> Salt C7 (3.6 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A7 (5.2 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and then the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone and 1 1H NMR measurement was carried out, and the cation / anion ratio was 1.01 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.20 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When X, Y, and Z were measured for the dried solid, X was 0.18 mol%, Y was 98.2%, and Z was 310 ppm. The solid was dissolved in 80 g of methylene chloride, the organic layer was washed five times with 80 g of water, and the organic layer was concentrated under reduced pressure. 80 g of diisopropyl ether was added to the residue, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When X, Y, and Z were measured for the dried solid, X was 0.18 mol%, Y was 98.8%, and Z was 10 ppm. The obtained solid was designated as lot 7-a-1.

[0438] <Synthesis of a-2 (Lot 7-a-2)> 7 g of Salt C7, 100 g of methylene chloride, and 100 g of water were mixed, and then 5.2 g of Salt A7 was added. The mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and then concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, 1 and 1H NMR measurement was performed. As a result, the cation / anion ratio was 1.02 / 1.00. When X was calculated for the obtained crude product by the above method, it was 1.0 mol%. As a measure to improve the purity, 75 g of isopropanol was added to the crude product and dissolved, and 25 g of hexane was added while stirring. The precipitated solid was collected by filtration and dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone, 1 and 1H NMR measurement was performed. The solid content value was determined from the integration ratio with residual isopropanol and hexane, and it was 98.4%. When X, Y, and Z were measured for the dried crystals, X was 0.14 mol%, Y was 99.2%, and Z was 13 ppm. The obtained crystals were designated as Lot 7-a-2.

[0439] <Synthesis of a-3 (Lot 7-a-3)> Lot 7-a-3 was synthesized by the same method as Lot 7-a-2. When X, Y, and Z were measured for Lot 7-a-3, X was 0.21 mol%, Y was 98.1%, and Z was 21 ppm.

[0440] <Synthesis of b-1 (Lot 7-b-1)> Lot 7-b-1 was synthesized by the same method as above. For the dried solid (Lot 7-b-1), X was 0.10 mol% and Z was 28 ppm. Y was not calculated, 1 and the solid content was taken as 99.5% calculated from 1H NMR measurement.

[0441] <Synthesis of b-2 (Lot 7-b-2) and Synthesis of b-3 (Lot 7-b-3)> Lot 7-b-2 and Lot 7-b-3 were each synthesized by the same method as above. For Lot 7-b-2, X was 0.25 mol% and Z was 14 ppm. For Lot 7-b-3, X was 0.11 mol% and Z was 10 ppm. Lot 7-b-2 1 had a solid content of 95.8% calculated from 1H NMR measurement, and similarly, Lot 7-b-3 had a solid content of 98.3%.

[0442] <Synthesis of c-1 (Lot 7-c-1)> Lot 7-c-1 was synthesized by the same method as above. For the solid after drying (Lot 7-c-1), X was 0.10 mol% and Y was 99.1%. Z was not calculated.

[0443] <Synthesis of c-2 (Lot 7-c-2) and Synthesis of c-3 (Lot 7-c-3)> Lot 7-c-2 and Lot 7-c-3 were each synthesized by the same method as above. For Lot 7-c-2, X was 0.15 mol% and Y was 97.4%. For Lot 7-c-3, X was 0.28 mol% and Y was 98.6%.

[0444] <Synthesis of R-1 (Lot 7-R-1), Synthesis of R-2 (Lot 7-R-2), and Synthesis of R-3 (Lot 7-R-3)> 3.6 g of Salt C7, 100 g of methylene chloride, and 100 g of water were mixed, then 5.2 g of Salt A7 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 and 1H NMR measurement was performed. The cation / anion ratio was 0.98 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was performed. The solid content value was determined from the integration ratio with residual diisopropyl ether to be 97.8%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 7-R-1. Lots 7-R-2 and 7-R-3 were synthesized by the same method as described above. Lot 7-R-2 had 1 a solid content of 97.1% calculated from 1H NMR measurement, and Lot 7-R-3 similarly had a solid content of 97.6%.

[0445] <Synthesis Example 8 Synthesis of Salt (P) (Salt B8)>

[0446] [Chemical formula]

[0447] Me represents a methyl group.

[0448] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C8 (4.3 g), 100 g of methylene chloride, and 100 g of water were mixed, then salt A8 (4.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.21 mol%. 100 g of isopropyl alcohol was added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was performed. When the solid content value was determined from the integration ratio with residual isopropyl alcohol, it was 99.7%. When X and Z were measured for the dried solid, X was 0.08 mol% and Z was 7 ppm. The obtained solid was designated as Lot 8-a-0. The concentration of the reference lot was set to 99.7% as described above.

[0449] <Synthesis of a-1 (Lot 8-a-1)> Salt C8 (4.3 g), 100 g of methylene chloride, and 100 g of water were mixed, then salt A8 (4.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1When performing \(^1H\) NMR measurement, the cation / anion ratio was 1.00 / 1.00. When calculating X for the obtained crude product by the above method, it was 0.22 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 98.6%. When measuring X, Y, and Z for the solid after drying, X was 0.22 mol%, Y was 99.6%, and Z was 9 ppm. The obtained solid is designated as Lot 8-a-1.

[0450] <Synthesis of a-2 (Lot 8-a-2)> Salt C8 (4.3 g), 100 g of methylene chloride, and 100 g of water were mixed, then salt A8 (4.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone and 1 \(^1H\) NMR measurement was performed. When the cation / anion ratio was measured, it was 1.01 / 1.00. When calculating X for the obtained crude product by the above method, it was 0.66 mol%. As a purity improvement measure, 75 g of isopropanol was added to the crude product to dissolve it, and 25 g of hexane was added while stirring. The precipitated solid was collected by filtration and dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining isopropanol and hexane, it was 98.7%. When measuring X, Y, and Z for the dried crystal, X was 0.12 mol%, Y was 99.6%, and Z was 13 ppm. The obtained crystal is designated as Lot 8-a-2.

[0451] <Synthesis of a-3 (Lot 8-a-3)> Lot 8-a-3 was synthesized by the same method as Lot 8-a-1. When measuring X, Y, and Z for Lot 8-a-3, X was 0.13 mol%, Y was 99.1%, and Z was 10 ppm.

[0452] <Synthesis of b-1 (Lot 8-b-1)> Lot 8-b-1 was synthesized by the same method as above. X of the dried solid (Lot 8-b-1) was 0.28 mol%, and Z was 17 ppm. Y was not calculated, 1 99.1% calculated from 1H NMR measurement was taken as the solid content.

[0453] <Synthesis of b-2 (Lot 8-b-2) and Synthesis of b-3 (Lot 8-b-3)> Lot 8-b-2 and Lot 8-b-3 were each synthesized by the same method as above. X of Lot 8-b-2 was 0.15 mol%, and Z was 31 ppm. X of Lot 8-b-3 was 0.12 mol%, and Z was 13 ppm. Lot 8-b-2 1 99.2% calculated from 1H NMR measurement was taken as the solid content, and similarly for Lot 8-b-3, 98.9% was taken as the solid content.

[0454] <Synthesis of c-1 (Lot 8-c-1)> Lot 8-c-1 was synthesized by the same method as above. X of the dried solid (Lot 8-c-1) was 0.12 mol%, and Y was 98.2%. Z was not calculated.

[0455] <Synthesis of c-2 (Lot 8-c-2) and Synthesis of c-3 (Lot 8-c-3)> Lot 8-c-2 and Lot 8-c-3 were each synthesized by the same method as above. X of Lot 8-c-2 was 0.12 mol%, and Y was 98.8%. X of Lot 8-c-3 was 0.13 mol%, and Y was 99.4%.

[0456] <Synthesis of R-1 (Lot 8-R-1), Synthesis of R-2 (Lot 8-R-2), and Synthesis of R-3 (Lot 8-R-3)> Salt C8 (4.3g), methylene chloride (100g), and water (100g) were mixed, then salt A8 (4.5g) was added and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100g of 0.1N hydrochloric acid and three times with 100g of water, and the organic layer was concentrated under reduced pressure. A portion of the obtained crude product was dissolved in deuterated acetone, 1 ¹H NMR measurement revealed a cation / anion ratio of 1.02 / 1.00. 100 g of diisopropyl ether was added to the crude material and stirred. The filtered solid was dried under reduced pressure for 5 hours. A portion of the obtained solid was dissolved in deuterated acetone. 1 ¹H NMR measurements were performed, and the solid content was determined from the integral ratio with the remaining diisopropyl ether to be 98.9%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 8-R-1. Lots 8-R-2 and 8-R-3 were synthesized using the same method as described above. Lot 8-R-2 is 1 Based on the 1H NMR measurement, 98.5% was considered solid content, and similarly, 99.8% was considered solid content for lot 8-R-3.

[0457] <Synthesis Example 9: Synthesis of Salt (P) (Salt B9)>

[0458] [ka]

[0459] <Preparation of a reference lot (concentration Y measurement)> Salt C1 (5.9g), methylene chloride (100g), and water (100g) were mixed, then salt A9 (4.8g) was added and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100g of 0.1N hydrochloric acid and three times with 100g of water, and the organic layer was concentrated under reduced pressure. To the obtained crude material, 100g of tert-butyl methyl ether and 50g of acetone were added and dissolved, and then the organic layer was washed 10 times with 150g of water and concentrated under reduced pressure. X was calculated from the obtained crude material using the above method and was found to be 0.11 mol%. 100g of diisopropyl ether was added to the crude material and stirred, and then filtered. This was repeated three times, and the resulting solid was dried under reduced pressure for 8 hours. A portion of the obtained solid was dissolved in deuterated acetone.1 1H NMR measurement was carried out, and the solid content value was determined to be 99.6% from the integration ratio with residual diisopropyl ether. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 6 ppm. The obtained solid was designated as Lot 9-a-0. The concentration of the reference lot was set to 99.6% as described above.

[0460] <Synthesis of a-1 (Lot 9-a-1)> Salt C1 (5.9 g), 100 g of methylene chloride, and 100 g of water were mixed, and then Salt A9 (4.4 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, 1 1H NMR measurement was carried out, and the cation / anion ratio was 1.02 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.13 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone 1 1H NMR measurement was carried out, and the solid content value was determined to be 99.1% from the integration ratio with residual diisopropyl ether. When X, Y, and Z were measured for the dried solid, X was 0.13 mol%, Y was 99.8%, and Z was 14 ppm. The obtained solid was designated as Lot 9-a-1.

[0461] <Synthesis of a-2 (Lot 9-a-2)> Salt C1 (5.9 g), 100 g of methylene chloride, and 100 g of water were mixed, and then Salt A9 (4.4 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, 1When performing \(^1H\) NMR measurement, the cation / anion ratio was 1.02 / 1.00. When calculating X for the obtained crude product by the above method, it was 0.74 mol%. As a purity improvement measure, 75 g of isopropanol was added to the crude product and dissolved, and 25 g of hexane was added while stirring. The precipitated solid was collected by filtration and dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 \(^1H\) NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual isopropanol and hexane, it was 98.3%. When measuring X, Y, and Z for the dried crystal, X was 0.09 mol%, Y was 99.5%, and Z was 10 ppm. The obtained crystal was designated as Lot 9-a-2.

[0462] <Synthesis of a-3 (Lot 9-a-3)> Lot 9-a-3 was synthesized by the same method as Lot 9-a-1. When measuring X, Y, and Z for Lot 9-a-3, X was 0.11 mol%, Y was 99.2%, and Z was 11 ppm.

[0463] <Synthesis of b-1 (Lot 9-b-1)> Lot 9-b-1 was synthesized by the same method as above. X of the dried solid (Lot 9-b-1) was 0.13 mol% and Z was 21 ppm. Y was not calculated, and 1 the solid content was 98.9% calculated from \(^1H\) NMR measurement.

[0464] <Synthesis of b-2 (Lot 9-b-2) and synthesis of b-3 (Lot 9-b-3)> Lot 9-b-2 and Lot 9-b-3 were each synthesized by the same method as above. X of Lot 9-b-2 was 0.16 mol% and Z was 9 ppm. X of Lot 9-b-3 was 0.16 mol% and Z was 14 ppm. Lot 9-b-2 1 had a solid content of 98.6% calculated from \(^1H\) NMR measurement, and similarly, Lot 9-b-3 had a solid content of 99.2%.

[0465] <Synthesis of c-1 (Lot 9-c-1)> Lot 9-c-1 was synthesized by the same method as above. For the solid (Lot 9-c-1) after drying, X was 0.18 mol%, Y was 99.2%, and Z was not calculated.

[0466] <Synthesis of c-2 (Lot 9-c-2) and Synthesis of c-3 (Lot 9-c-3)> Lot 9-c-2 and Lot 9-c-3 were each synthesized by the same method as above. For Lot 9-c-2, X was 0.16 mol% and Y was 98.6%. For Lot 9-c-3, X was 0.10 mol% and Y was 99.2%.

[0467] <Synthesis of R-1 (Lot 9-R-1), Synthesis of R-2 (Lot 9-R-2), and Synthesis of R-3 (Lot 9-R-3)> 5.9 g of Salt C1, 100 g of methylene chloride, and 100 g of water were mixed, then 4.4 g of Salt A9 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 1 in 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, <B 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone <B 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 98.8%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 9-R-1. Lot 9-R-2 and Lot 9-R-3 were each synthesized by the same method as above. Lot 9-R-2 <B 1 had a solid content of 99.9% calculated from 1H NMR measurement, and similarly, Lot 9-R-3 had a solid content of 99.8%.

[0468] <Synthesis Example 10 Synthesis of Salt (P) (Salt B10)>

[0469]

Chem.

[0470] <Preparation of Reference Lot (Measurement of Concentration Y)> 9.0 g of Salt C9, 200 g of methylene chloride, and 200 g of water were mixed, and then 19.2 g of Salt A1 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and seven times with 200 g of water, and then concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.10 mol%. When X was calculated by the above method, it was 0.10 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 H NMR measurement was performed, and the solid content value was determined from the integration ratio with residual diisopropyl ether to be 99.3%. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 8 ppm. The obtained solid was designated as Lot 10-a-0. The concentration of the reference lot was set to 99.3% as described above.

[0471] <Synthesis of a-1 (Lot 10-a-1)> 8.4 g of Salt C9, 200 g of methylene chloride, and 200 g of water were mixed, and then 19.2 g of Salt A1 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and three times with 200 g of water, and then concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone and 1 H NMR measurement was performed, and the cation / anion ratio was 2.99 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.14 mol%. Since X was sufficiently low, 200 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and 1The solid content value was determined to be 97.5% from the integration ratio with residual diisopropyl ether by performing \(^1H\) NMR measurement. When measurements of X, Y, and Z were carried out on the solid after drying, X was 0.14 mol%, Y was 96.2%, and Z was 14 ppm. The obtained solid was designated as Lot 10-a-1.

[0472] <Synthesis of a-2 (Lot 10-a-2), and synthesis of a-3 (Lot 10-a-3)> Lot 10-a-2 and Lot 10-a-3 were each synthesized by the same method as Lot 10-a-1. For Lot 10-a-2, X was 0.16 mol%, Y was 97.2%, and Z was 24 ppm. For Lot 10-a-3, X was 0.19 mol%, Y was 95.8%, and Z was 17 ppm.

[0473] <Synthesis of b-1 (Lot 10-b-1)> Lot 10-b-1 was synthesized by the same method as above. For the solid after drying (Lot 10-b-1), X was 0.20 mol% and Z was 20 ppm. Y was not calculated, 1 98.0% calculated from \(^1H\) NMR measurement was taken as the solid content.

[0474] <Synthesis of b-2 (Lot 10-b-2), and synthesis of b-3 (Lot 10-b-3)> Lot 10-b-2 and Lot 10-b-3 were each synthesized by the same method as above. For Lot 10-b-2, X was 0.15 mol% and Z was 11 ppm. For Lot 10-b-3, X was 0.13 mol% and Z was 12 ppm. Lot 10-b-2 1 had 95.8% calculated from \(^1H\) NMR measurement as the solid content, and similarly, Lot 10-b-3 had 97.1% as the solid content.

[0475] <Synthesis of c-1 (Lot 10-c-1)> Lot 10-c-1 was synthesized by the same method as described above. For the dried solid (Lot 10-c-1), X was 0.12 mol% and Y was 96.6%. Z was not calculated.

[0476] <Synthesis of c-2 (Lot 10-c-2) and Synthesis of c-3 (Lot 10-c-3)> Lot 10-c-2 and Lot 10-c-3 were each synthesized by the same method as described above. For Lot 10-c-2, X was 0.18 mol% and Y was 96.9%. For Lot 10-c-3, X was 0.22 mol% and Y was 95.5%.

[0477] <Synthesis of R-1 (Lot 10-R-1), Synthesis of R-2 (Lot 10-R-2), and Synthesis of R-3 (Lot 10-R-3)> 9(8.4 g) of salt C, 200 g of methylene chloride, and 200 g of water were mixed, and then A1(19.2 g) of salt was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 200 g of 0.1 N hydrochloric acid and three times with 200 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 3.02 / ".00. 200 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone, 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 95.6%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 10-R-1. Lot 10-R-2 and Lot 10-R-3 were each synthesized by the same method as described above. Lot 10-R-2 1 had a solid content of 96.0% calculated from 1H NMR measurement, and similarly, Lot 10-R-3 had a solid content of 97.3%.

[0478] <Synthesis Example 11 Synthesis of Salt (P) (Salt B11)>

[0479] [Chemical]

[0480] <Preparation of Reference Lot (Measurement of Concentration Y)> Mix 10 (5.2 g) of Salt C, 100 g of methylene chloride, and 100 g of water, then add 10 (4.0 g) of Salt A and stir at room temperature for 30 minutes. After removing the aqueous layer, wash the organic layer once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and concentrate the organic layer under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.13 mol%. The crude product was purified by silica gel chromatography (solvent: chloroform), and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with residual chloroform, it was 99.8%. When X and Z were measured for the solid after drying, X was 0.08 mol% and Z was 4 ppm. The obtained solid was designated as Lot 11-a-0. The concentration of the reference lot was set to 99.8% as described above.

[0481] <Synthesis of a-1 (Lot 11-a-1)> Mix 10 (5.2 g) of Salt C, 100 g of methylene chloride, and 100 g of water, then add 10 (4.0 g) of Salt A and stir at room temperature for 30 minutes. After removing the aqueous layer, wash the organic layer once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and concentrate the organic layer under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone, and 1When \(^1H\) NMR measurement was carried out, the cation / anion ratio was 0.99 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.17 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When X, Y, and Z were measured for the dried solid, X was 0.17 mol%, Y was 98.1%, and Z was 540 ppm. The solid was dissolved in 80 g of methylene chloride, the organic layer was washed 5 times with 80 g of water, and the organic layer was concentrated under reduced pressure. 80 g of diisopropyl ether was added to the residue, stirred, and the filtered solid was dried under reduced pressure for 5 hours. When X, Y, and Z were measured for the dried solid, X was 0.16 mol%, Y was 97.2%, and Z was 20 ppm. The obtained solid was designated as Lot 11-a-1.

[0482] <Synthesis of a-2 (Lot 11-a-2)> C10 salt (5.2 g), 100 g of methylene chloride, and 100 g of water were mixed, and then A10 salt (4.0 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When \(^1H\) NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.81 mol%. As a purity improvement measure, the crude product was mixed with C10 salt (0.044 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1 N hydrochloric acid and five times with 80 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.11 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 \(^1H\) NMR measurement was carried out, and the solid content value was determined from the integration ratio with residual diisopropyl ether to be 97.7%. When X, Y, and Z were measured for the dried solid, X was 0.11 mol%, Y was 98.6%, and Z was 11 ppm. The obtained solid was designated as Lot 11-a-2.

[0483] <Synthesis of a-3 (Lot 11-a-3)> Lot 11-a-3 was synthesized by the same method as Lot 11-a-1. For Lot 11-a-3, when the measurements of X, Y, and Z were carried out, X was 0.15 mol%, Y was 99.2%, and Z was 12 ppm.

[0484] <Synthesis of b-1 (Lot 11-b-1)> Lot 11-b-1 was synthesized by the same method as above. For the solid after drying (Lot 11-b-1), X was 0.12 mol% and Z was 9 ppm. Y was not calculated, 1 98.8% calculated from 1H NMR measurement was taken as the solid content.

[0485] <Synthesis of b-2 (Lot 11-b-2) and synthesis of b-3 (Lot 11-b-3)> Lot 11-b-2 and Lot 11-b-3 were each synthesized by the same method as above. For Lot 11-b-2, X was 0.19 mol% and Z was 9 ppm. For Lot 11-b-3, X was 0.12 mol% and Z was 14 ppm. Lot 11-b-2 1 98.8% calculated from 1H NMR measurement was taken as the solid content, and similarly for Lot 11-b-3, 98.0% was taken as the solid content.

[0486] <Synthesis of c-1 (Lot 11-c-1)> Lot 11-c-1 was synthesized by the same method as above. For the solid after drying (Lot 11-c-1), X was 0.18 mol% and Y was 98.4%. Z was not calculated.

[0487] <Synthesis of c-2 (Lot 11-c-2) and synthesis of c-3 (Lot 11-c-3)> Lot 11-c-2 and Lot 11-c-3 were each synthesized by the same method as above. For Lot 11-c-2, X was 0.12 mol% and Y was 98.2%. For Lot 11-c-3, X was 0.16 mol% and Y was 98.4%.

[0488] <Synthesis of R-1 (Lot 11-R-1), Synthesis of R-2 (Lot 11-R-2), and Synthesis of R-3 (Lot 11-R-3)> 5.2 g of Salt C10, 100 g of methylene chloride, and 100 g of water were mixed, then 4.0 g of Salt A10 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was performed, the cation / anion ratio was 1.02 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 1H NMR measurement was performed, and the solid content value was determined from the integration ratio with residual diisopropyl ether to be 97.4%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 11-R-1. Lot 11-R-2 and Lot 11-R-3 were synthesized by the same method as above. Lot 11-R-2 1 had a solid content of 98.0% calculated from 1H NMR measurement, and similarly, Lot 11-R-3 had a solid content of 97.7%.

[0489] <Synthesis Example 12 Synthesis of Salt (P) (Salt B12)>

[0490] ​​​​​​​​​​​Salt C11 (3.5 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A11 (3.6 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.10 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. This was repeated three times, and the obtained solid was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 99.5%. When X and Z were measured for the dried solid, X was 0.09 mol% and Z was 7 ppm. The obtained solid was designated as Lot 12-a-0. The concentration of the reference lot was set to 99.5% as described above.

[0492] <Synthesis of a-1 (Lot 12-a-1)> Salt C11 (3.5 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A11 (3.6 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, and 1 1H NMR measurement was performed, and the cation / anion ratio was 1.00 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.20 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with the remaining diisopropyl ether, it was 99.3%. When X, Y, and Z were measured for the dried solid, X was 0.20 mol%, Y was 98.9%, and Z was 19 ppm. The obtained solid was designated as Lot 12-a-1.

[0493] <Synthesis of a-2 (Lot 12-a-2) and Synthesis of a-3 (Lot 12-a-3)> Lots 12-a-2 and 12-a-3 were each synthesized by the same method as Lot 12-a-1. For Lot 12-a-2, X was 0.18 mol%, Y was 99.4%, and Z was 15 ppm. For Lot 12-a-3, X was 0.25 mol%, Y was 98.2%, and Z was 14 ppm.

[0494] <Synthesis of <b-1> (Lot 12-b-1)> Lot 12-b-1 was synthesized by the same method as above. For the solid after drying (Lot 12-b-1), X was 0.11 mol% and Z was 16 ppm. Y was not calculated. 1 98.5% calculated from 1H NMR measurement was taken as the solid content.

[0495] <Synthesis of <b-2> (Lot 12-b-2) and <b-3> (Lot 12-b-3)> Lots 12-b-2 and 12-b-3 were each synthesized by the same method as above. For Lot 12-b-2, X was 0.18 mol% and Z was 30 ppm. For Lot 12-b-3, X was .16 mol% and Z was 10 ppm. Lot 12-b-2 1 99.2% calculated from 1H NMR measurement was taken as the solid content. Similarly, for Lot 12-b-3, 98.5% was taken as the solid content.

[0496] <Synthesis of <c-1> (Lot 12-c-1)> Lot 12-c-1 was synthesized by the same method as above. For the solid after drying (Lot 12-c-1), X was 0.17 mol% and Y was 98.7%. Z was not calculated.

[0497] <Synthesis of <c-2> (Lot 12-c-②) and <c-3> (Lot 12-c-3)> Lots 12-c-2 and 12-c-3 were each synthesized by the same method as above. [[ID=J39]] For Lot 12-c-2, X was 0.19 mol% and Y was 99.3%. For Lot 12-c-3, X was 0.16 mol% and Y was 99.2%.

[0498] <Synthesis of R-1 (Lot 12-R-1), Synthesis of R-2 (Lot 12-R-2), and Synthesis of R-3 (Lot 12-R-3)> 3.5 g of Salt C11, 100 g of methylene chloride, and 100 g of water were mixed, and then 3.6 g of Salt A11 was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and then the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 and when 1H NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 and 1H NMR measurement was performed. When the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 98.3%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 12-R-1. Lot 12-R-2 and Lot 12-R-3 were each synthesized by the same method as above. Lot 12-R-2 1 had a solid content of 98.2% calculated from 1H NMR measurement, and similarly, Lot 12-R-3 had a solid content of 99.0%.

[0499] <Synthesis Example 13 Synthesis of Salt (P) (Salt B13)>

[0500]

Chemical formula

[0501] <Preparation of Reference Lot (Measurement of Concentration Y)> Salt C12 (4.9 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A12 (4.9 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and five times with 100 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated for the obtained crude product by the above method, it was 0.12 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and filtered. The solid obtained by repeating this three times was dried under reduced pressure for 8 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 1H NMR measurement was performed, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.4%. When X and Z were measured for the solid after drying, X was 0.10 mol% and Z was 8 ppm. The obtained solid was designated as Lot 13-a-0. The concentration of the reference lot was set to the above 99.4%.

[0502] <Synthesis of a-1 (Lot 13-a-1)> Salt C12 (4.9 g), 100 g of methylene chloride, and 100 g of water were mixed, and then salt A12 (4.9 g) was added, followed by stirring at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone and 1 1H NMR measurement was performed, and the cation / anion ratio was 1.02 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.94 mol%. As a measure to improve purity, the crude product was mixed with salt C12 (, (0.046 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1 N hydrochloric acid and five times with 80 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.12 mol%. 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and 1When performing \(^1H\) NMR measurement and determining the solid content value from the integration ratio with residual diisopropyl ether, it was 98.8%. When measuring X, Y, and Z for the solid after drying, X was 0.12 mol%, Y was 99.5%, and Z was 9 ppm. The obtained solid was designated as Lot 13-a-1.

[0503] <Synthesis of a-2 (Lot 13-a-2)> Salt C12 (4.9 g), 100 g of methylene chloride, and 100 g of water were mixed, then Salt A12 (4.9 g) was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in deuterated acetone and 1 When performing \(^1H\) NMR measurement, the cation / anion ratio was 1.01 / 1.00. When calculating X for the obtained crude product by the above method, it was 0.14 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product, stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and 1 When performing \(^1H\) NMR measurement and determining the solid content value from the integration ratio with residual diisopropyl ether, it was 98.7%. When measuring X, Y, and Z for the solid after drying, X was 0.14 mol%, Y was 99.3%, and Z was 15 ppm. The obtained solid was designated as Lot 13-a-2.

[0504] <Synthesis of a-3 (Lot 13-a-3)> Lot 13-a-3 was synthesized by the same method as Lot 13-a-1. When measuring X, Y, and Z for Lot 13-a-3, X was 0.18 mol%, Y was 99.0%, and Z was 11 ppm.

[0505] <Synthesis of b-1 (Lot 13-b-1)> Lot 13-b-1 was synthesized by the same method as above. For the solid after drying (Lot 13-b-1), X was 0.16 mol% and Z was 18 ppm. Y was not calculated, and 1 The solid content calculated from \(^1H\) NMR measurement was 98.1%.

[0506] <Synthesis of b-2 (Lot 13-b-2) and synthesis of b-3 (Lot 13-b-3)> Lot 13-b-2 and Lot 13-b-3 were synthesized respectively by the same method as above. For Lot 13-b-2, X was 0.10 mol% and Z was 29 ppm. For Lot 13-b-3, X was 0.13 mol% and Z was 28 ppm. Lot 13-b-2 1 had a solid content of 96.8% calculated from 1H NMR measurement, and similarly, Lot 13-b-3 had a solid content of 98.1%.

[0507] <Synthesis of c-1 (Lot 13-c-1)> Lot 13-c-1 was synthesized by the same method as above. For the solid after drying (Lot 13-c-1), X was 0.26 mol% and Y was 99.1%. Z was not calculated.

[0508] <Synthesis of c-2 (Lot 13-c-2) and synthesis of c-3 (Lot 13-c-3)> Lot 13-c-2 and Lot 13-c-3 were synthesized respectively by the same method as above. For Lot 13-c-2, X was 0.12 mol% and Y was 99.5%. For Lot 13-c-3, X was 0.13 mol% and Y was 98.8%.

[0509] <Synthesis of R-1 (Lot 13-R-1), synthesis of R-2 (Lot 13-R-2), and synthesis of R-3 (Lot 13-R-3)> 4.9 g of salt C12, 100 g of methylene chloride, and 100 g of water were mixed, then 4.9 g of salt A12 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1¹H NMR measurement revealed a cation / anion ratio of 1.02 / 1.00. 100 g of diisopropyl ether was added to the crude material and stirred. The filtered solid was dried under reduced pressure for 5 hours. A portion of the obtained solid was dissolved in deuterated acetone. 1 ¹H NMR measurements were performed, and the solid content was determined from the integral ratio with the remaining diisopropyl ether to be 98.2%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 13-R-1. Lots 13-R-2 and 13-R-3 were synthesized using the same method as described above. Lot 13-R-2 is 1 Based on the 1H NMR measurement, 97.6% was considered solid content, and similarly, 98.4% was considered solid content for lot 13-R-3.

[0510] <Synthesis Example 14: Synthesis of Salt (P) (Salt B14)>

[0511] [ka]

[0512] <Preparation of a reference lot (concentration Y measurement)> Salt C13 (4.5g), methylene chloride (100g), and water (100g) were mixed, then salt A13 (3.7g) was added and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100g of 0.1N hydrochloric acid and five times with 100g of water, and the organic layer was concentrated under reduced pressure. When X was calculated from the obtained crude material using the above method, it was found to be 0.19 mol%. 100g of isopropyl alcohol and 20g of hexane were added to the crude material and stirred, then filtered. This was repeated three times, and the resulting solid was dried under reduced pressure for 8 hours. A portion of the obtained solid was dissolved in biacetone. 1 ¹H NMR measurements were performed, and since no hexane peak was observed, the solid content was determined from the integral ratio with the remaining diisopropyl ether to be 99.6%. After drying, X and Z were measured on the solid, and X was found to be 0.09 mol% and Z was 7 ppm. The obtained solid was designated as lot 13-a-0. The concentration of the reference lot was set to the above 99.6%.

[0513] <Synthesis of a-1 (Lot 14-a-1)> 100 g of methylene chloride, 100 g of water and 4.5 g of salt C13 were mixed, then 3.7 g of salt A13 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.03 / 1.00. When X was calculated for the obtained crude product by the above method, it was 1.13 mol%. As a measure to improve the purity, the crude product was mixed with 0.051 g of salt C13, 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1 N hydrochloric acid and five times with 80 g of water, and the organic layer was concentrated under reduced pressure. When X was calculated again for the obtained crude product, it was 0.19 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 1H NMR measurement was carried out, and when the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 98.9%. When X, Y, and Z were measured for the dried solid, X was 0.19 mol%, Y was 98.1%, and Z was 21 ppm. The obtained solid was designated as Lot 14-a-1.

[0514] <Synthesis of a-2 (Lot 14-a-2)> 100 g of methylene chloride, 100 g of water and 4.5 g of salt C13 were mixed, then 3.7 g of salt A13 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1 N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.02 / 1.00. When X was calculated for the obtained crude product by the above method, it was 0.11 mol%. Since X was sufficiently low, 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1When performing \(^{1}H\) NMR measurement and determining the solid content value from the integration ratio with residual diisopropyl ether, it was 98.4%. When measuring X, Y, and Z for the solid after drying, X was 0.10 mol%, Y was 99.0%, and Z was 10 ppm. The obtained solid was designated as Lot 14-a-2.

[0515] <Synthesis of a-3 (Lot 14-a-3)> Lot 14-a-3 was synthesized by the same method as Lot 14-a-1. When measuring X, Y, and Z for Lot 14-a-3, X was 0.19 mol%, Y was 99.1%, and Z was 12 ppm.

[0516] <Synthesis of b-1 (Lot 14-b-1)> Lot 14-b-1 was synthesized by the same method as above. For the solid after drying (Lot 14-b-1), X was 0.16 mol% and Z was 13 ppm. Y was not calculated, 1 The solid content was taken as 98.0% calculated from \(^{1}H\) NMR measurement.

[0517] <Synthesis of b-2 (Lot 14-b-2) and synthesis of b-3 (Lot 14-b-3)> Lot 14-b-2 and Lot 14-b-3 were each synthesized by the same method as above. For Lot 14-b-2, X was 0.26 mol% and Z was 19 ppm. For Lot 14-b-3, X was 0.12 mol% and Z was 18 ppm. Lot 14-b-2 [[ID=!]] 1 had a solid content of 98.7% calculated from \(^{1}H\nMR\) measurement, and similarly, Lot 14-b-3 had a solid content of 98.3%.

[0518] <Synthesis of c-1 (Lot 14-c-1)> Lot 14-c-1 was synthesized by the same method as above. For the solid after drying (Lot 14-c-1), X was 0.12 mol% and Y was 98.8%. Z was not calculated.

[0519] <Synthesis of c-2 (Lot 14-c-2) and synthesis of c-3 (Lot 14-c-3)> Lot 14-c-2 and Lot 14-c-3 were synthesized respectively by the same method as above. For Lot 14-c-2, X was 0.19 mol% and Y was 99.4%. For Lot 14-c-3, X was 0.15 mol% and Y was 98.0%.

[0520] <Synthesis of R-1 (Lot 14-R-1), synthesis of R-2 (Lot 14-R-2), and synthesis of R-3 (Lot 14-R-3)> 4.5 g of Salt C13, 100 g of methylene chloride, and 100 g of water were mixed, then 3.7 g of Salt A13 was added, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and the organic layer was concentrated under reduced pressure. A part of the obtained crude product was dissolved in heavy acetone, 1 When 1H NMR measurement was carried out, the cation / anion ratio was 1.01 / 1.00. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in heavy acetone 1 When 1H NMR measurement was carried out and the solid content value was determined from the integration ratio with residual diisopropyl ether, it was 99.1%. X, Y, and Z were not calculated. The obtained solid was designated as Lot 14-R-1. Lot 14-R-2 and Lot 14-R-3 were synthesized respectively by the same method as above. Lot 14-R-2 1 had a solid content of 97.9% calculated from 1H NMR measurement, and similarly, Lot 14-R-3 had a solid content of 98.6%.

[0521] <Synthesis Example 15 Synthesis of Salt (P) (Salt B15)>

[0522]

Chemical formula

[0523] <Preparatio...

Claims

1. A method for producing a photosensitive or radiation-sensitive resin composition, The method for producing a salt (P) of an organic cation and an organic anion comprises the following steps: (1) A step to obtain a product containing the salt (P) by performing anion exchange with the salt (I) of the organic cation and halide ion and the metal salt (M) of the organic anion. (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the product. (3) A step to determine whether the molar ratio X is 0.5 mol% or less. (4) If the molar ratio X in step (3) exceeds 0.5 mol%, a step to obtain a product containing salt (P) in which the molar ratio X is 0.5 mol% or less, by applying a measure to improve the purity of salt (P) to the product containing salt (P). (5) A step of determining the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) with a molar ratio X of 0.5 mol% or less, by high-performance liquid chromatography. (6) A step of obtaining the concentration Z of the residual acid contained in the product containing the salt (P) by ultraviolet-visible absorption spectroscopy. (7) A step of determining whether the concentration Z of the residual acid is 100 ppm or less, and (8) A step in which, if the concentration Z of the residual acid exceeds 100 ppm in step (7), measures are taken to reduce the concentration Z of the residual acid. The measure to improve the purity of the salt (P) in step (4) is purification by removing the salt (I) from the product containing the salt (P), The measures to reduce the concentration Z of the residual acid in step (8) are, The product containing the salt (P) is purified and extracted by adding a basic compound. The organic layer is washed by adding an organic solvent to the product containing the salt (P) and then adding water or water containing a basic compound. Crystallization of the product containing the salt (P), or Applying chromatography to the product containing the aforementioned salt (P). And, The cation in the salt (P) is a cation represented by the following formula (ZaI), The salt (P) is contained as a compound that generates acid upon irradiation with active light or radiation. The amount of the product containing the salt (P) in the composition is defined as the planned amount of the salt (P) × (100 / Y) (where Y represents the concentration Y of the salt (P) determined in step (5)). A method for producing a photosensitive or radiation-sensitive resin composition. 【Chemistry 1】 In equation (ZaI), R ２０１ , R ２０２ , and R ２０３ Each of these independently represents an organic group.

2. A method for producing a photosensitive or radiation-sensitive resin composition, The method for producing a salt (P) of an organic cation and an organic anion comprises the following steps: (1) A step to obtain a product containing the salt (P) by performing anion exchange with the salt (I) of the organic cation and halide ion and the metal salt (M) of the organic anion. (2) A step to obtain the molar ratio X of salt (I) to salt (P) by applying a potentiometric titration method using an aqueous silver nitrate solution to the product. (3) A step to determine whether the molar ratio X is 0.5 mol% or less. (4) If the molar ratio X in step (3) exceeds 0.5 mol%, a step to obtain a product containing salt (P) in which the molar ratio X is 0.5 mol% or less, by applying a measure to improve the purity of salt (P) to the product containing salt (P). (5) A step of determining the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) with a molar ratio X of 0.5 mol% or less, by high-performance liquid chromatography. (6) A step of obtaining the concentration Z of the residual acid contained in the product containing the salt (P) by ultraviolet-visible absorption spectroscopy. (7) A step of determining whether the concentration Z of the residual acid is 100 ppm or less, and (8) A step in which, if the concentration Z of the residual acid exceeds 100 ppm in step (7), measures are taken to reduce the concentration Z of the residual acid. The measure to improve the purity of the salt (P) in step (4) is to add the metal salt (M) of the organic anion to the product and perform the anion exchange. The measures to reduce the concentration Z of the residual acid in step (8) are, The product containing the salt (P) is purified and extracted by adding a basic compound. The organic layer is washed by adding an organic solvent to the product containing the salt (P) and then adding water or water containing a basic compound. Crystallization of the product containing the salt (P), or Applying chromatography to the product containing the aforementioned salt (P). And, The cation in the salt (P) is a cation represented by the following formula (ZaI), The salt (P) is contained as a compound that generates acid upon irradiation with active light or radiation. The amount of the product containing the salt (P) in the composition is defined as the planned amount of the salt (P) × (100 / Y) (where Y represents the concentration Y of the salt (P) determined in step (5)). A method for producing a photosensitive or radiation-sensitive resin composition. 【Chemistry 2】 In equation (ZaI), R ２０１ , R ２０２ , and R ２０３ Each of these independently represents an organic group.

3. In the above formula (ZaI), R ２０１ ~R ２０３ A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein at least one of the members is an aryl group.

4. A step of forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition produced by the method for producing an active photosensitive or radiation-sensitive resin composition according to claim 1 or 2, The step of exposing the aforementioned photosensitive or radiation-sensitive film, and The process of developing the exposed light-sensitive or radiation-sensitive film using a developer. A pattern forming method having the following characteristics.

5. A method for manufacturing an electronic device, comprising the pattern formation method described in claim 4.

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