Method for producing a resin, method for producing a photosensitive or radiation-sensitive resin composition, method for forming a pattern, and resin

Abstract

To provide a production method that can produce, with ease and accuracy, a useful resin in the production of an active ray-sensitive or radiation-sensitive resin composition, capable of forming a pattern having high roughness performance and etching resistance, a method for producing an active ray-sensitive or radiation-sensitive resin composition, a patterning method, and a resin that serves as a reaction intermediate of said resin.SOLUTION: The present invention relates to a method for producing a resin having a repeat unit that is decomposed upon exposure to active rays or radiation to generate an acid, including the step of polymerizing a compound represented by general formula (P-1) and a copolymerizable monomer compound, a method for producing an active ray-sensitive or radiation-sensitive resin composition, a patterning method, and a resin that serves as a reaction intermediate of said resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a resin that can be used in a photoactive ray-sensitive or radiation-sensitive resin composition, a method for producing a photoactive ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a resin.

Background Art

[0002] In the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), microfabrication by lithography using a photosensitive composition is performed. As a lithography method, there is a method in which a resist film is formed from a photosensitive composition, the obtained film is then exposed, and then developed. In particular, in recent years, in addition to an ArF excimer laser, consideration has been given to using EB (Electron Beam) and EUV (Extreme ultraviolet) light during exposure, and a photoactive ray-sensitive or radiation-sensitive resin composition suitable for EUV exposure has been developed.

[0003] As a resin used in such a composition, a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid is known.

[0004] For example, Patent Document 1 discloses a method for producing a polymer compound having a structural unit that decomposes upon exposure to generate an acid, which comprises polymerizing a water-soluble monomer having an anion group to synthesize a precursor polymer, washing the precursor polymer with water, and then performing salt exchange of the precursor polymer with an organic cation. Patent Document 2 discloses a method for producing a photoactive ray-sensitive or radiation-sensitive resin, which includes polymerizing a reaction system containing a first monomer having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid and a second monomer having a group that decomposes upon the action of an acid to generate an alkali-soluble group, in the presence of a basic compound.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] By the way, various performances are required for a photosensitive or radiation - sensitive film formed from a photosensitive or radiation - sensitive resin composition, and the compatibility of high roughness performance and high etching resistance performance is important as a required performance. Also, a manufacturing method that can more easily manufacture a photosensitive or radiation - sensitive resin composition satisfying the above requirements is demanded.

[0007] Therefore, an object of the present invention is to provide a manufacturing method capable of easily and highly precisely manufacturing a resin useful in the production of a photosensitive or radiation - sensitive resin composition capable of forming a pattern excellent in roughness performance and etching resistance performance, a manufacturing method of a photosensitive or radiation - sensitive resin composition, a pattern formation method, and a resin corresponding to a reaction intermediate of the above resin.

Means for Solving the Problems

[0008] The present inventors have found that the above problems can be solved by the following configuration. 〔1〕 A method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid, including a step of polymerizing a compound represented by the following general formula (P - 1) and a copolymerizable monomer compound.

Chemical Formula

Chem.

Chem.

[15] . 〔17〕 A step of producing the resin by the method for producing a resin according to any one of [1] to

[15] , a step of forming a photosensitive or radiation-sensitive film on a substrate using the photosensitive or radiation-sensitive resin composition containing the resin, 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 to form a pattern. A patterning method having the above steps. 〔18〕 A resin having a repeating unit derived from a compound represented by the following general formula (P-1) and a repeating unit derived from a compound represented by any one of the following formulas (A-2) to (A-5).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[18] , but hereinafter, other matters (for example, the following [1] to

[18] ) are also described.

[0009] [1] A method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid, the method including a step of polymerizing a compound represented by the following general formula (P-1) and a copolymerizable monomer compound.

[0010]

Chemical formula

[0011] In general formula (P-1), R 1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L 1 represents a single bond or a divalent linking group. Ar p1 represents an aromatic ring group or an aromatic heterocyclic group. M + represents a lithium cation, a potassium cation, or an ammonium cation.

[0012] [2] The method for producing the resin according to [1], wherein at least one of the copolymerizable monomer compounds is a compound represented by the following general formula (A-1).

[0013]

Chemical formula

[0014] In the general formula (A-1), R 2 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Ar a1 represents an (n + 1)-valent aromatic ring group or an (n + 1)-valent aromatic heterocyclic group. n represents an integer from 1 to 4. Y 1 represents a hydrogen atom or a substituent. When n represents an integer from 2 to 4, a plurality of Y's 1 may be the same or different.

[0015] [3] The method for producing the resin according to [1] or [2], wherein the compound represented by the general formula (P-1) is a compound represented by the following general formula (P-2).

[0016]

Chemical formula

[0017] In the general formula (P-2), M +is synonymous with M in the general formula (P-1). + is synonymous with.

[0018] [4] The method for producing a resin according to any one of [1] to [3], wherein a solvent is used in the polymerization step, and the content of the alcohol-based solvent is 20% by mass or more based on the total amount of the solvent. [5] The method for producing a resin according to [4], wherein the content of the alcohol-based solvent is 50% by mass or more based on the total amount of the solvent. [6] The method for producing a resin according to [4] or [5], wherein the alcohol-based solvent is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, methyl lactate, ethyl lactate, and diacetone alcohol.

[0019] [7] The method for producing a resin according to any one of [1] to [6], wherein before carrying out the polymerization step, a solution containing the compound represented by the general formula (P-1) is passed through a filter having a pore size of 0.05 to 5 μm and then the polymerization step is carried out. [8] After the polymerization step, a step of exchanging the cation M + in the repeating unit derived from the compound represented by the general formula (P-1) with an organic cation is included. The method for producing a resin according to any one of [1] to [7]. [9] The method for producing a resin according to any one of [1] to [8], wherein the resin further has a repeating unit having an acid-decomposable group.

[0020]

[10] Y in the general formula (A-1) 1 is a hydrogen atom or a group represented by any one of the following formulas (AY-1) to (AY-3). The method for producing a resin according to any one of [2] to [9].

[0021] [Chemical formula]

[0022] In formula (AY-1), R a11 , and R a12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R a2 represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0023] [Chemical formula]

[0024] In formula (AY-2), R a3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group. * represents the bonding position.

[0025] [Chemical formula]

[0026] In formula (AY-3), R a4 ~R a6 each independently represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0027]

[11] The method for producing a resin according to any one of [2] to

[10] , wherein the compound represented by the general formula (A-1) is a compound represented by any one of the following formulas (A-2) to (A-5).

[0028] [Chemical formula]

[0029] In formula (A-3), Rb11 and R b12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R b2 represents an alkyl group, an aryl group, or a heteroaryl group.

[0030] [Chemical formula]

[0031] In formula (A-4), R b3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group.

[0032] [Chemical formula]

[0033] In formula (A-5), R b4 to R b6 each independently represents an alkyl group, an aryl group, or a heteroaryl group.

[0034]

[12] The method for producing a resin according to

[11] , wherein the compound represented by the general formula (A-1) is a compound represented by any one of the above formulas (A-3) to (A-5), and includes a step of converting a repeating unit derived from the compound represented by the general formula (A-1) after the polymerization step into a repeating unit represented by the following formula (AP-1).

[0035] [Chemical formula]

[0036]

[13] The method for producing a resin according to

[12] , including a step of converting at least a part of the repeating unit represented by the above formula (AP-1) into a repeating unit represented by the following formula (AP-2).

[0037] [Chemical formula]

[0038] In formula (AP-2), Y 2 represents a group that is eliminated by the action of an acid.

[0039]

[14] The method for producing a resin according to

[11] , wherein the compound represented by the general formula (A-1) is the compound represented by the above formula (A-2), and includes a step of converting at least a part of the repeating unit represented by the general formula (A-2) into a repeating unit represented by the following formula (AP-2) after the polymerization step.

[0040] [Chemical formula]

[0041] In formula (AP-2), Y 2 represents a group that is eliminated by the action of an acid.

[0042]

[15] In the above formula (AP-2), Y 2 is a group represented by the following formula (AY-4), and the method for producing a resin according to

[13] or

[14] .

[0043] [Chemical formula]

[0044] In formula (AY-4), R c11 , and R c12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R c2 represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0045]

[16] A method for producing a photosensitive or radiation-sensitive resin composition containing the above resin, which includes the method for producing a resin according to any one of [1] to

[15] .

[17] A step of producing the above resin by the method for producing a resin according to any one of [1] to

[15] ; A step of forming a radiation-sensitive or radiation-sensitive resin film on a substrate using the radiation-sensitive or radiation-sensitive resin composition containing the above resin; A step of exposing the radiation-sensitive or radiation-sensitive resin film; A step of developing the exposed radiation-sensitive or radiation-sensitive resin film with a developer to form a pattern, the pattern forming method comprising:

[0046]

[18] A resin having a repeating unit derived from a compound represented by the following general formula (P-1) and a repeating unit derived from a compound represented by any one of the following formulas (A-2) to (A-5).

[0047] [Chemical formula]

[0048] In the general formula (P-1), R 1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L 1 represents a single bond or a divalent linking group. Ar p1 represents an aromatic ring group or an aromatic heterocyclic group. M + represents a lithium cation, a potassium cation, or an ammonium cation.

[0049] [Chemical formula]

[0050] In formula (A-3), R b11 , and R b12 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R b2 represents an alkyl group, an aryl group, or a heteroaryl group.

[0051]

Chem.

[0052] In formula (A-4), R b3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group.

[0053]

Chem.

[0054] In formula (A-5), R b4 ~R b6 each independently represents an alkyl group, an aryl group, or a heteroaryl group.

Advantages of the Invention

[0055] According to the present invention, there can be provided a production method capable of easily and highly precisely producing a resin useful in the production of a radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in roughness performance and etching resistance, a production method of a radiation-sensitive or radiation-sensitive resin composition, a pattern forming method, and a resin corresponding to a reaction intermediate of the above resin.

Embodiments for Carrying Out the Invention

[0056] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. Regarding the notation of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations without indicating substitution and unsubstitution include groups containing substituents together with groups having no substituents. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, in this specification, the "organic group" means a group containing at least one carbon atom. As the substituent, unless otherwise specified, a monovalent substituent is preferred.

[0057] In this specification, the "actinic ray" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). In this specification, the "light" means actinic rays or radiation. In this specification, unless otherwise specified, the "exposure" includes not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays, X-rays, and EUV light, etc., but also drawing by particle beams such as electron beams and ion beams. In this specification, "~" is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[0058] In this specification, unless otherwise specified, the bonding direction of the divalent group described is not limited. For example, in a compound represented by the formula "X-Y-Z", when Y is -COO-, Y may be -CO-O- or -O-CO-. Further, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0059] In this specification, (meth)acrylate represents acrylate and methacrylate, and (meth)acrylic represents acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-equivalent values by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: dimethylformamide, 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: refractive index detector).

[0060] In this specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. Specifically, it is a value obtained by calculation based on Hammett substituent constants and a database of known literature values using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0061] Also, pKa can be determined by a molecular orbital calculation method. As a specific method, there is a method of calculating by calculating the dissociation free energy of H in an aqueous solution based on a thermodynamic cycle. + Regarding the calculation method of the dissociation free energy of H, for example, it can be calculated by DFT (density functional theory), but various other methods have been reported in the literature and the like, and it is not limited to this. Although there are multiple software that can perform DFT, for example, Gaussian16 can be mentioned. +

[0062] ​In this specification, as described above, pKa refers to a value calculated using software package 1 based on Hammett's substituent constants and a database of known literature values. When pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional theory) shall be adopted. Also, in this specification, pKa refers to "pKa in an aqueous solution" as described above. When pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted. "Solid content" means a component that forms a radiation-sensitive or actinic ray-sensitive film and does not include a solvent. Also, any component that forms a radiation-sensitive or actinic ray-sensitive film, even if its property is liquid, shall be regarded as a solid content.

[0063] Also, in this specification, when it is stated that "it may have a substituent", the type, position, and number of the substituent are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent non-metal atomic groups excluding a hydrogen atom, and can be selected, for example, from the following substituent T.

[0064] (Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxysilyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl group; alkenyl group; cycloalkyl group; aryl group; heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; and combinations thereof.

[0065] [Method for producing resin] The method for producing a resin of the present invention is a method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid, including a step of polymerizing a compound represented by the following general formula (P-1) and a copolymerizable monomer compound.

[0066] [Chemical formula]

[0067] In general formula (P-1), R 1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L 1 represents a single bond or a divalent linking group. Ar p1 represents an aromatic ring group or an aromatic heterocyclic group. M +represents a lithium cation, a potassium cation, or an ammonium cation. Each group in the general formula (P-1) will be described later.

[0068] Although the mechanism by which a resin useful in the production of a chemically amplified photosensitive or radiation-sensitive resin composition capable of forming a pattern excellent in roughness performance and etching resistance performance can be produced easily and with high precision is not necessarily clear, the present inventors consider it as follows. First, the method for producing the resin of the present invention is a method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid. Thus, in the resin to be produced, since the acid generation sites are incorporated into the resin, it is considered that the acid generated in the exposed portion of the chemically amplified photosensitive or radiation-sensitive film is suppressed from diffusing too much into the unexposed portion, and a pattern excellent in roughness performance can be obtained. In addition, the method for producing the resin of the present invention includes a step of polymerizing a compound represented by the above general formula (P-1) and a copolymerizable monomer compound. Here, the compound represented by the general formula (P-1) has an aromatic ring group or an aromatic heterocyclic group, and these groups are rigid groups. And since the resin used in the chemically amplified photosensitive or radiation-sensitive resin composition will similarly have an aromatic ring group or an aromatic heterocyclic group as a rigid group, it is considered that a pattern excellent in etching resistance performance can be obtained. In addition, the compound represented by the general formula (P-1) as an ionic monomer compound has M as a counter cation + represents a lithium cation, a potassium cation, or an ammonium cation, whereby the solubility of the ionic monomer compound in the monomer solution is improved as compared with, for example, the case where the counter cation is a sodium cation. The detailed reason is not clear, but in the case of a sodium cation, it is presumed that it is difficult to be solvated by an organic solvent and the solubility is lowered. As described above, if the solubility of the ionic monomer compound in the monomer solution is improved, it is possible to reduce the production cost by reducing the amount of the polymerization solvent used in the monomer solution. For example, when the counter cation is a sodium cation, for a monomer that is difficult to copolymerize itself from the viewpoint of solubility in the polymerization solvent, by using a lithium cation, a potassium cation, or an ammonium cation as the counter cation, the copolymerization of the monomer can be carried out as desired, and the manufacturing application range can be expanded. For the reasons described above, etc., it is considered that a resin can be easily produced by using the compound represented by the general formula (P-1) in the copolymerization step. Furthermore, in the method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid according to the present invention, M as the counter cation + represents a lithium cation, a potassium cation, or an ammonium cation. Therefore, it passes through a step of polymerizing a compound represented by the general formula (P-1) that is difficult to decompose upon irradiation with actinic rays or radiation to generate an acid. Thereby, in the polymerization step, unintended reactions such as decomposition of the resin by an acid can be suppressed in a high dimension, and thus it is considered that a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid can be produced with high precision.

[0069] Hereinafter, the step of polymerizing the compound represented by the general formula (P-1) and the copolymerizable monomer compound (also referred to as step (1)) in such a resin production method will be described.

[0070] <Step (1) (Polymerization Step)> Step (1) in the present invention refers to a step of polymerizing a compound represented by the general formula (P-1) and a copolymerizable monomer compound.

[0071] (Polymerization Initiator) The reaction in the above step (1) usually further contains a polymerization initiator. As the polymerization initiator, for example, radical initiators such as azo initiators and peroxides are used to initiate the polymerization. As the radical initiator, an azo initiator is preferred, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferred. Preferred initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), and the like. Incidentally, if desired, the initiator may be added in multiple portions.

[0072] (Solvent) The reaction in the above step (1) is typically carried out in the liquid phase. That is, the above reaction system typically further contains a solvent. The solvent is not particularly limited as long as it can dissolve each component. For example, alcohol solvents, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, cyclic lactones, chain or cyclic ketones, alkylene carbonates, alkyl carboxylates, alkyl alkoxyacetates, alkyl pyruvates, and the like can be mentioned. Other solvents that can be used include, for example, the solvents described in

[0244] and subsequent paragraphs of US Patent Application Publication No. 2008 / 0248425A1.

[0073] The alcohol solvent is not particularly limited as long as it contains -OH. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, diacetone alcohol, and the like can be mentioned.

[0074] Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0075] Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. The alkylene glycol monoalkyl ether is included in the alcohol-based solvents.

[0076] Examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate. Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone.

[0077] Examples of chain or cyclic ketones include, for example, 2-butanone (methyl ethyl ketone), 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone.

[0078] Examples of alkylene carbonates include, for example, propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate. Examples of alkyl carboxylates include, for example, butyl acetate.

[0079] Examples of alkyl alkoxyacetates include, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, 1-methoxy-2-propyl acetate. Examples of alkyl pyruvates include, for example, methyl pyruvate, ethyl pyruvate, propyl pyruvate.

[0080] These solvents may be used alone or in combination of two or more.

[0081] The above polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Further, if necessary, the polymerization may be carried out in the presence of a chain transfer agent (for example, an alkyl mercaptan).

[0082] The monomer concentration in the reaction system is preferably 20 to 70% by mass, more preferably 25 to 50% by mass. The reaction temperature is usually 10°C to 150°C, preferably 30°C to 120°C, and more preferably 40 to 100°C. The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and more preferably 1 to 12 hours.

[0083] In a preferred embodiment, a solvent is used in the above polymerization step, and the content of the alcohol-based solvent based on the total amount of the above solvent is preferably 20% by mass or more. The content of the alcohol-based solvent based on the total amount of the above solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.

[0084] The above alcohol-based solvent is preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, methyl lactate, ethyl lactate, and diacetone alcohol.

[0085] 〔Compound represented by general formula (P-1)〕 The compound represented by general formula (P-1) will be described below.

[0086]

Chemical formula

[0087] In the general formula (P-1), R 1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L 1 represents a single bond or a divalent linking group. Ar p1 represents an aromatic ring group or an aromatic heterocyclic group. M + represents a lithium cation, a potassium cation, or an ammonium cation.

[0088] R 1 The alkyl group of R is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. The aryl group is not particularly limited, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T. R 1 is preferably a hydrogen atom.

[0089] L 1 The divalent linking group of L is not particularly limited, and examples thereof include an alkylene group, a cycloalkylene group, an aromatic ring group, an aromatic heterocyclic group, -C(=O)-, -O-, and a divalent linking group formed by combining a plurality of these. The alkylene group is not particularly limited, and may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and even more preferably has 1 to 3 carbon atoms. The cycloalkylene group is not particularly limited, but a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 10 carbon atoms is more preferable, and a cycloalkylene group having 1 to 6 carbon atoms is even more preferable.

[0090] The aromatic ring group is not particularly limited, and it may be a monocyclic or polycyclic group. An aromatic ring group having 6 to 20 carbon atoms is preferable, an aromatic ring group having 6 to 14 carbon atoms is more preferable, and an aromatic ring group having 6 to 10 carbon atoms is even more preferable. The aromatic heterocyclic group is not particularly limited, and it may be a monocyclic or polycyclic group. The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. The alkylene group, cycloalkylene group, aromatic ring group, and aromatic heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T. In a preferred embodiment, L 1 is preferably a single bond.

[0091] Ar p1 The aromatic ring group of is not particularly limited, and it may be a monocyclic or polycyclic group. An aromatic ring group having 6 to 20 carbon atoms is preferable, an aromatic ring group having 6 to 14 carbon atoms is more preferable, and an aromatic ring group having 6 to 10 carbon atoms is even more preferable. The aromatic heterocyclic group is not particularly limited, and it may be a monocyclic or polycyclic group. The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. The aromatic ring group and the aromatic heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T.

[0092] M + represents a lithium cation, a potassium cation, or an ammonium cation. Examples of the ammonium cation include ammonium cation (NH4 + ), tetraalkylammonium cation, etc., but ammonium cation (NH4 + ) is preferred. As for the alkyl group in the tetraalkylammonium cation, an alkyl group having 1 to 6 carbon atoms is preferred, and a plurality of alkyl groups may be the same or different. M + is preferably a lithium cation or an ammonium cation (NH4 + ), and more preferably a lithium cation.

[0093] The compound represented by the general formula (P-1) is preferably a compound represented by the following general formula (P-2).

[0094]

Chemical formula

[0095] In the general formula (P-2), M + has the same meaning as M + in the general formula (P-1), and the preferred range is also the same.

[0096] Hereinafter, specific examples of the compound represented by the general formula (P-1) are exemplified, but the present invention is not limited thereto.

[0097]

Chemical formula

[0098] The compound represented by the general formula (P-1) can be synthesized by a conventional method. For example, the synthesis method described in Patent No. 6705121 etc. can be used.

[0099] The compound represented by the general formula (P-1) may be used alone or in combination of two or more. The content of the compound represented by the general formula (P-1) in step (1) is preferably 0.5 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, based on the total amount of the monomers.

[0100] Before carrying out the polymerization step (step (1)), it is preferable to pass the solution containing the compound represented by the general formula (P-1) through a filter with a pore size of 0.05 to 5 μm and then carry out the polymerization step. The pore size is 0.05 to 5 μm, more preferably 0.1 to 3 μm. The filter is not particularly limited, and examples thereof include membrane filters, cartridge filters, syringe filters, and the like.

[0101] (Copolymerizable monomer compound) The copolymerizable monomer compound will be described below. The copolymerizable monomer compound is a compound copolymerizable with the compound represented by the general formula (P-1). The copolymerizable monomer compound is not particularly limited, but it is preferable that at least one of the copolymerizable monomer compounds is a compound represented by the following general formula (A-1).

[0102] [Chemical formula]

[0103] In the general formula (A-1), R 2 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Ar a1 represents an (n + 1)-valent aromatic ring group or an (n + 1)-valent aromatic heterocyclic group. n represents an integer of 1 to 4. Y 1 represents a hydrogen atom or a substituent. When n represents an integer of 2 to 4, a plurality of Y1 They may be the same or different.

[0104] R 2 The alkyl group of R is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. The aryl group is not particularly limited, and preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferable. The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T. R 2 is preferably a hydrogen atom or an alkyl group.

[0105] Ar a1 represents an (n + 1)-valent aromatic ring group or an (n + 1)-valent aromatic heterocyclic group. First, the divalent aromatic ring group and the divalent aromatic heterocyclic group in the case where n is 1 will be described below. The divalent aromatic ring group is not particularly limited, and may be monocyclic or polycyclic, preferably an aromatic ring group having 6 to 20 carbon atoms, more preferably an aromatic ring group having 6 to 14 carbon atoms, and even more preferably an aromatic ring group having 6 to 10 carbon atoms. The divalent aromatic heterocyclic group is not particularly limited, and may be monocyclic or polycyclic. The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. The above aromatic ring group and aromatic heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T.

[0106] Examples of the (n + 1)-valent aromatic ring group include groups formed by removing (n - 1) hydrogen atoms from the above divalent aromatic ring group. Examples of the (n + 1)-valent aromatic heterocyclic group include groups formed by removing (n - 1) hydrogen atoms from the above divalent aromatic heterocyclic group.

[0107] Y 1 The substituents of Y are not particularly limited, and examples thereof include an alkyl group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like. The alkyl group is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 1 to 6 carbon atoms. The alkyl group in the alkylcarbonyl group is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 1 to 6 carbon atoms. The aryl group in the arylcarbonyl group is not particularly limited, and preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The heteroaryl group in the heteroarylcarbonyl group is not particularly limited, and may be monocyclic or polycyclic. The aromatic heterocycle constituting the heteroaryl group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. The alkoxy group in the alkoxycarbonyl group is not particularly limited, and examples thereof include linear or branched alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 12 carbon atoms, and more preferably alkoxy groups having 1 to 6 carbon atoms. The aryl group in the aryloxycarbonyl group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0108] The above alkyl group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, and aryloxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T. The above alkyl group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, and aryloxycarbonyl group may have a plurality of substituents. As a preferable embodiment, examples of the substituent include an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group.

[0109] Examples of the aryl group include the same ones as those in the arylcarbonyl group described above, and the preferable range is also the same. Examples of the heteroaryl group include the same ones as those in the heteroarylcarbonyl group described above, and the preferable range is also the same. The alkoxy group is not particularly limited, and examples thereof include a linear or branched alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 12 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms. The aryl group in the aryloxy group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The heteroaryl group in the heteroaryloxy group is not particularly limited, and examples thereof include the same ones as those in the heteroarylcarbonyl group described above, and the preferable range is also the same.

[0110] Y in the above general formula (A-1) 1is preferably a hydrogen atom or a group represented by any of the following formulas (AY-1) to (AY-3).

[0111]

Chemical formula

[0112] In formula (AY-1), R a11 , and R a12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R a2 represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0113]

Chemical formula

[0114] In formula (AY-2), R a3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group. * represents the bonding position.

[0115]

Chemical formula

[0116] In formula (AY-3), R a4 to R a6 each independently represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0117] In formula (AY-1), the alkyl groups of R a11 , R a12 , and R a2 are not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms. Alkyl groups having 1 to 12 carbon atoms are preferred, and alkyl groups having 1 to 6 carbon atoms are more preferred. R a11 、R a12 、and R a2 The aryl group of R R a11 、R a12 、and R a2 The heteroaryl group of R The above alkyl group, aryl group, and heteroaryl group may have substituents. The substituents are not particularly limited, and for example, the above-mentioned substituent T can be mentioned. In a preferred embodiment, R a12 、R a2 are each independently an alkyl group. Also, in a preferred embodiment, R a11 is a hydrogen atom, and R a12 、R a2 are each independently an alkyl group.

[0118] In formula (AY-2), the alkyl group of R a3 is not particularly limited, and examples thereof include the same ones as the alkyl groups of the above R a11 、R a12 、and R a2 and the preferred range is also the same. R a3 The alkoxy group of R R a3 The aryl group of R a11 、Ra12 and R a2 The aryl groups similar to those of R can be mentioned, and the preferable ranges are also the same. R a3 The aryl group in the aryloxy group of R is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. R a3 The heteroaryl group of R is not particularly limited, but the same as the heteroaryl groups of the above R a11 R a12 and R a2 The heteroaryl groups similar to those of R can be mentioned, and the preferable ranges are also the same. R a3 is preferably an alkyl group.

[0119] In formula (AY-3), the alkyl groups of R a4 to R a6 are not particularly limited, but the same as the alkyl groups of the above R a11 R a12 and R a2 The alkyl groups similar to those of R can be mentioned, and the preferable ranges are also the same. R a4 to R a6 The aryl groups of R are not particularly limited, but the same as the aryl groups of the above R a11 R a12 and R a2 The aryl groups similar to those of R can be mentioned, and the preferable ranges are also the same. R a4 to R a6 The heteroaryl groups of R are not particularly limited, but the same as the heteroaryl groups of the above R a11 R a12 and R a2 The heteroaryl groups similar to those of R can be mentioned, and the preferable ranges are also the same. R a4 to R a6 are each independently preferably an alkyl group.

[0120] It is preferable that the compound represented by the general formula (A-1) is a compound represented by any of the following formulas (A-2) to (A-5).

[0121]

Chemical formula

[0122] In formula (A-3), R b11 , and R b12 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R b2 represents an alkyl group, an aryl group, or a heteroaryl group.

[0123]

Chemical formula

[0124] In formula (A-4), R b3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group.

[0125]

Chemical formula

[0126] In formula (A-5), R b4 ~R b6 each independently represent an alkyl group, an aryl group, or a heteroaryl group.

[0127] In formula (A-3), the alkyl groups of R b11 , R b12 , and R b2 are not particularly limited, and examples thereof include the same alkyl groups as those of R a11 , R a12 , and R a2 in the above formula (AY-1), and the preferable ranges are also the same. R b11 , R b12 , and Rb2 The aryl group of is not particularly limited, but R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the aryl groups of, and the preferred ranges are also the same. R b11 , R b12 , and R b2 The heteroaryl group of is not particularly limited, but R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the heteroaryl groups of, and the preferred ranges are also the same.

[0128] In formula (A-4), the alkyl group of R b3 is not particularly limited, but R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the alkyl groups of, and the preferred ranges are also the same. R b3 The alkoxy group of is not particularly limited, and examples thereof include linear or branched alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 12 carbon atoms, and more preferably alkoxy groups having 1 to 6 carbon atoms. R b3 The aryl group of is not particularly limited, but R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the aryl groups of, and the preferred ranges are also the same. R b3 The aryl group in the aryloxy group of is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferred, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. R b3 The heteroaryl group of is not particularly limited, but R in the above formula (AY-1) a11 , R a12 , and R a2Those similar to the heteroaryl group can be mentioned, and the preferable ranges are also the same.

[0129] In formula (A-5), R b4 ~R b6 As the alkyl group, it is not particularly limited, but those similar to the R a11 , R a12 , and R a2 in the above formula (AY-1) can be mentioned, and the preferable ranges are also the same. R b4 ~R b6 As the aryl group, it is not particularly limited, but those similar to the R a11 , R a12 , and R a2 in the above formula (AY-1) can be mentioned, and the preferable ranges are also the same. R b4 ~R b6 As the heteroaryl group, it is not particularly limited, but those similar to the R a11 , R a12 , and R a2 in the above formula (AY-1) can be mentioned, and the preferable ranges are also the same. It is preferable that the compound represented by the above general formula (A-1) is a compound represented by any of the above formulas (A-3) to (A-5).

[0130] As the copolymerizable monomer compound, a compound copolymerizable with the compound represented by the above general formula (P-1) other than the compound represented by the above general formula (A-1) can be appropriately used.

[0131] Hereinafter, specific examples of the copolymerizable monomer compound will be illustrated, but the present invention is not limited thereto.

[0132]

Chemical formula

[0133] The above copolymerizable monomer compound may be used alone or in combination of two or more. The content of the above copolymerizable monomer compound in step (1) is preferably 70 mol% to 99.5 mol%, more preferably 80 mol% to 99 mol%, based on the total amount of monomers.

[0134] The total content of the compound represented by the general formula (P-1) and the compound represented by the general formula (A-1) in step (1) is preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, based on the total amount of monomers.

[0135] In step (1), the compound represented by the general formula (P-1) and the above copolymerizable monomer compound can be polymerized to synthesize resin P. Resin P corresponds to the reaction intermediate of the above resin. Resin P can be synthesized according to a conventional method (for example, radical polymerization).

[0136] The weight average molecular weight of resin P in terms of polystyrene conversion value by the GPC method is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution) of resin P is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0.

[0137] The method for producing the resin of the present invention preferably includes a step of exchanging the cation M in the repeating unit derived from the compound represented by the general formula (P-1) with an organic cation after the above polymerization step (step (1)). + with an organic cation. Hereinafter, the step of exchanging the cation M in the repeating unit derived from the compound represented by the general formula (P-1) with an organic cation (also referred to as step (2)) in the method for producing the resin of the present invention after the above step (1) will be described. + will be described.

[0138] <Step (2)> Step (2) in the present invention refers to a step of exchanging the cation M in the repeating unit derived from the compound represented by the general formula (P-1) + with an organic cation.

[0139] The above exchange (salt exchange) can be carried out by reacting the resin P with a compound having an organic cation (hereinafter also referred to as compound A) in a solvent.

[0140] Compound A is a compound used in the above exchange and has an organic cation as the cation part and an anion part. As the anion part, a non-nucleophilic ion is preferable, and examples thereof include halogen ions such as bromine ions and chlorine ions, carbonate ions, trifluoroacetate ions, and the like.

[0141] The organic cation in the cation part of compound A is not particularly limited, but a cation represented by the formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferable.

[0142]

Chemical formula

[0143] In the above formula (ZaI), R 201 、R 202 、and R 203 each independently represent an organic group. R 201 、R 202 、and R 203 The number of carbon atoms of the organic group as is preferably 1 to 30, more preferably 1 to 20. Further, two of R 201 ~R 203 may be bonded 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. R 201 ~R 203Examples of the group formed by combining two of them include an alkylene group (e.g., a butylene group and a pentylene group) and -CH2-CH2-O-CH2-CH2-.

[0144] Preferable embodiments of the organic cation in formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0145] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 ~R 203 is an aryl group. For the arylsulfonium cation, all of R 201 ~R 203 may be aryl groups, or some of R 201 ~R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups. Also, one of R 201 ~R 203 is an aryl group, and the remaining two of R 201 ~R 203 may combine 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. Examples of the group formed by combining two of R 201 ~R 203 include an alkylene group (e.g., a butylene group, a 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. Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0146] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, 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, or the like. 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 group or cycloalkyl group that the arylsulfonium cation may have as necessary 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, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0147] R 201 ~R 203 Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R~R may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom (for example, fluorine and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above substituents may further have substituents when possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0148] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation in which R in the formula (ZaI) 201 ~R 203 each independently represents an organic group having no aromatic ring. The aromatic ring includes an aromatic ring containing a heteroatom. R 201 ~R 203 The carbon number of the organic group having no aromatic ring as R ~R 201 ~R 203 is preferably from 1 to 30, more preferably from 1 to 20. Each independently, R

[0149] R 201 ~R 203 is preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group. The alkyl group and cycloalkyl group of R R 201 ~R 203 may be further substituted by a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0150] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0151]

Chemical formula

[0152] In formula (ZaI-3b), R 1c ~R 5c each 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 independently represents a hydrogen atom, an alkyl group (e.g., t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each 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.

[0153] R 1c ~R 5c Any two or more of R 5c and R 6c 、R 6c and R 7c 、R 5c and R x 、and R x and R y may be bonded to each other to form a ring, and this ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0154] R 1c ~R 5c Any two or more of R 6c and R 7c 、and R x and R yExamples of the group formed by the combination of include alkylene groups such as butylene groups and pentylene groups. The methylene groups in this alkylene group may be substituted with heteroatoms such as oxygen atoms. R 5c and R 6c , and R 5c and R x The group formed by the combination of and is preferably a single bond or an alkylene group. Examples of the alkylene group include methylene groups and ethylene groups.

[0155] R 1c ~R 5c R 6c R 7c R x R y and, R 1c ~R 5c Any two or more of , 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 mutual connection of respectively may have substituents.

[0156] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0157] [Chemical formula]

[0158] In formula (ZaI-4b), l represents an integer from 0 to 2. r represents an integer from 0 to 8. R 13represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have substituents. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), an alkyl group, a halogenated alkyl group, 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 partially containing a cycloalkyl group). These groups may have substituents. R 14 When there are a plurality of R's, each independently represents the above-mentioned group such as a hydroxyl group. R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R's 15 may be bonded to each other to form a ring. When two R's 15 are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferable that two R's 15 are an alkylene group and are bonded to each other to form a ring structure. Note that the above-mentioned alkyl group, the above-mentioned cycloalkyl group, and the above-mentioned naphthyl group, and the ring formed by two R's 15 bonded to each other may have substituents.

[0159] In formula (ZaI-4b), the alkyl groups of R 13 , R 14 , and R 15 may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group, etc. Also, R 13 ~R 15 , and R x and R yEach of the substituents preferably forms an acid-decomposable group by any combination of substituents, respectively independently.

[0160] Next, the formula (ZaII) will be described. In the formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 As the aryl group of R 204 and R 205 a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R R 204 and R 205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0161] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Further, the substituents of R 204 and R 205 preferably form an acid-decomposable group by any combination of substituents, respectively independently.

[0162] Specific examples of the organic cation are shown below, but the present invention is not limited thereto.

[0163]

Chemical formula

[0164]

Chemical formula

[0165]

Chemical formula

[0166] (Solvent) The reaction in the above step (2) is typically carried out in the liquid phase. That is, the above reaction system typically contains a solvent. The solvent is not particularly limited as long as it can dissolve each component and carry out the above salt exchange. For example, water, alcohol solvents, nitrile solvents, halogen solvents, ester solvents, and mixed solvents using two or more of them can be mentioned.

[0167] The reaction temperature is preferably about 0 to 40 °C, more preferably about 10 to 30 °C. The reaction time varies depending on the reactivity between resin A and the exchange compound (compound A), the reaction temperature, etc., but usually, it is preferably 10 minutes or more and 24 hours or less, more preferably 0.25 to 6 hours. The amount of compound A used in the exchange in the above step (2) is usually preferably about 1 to 3 moles relative to the number of moles of the repeating unit derived from the compound represented by the general formula (P-1) in 1 mole of the above resin P.

[0168] The method for producing the resin of the present invention preferably includes the following aspects. The compound represented by the general formula (A-1) is a compound represented by any of the above formulas (A-3) to (A-5), and a step of converting a repeating unit derived from the compound represented by the general formula (A-1) into a repeating unit represented by the following formula (AP-1) after the polymerization step is included. A method for producing a resin.

[0169]

Chemical formula

[0170] The reaction in the step of converting a repeating unit derived from the compound represented by the general formula (A-1) into a repeating unit represented by the following formula (AP-1) after the polymerization step (hereinafter, also referred to as step (3)) is typically a hydrolysis reaction and is not particularly limited as long as it is after the polymerization step (step (1)). As a preferred embodiment, step (3) may be before step (2), may be after step (2), or may be carried out simultaneously with step (2). It is preferable that step (3) is before step (2). Step (3) can be carried out by a conventional method.

[0171] Further, the production method of the present invention preferably includes a step (hereinafter, also referred to as step (4)) of converting at least a part of the repeating unit represented by the above formula (AP-1) into a repeating unit represented by the following formula (AP-2).

[0172]

Chemical formula

[0173] In formula (AP-2), Y 2 represents a group that is eliminated by the action of an acid.

[0174] Examples of the group that is eliminated by the action of an acid (leaving group) include groups represented by formulas (Y1) to (Y5). 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) Formula (Y5): -C(=O)R 51

[0175] In Formula (Y1) and Formula (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), an aryl group (monocyclic or polycyclic), or a heteroaryl 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. Among them, Rx1 to Rx3 each preferably independently represent a linear or branched alkyl group, and more preferably each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring. The alkyl group of Rx1 to Rx3 is not particularly limited, and examples thereof include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group are preferable. The cycloalkyl group of Rx1 to Rx3 is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 20 carbon atoms, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are preferable. The aryl group of Rx1 to Rx3 is not particularly limited, and examples thereof include aryl groups having 6 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms are preferable, and examples thereof include phenyl group, naphthyl group, and anthryl group. Although the heteroaryl groups of Rx1 to Rx3 are not particularly limited, they may be monocyclic or polycyclic. The aromatic heterocyclic ring constituting the heteroaryl group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like. Although the alkenyl groups of Rx1 to Rx3 are not particularly limited, a vinyl group is preferred. As the ring formed by bonding two of Rx1 to Rx3, a cycloalkyl group is preferred. As the cycloalkyl group formed by bonding two of Rx1 to Rx3, 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 is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. One of the methylene groups constituting the ring of the cycloalkyl group formed by bonding two of Rx1 to Rx3 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. Further, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by a vinylene group. For the group represented by formula (Y1) or formula (Y2), for example, a mode in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group is preferred.

[0176] In formula (Y3), R 36 ~R 38 each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, and an alkenyl group. It is also preferred that R 36 is a hydrogen atom. In addition, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced by a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. Also, R 38 may combine with another substituent on the main chain of the repeating unit to form a ring. R 38 The group formed by the combination of R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0177] As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

[0178] [Chemical formula]

[0179] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl 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, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one methylene group may be replaced by a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It should be noted that it is preferable that 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 combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be combined to form a ring (preferably a 5- or 6-membered ring).

[0180] 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 be bonded to each other to form a non-aromatic ring. As Ar, an aryl group is preferred.

[0181] In formula (Y5), R 51 represents an alkyl group (linear or branched), an alkoxy group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an aryl group (monocyclic or polycyclic), an aryloxy group, or a heteroaryl group (monocyclic or polycyclic). The above alkyl group (linear or branched), cycloalkyl group (monocyclic or polycyclic), alkenyl group (linear or branched), aryl group (monocyclic or polycyclic), or heteroaryl group (monocyclic or polycyclic) is the same as the alkyl group (linear or branched), cycloalkyl group (monocyclic or polycyclic), alkenyl group (linear or branched), aryl group (monocyclic or polycyclic), or heteroaryl group (monocyclic or polycyclic) as Rx1 to Rx3 above, and the preferred ranges are also the same.

[0182] R 51 The alkoxy group of is not particularly limited, but examples include linear or branched alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 12 carbon atoms, and more preferably alkoxy groups having 1 to 6 carbon atoms. R 51 The aryl group in the aryloxy group of is not particularly limited, but preferably an aryl group having 6 to 20 carbon atoms, and examples include a phenyl group, a naphthyl group, and an anthryl group.

[0183] The above step (4) is after the above polymerization step (step (1)) and after the above step (3), and is not particularly limited. However, as a preferred embodiment, step (4) may be before the above step (2) or after the above step (2). Further, step (4) may be carried out simultaneously with the above step (2).

[0184] The above step is a step of protecting at least a part of the phenolic hydroxyl group in the repeating unit represented by the above formula (AP-1) with a group Y that is eliminated by the action of an acid, and can be carried out by a conventional method. 2 and can be carried out by a conventional method. Protecting at least a part of the phenolic hydroxyl group in the repeating unit represented by the above formula (AP-1) with a group Y that is eliminated by the action of an acid 2 which protects with a group Y that is eliminated by the action of an acid of the above phenolic hydroxyl group 2 The ratio of protection with the group Y that is eliminated by the action of an acid of the above phenolic hydroxyl group can be appropriately selected according to the composition of the resin to be synthesized.

[0185] Further, the method for producing the resin of the present invention preferably includes the following aspects. The compound represented by the above general formula (A-1) is the compound represented by the above formula (A-2), and includes a step of converting at least a part of the repeating unit represented by the above formula (A-2) into a repeating unit represented by the following formula (AP-2) after the above polymerization step. A method for producing a resin.

[0186]

Chemical formula

[0187] In formula (AP-2), Y 2 represents a group that is eliminated by the action of an acid. Y 2 has the same meaning as Y in formula (AP-2) in the above step (4), and the preferred range is also the same. 2 has the same meaning as Y in formula (AP-2) in the above step (4), and the preferred range is also the same.

[0188] The step of converting the repeating unit derived from the compound represented by the general formula (A-2) into a repeating unit represented by the following formula (AP-1) after the above polymerization step (hereinafter, also referred to as step (5)) is not particularly limited as long as it is after the above polymerization step (step (1)). As a preferred embodiment, step (5) may be before step (2) or after step (2). Further, step (5) may be carried out simultaneously with step (2).

[0189] The above step is a step of protecting at least a part of the phenolic hydroxyl group in the repeating unit represented by the above formula (A-2) with a group Y 2 that is eliminated by the action of an acid, and can be carried out by a conventional method. At least a part of the phenolic hydroxyl group in the repeating unit represented by the above formula (A-2) is protected with a group Y 2 that is eliminated by the action of an acid, and the ratio of protecting the phenolic hydroxyl group with the group Y 2 that is eliminated by the action of an acid can be appropriately selected according to the composition of the resin to be synthesized.

[0190] In the above formula (AP-2), Y 2 is preferably a group represented by the following formula (AY-4).

[0191]

Chemical formula

[0192] In formula (AY-4), R c11 , and R c12 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R c2 represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

[0193] In formula (AY-4), R c11 , R c12 , and R c2The alkyl group is not particularly limited, but the R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the alkyl groups of, and the preferred ranges are also the same as, those of the alkyl groups of R R c11 , R c12 , and R c2 The aryl group is not particularly limited, but the R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the aryl groups of, and the preferred ranges are also the same as, those of the aryl groups of R R c11 , R c12 , and R c2 The heteroaryl group is not particularly limited, but the R in the above formula (AY-1) a11 , R a12 , and R a2 can be the same as the heteroaryl groups of, and the preferred ranges are also the same as, those of the heteroaryl groups of R In a preferred embodiment, R c12 , R c2 are each independently an alkyl group. Also, in a preferred embodiment, R c11 is a hydrogen atom, and R c12 , R c2 are each independently an alkyl group.

[0194] The resin produced by the method for producing a resin of the present invention can be isolated and purified according to a conventional method after the reaction is completed.

[0195] ((A) Resin) The resin produced by the method for producing a resin of the present invention (hereinafter also referred to as resin (A)) has a repeating unit (hereinafter also referred to as repeating unit (a1)) that decomposes upon irradiation with actinic rays or radiation to generate an acid. The above resin is a compound that generates an acid upon exposure. The above repeating unit (a1) is typically a repeating unit represented by the following general formula (P-11).

[0196]

Chem.

[0197] In the general formula (P-11), R 11 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L 11 represents a single bond or a divalent linking group. Ar p11 represents an aromatic ring group or an aromatic heterocyclic group. M 11 + represents an organic cation.

[0198] R 11 The alkyl group of R is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 12 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. The aryl group is not particularly limited, and preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T. R 11 is preferably a hydrogen atom.

[0199] L 11 The divalent linking group of L is not particularly limited, and examples thereof include an alkylene group, a cycloalkylene group, an aromatic ring group, an aromatic heterocyclic group, -C(=O)-, -O-, and a divalent linking group formed by combining a plurality of these. The alkylene group is not particularly limited, and may be linear or branched. An alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is even more preferred. The cycloalkylene group is not particularly limited, but a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group having 3 to 10 carbon atoms is more preferred, and a cycloalkylene group having 1 to 6 carbon atoms is even more preferred.

[0200] The aromatic ring group is not particularly limited, and may be monocyclic or polycyclic. An aromatic ring group having 6 to 20 carbon atoms is preferred, an aromatic ring group having 6 to 14 carbon atoms is more preferred, and an aromatic ring group having 6 to 10 carbon atoms is even more preferred. The aromatic heterocyclic group is not particularly limited, and may be monocyclic or polycyclic. The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. The alkylene group, cycloalkylene group, aromatic ring group, and aromatic heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T. In a preferred embodiment, L 1 is preferably a single bond.

[0201] Ar p11 The aromatic ring group of is not particularly limited, and may be monocyclic or polycyclic. An aromatic ring group having 6 to 20 carbon atoms is preferred, an aromatic ring group having 6 to 14 carbon atoms is more preferred, and an aromatic ring group having 6 to 10 carbon atoms is even more preferred. The aromatic heterocyclic group is not particularly limited and may be monocyclic or polycyclic. The aromatic heterocyclic ring constituting the aromatic heterocyclic group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like. The aromatic ring group and the aromatic heterocyclic group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-described substituent T.

[0202] M 11 + The organic cation of M is not particularly limited, but the cation represented by the above formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by the above formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferable.

[0203] In the above resin, the repeating unit (a1) may be used alone or in combination of two or more.

[0204] In the above resin, the content of the repeating unit (a1) is preferably 0.5 to 30 mol%, more preferably 1 to 20 mol%, and still more preferably 2 to 15 mol% based on all the repeating units of the resin.

[0205] When the above resin is used in the method for producing a photosensitive or radiation-sensitive resin composition containing the above resin including the method for producing the above resin (hereinafter also referred to as "the method for producing the composition of the present invention"), the resin (A) is typically an acid-decomposable resin and usually contains a group (hereinafter also referred to as "acid-decomposable group") that decomposes by the action of an acid and increases in polarity, and preferably contains a repeating unit having an acid-decomposable group. Therefore, in the pattern forming method of the present invention, typically, when an alkaline developer is employed as the developer, a positive pattern is preferably formed, and when an organic developer is employed as the developer, a negative pattern is preferably formed. As the repeating unit having an acid-decomposable group, in addition to the (repeating unit having an acid-decomposable group) described later, a (repeating unit having an acid-decomposable group containing an unsaturated bond) is preferable.

[0206] (Repeating unit (a2) having an acid-decomposable group) The above resin (A) may further have a repeating unit having an acid-decomposable group (also referred to as "repeating unit (a2)").

[0207] The acid-decomposable group refers to a group that decomposes by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group that dissociates by the action of an acid. That is, the resin (A) has a repeating unit having a group that decomposes by the action of an acid to generate a polar group. The resin having this repeating unit increases in polarity by the action of an acid, increases its solubility in an alkaline developer, and decreases its solubility in an organic solvent. As the polar group, an alkali-soluble group is preferable. For example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, etc. acidic groups (typically, groups that dissociate in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide), and an alcoholic hydroxyl group can be mentioned.

[0208] The alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group and other than the hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom (for example, a hexafluoroisopropanol group, etc.) is excluded. The alcoholic hydroxyl group preferably has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0209] Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

[0210] Examples of the group (leaving group) that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y5). 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) Formula (Y5): -C(=O)R 51

[0211] In formula (Y1) and formula (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), or a heteroaryl 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. Among them, Rx1 to Rx3 each preferably independently represent a linear or branched alkyl group, and more preferably each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring. The alkyl group of Rx1 to Rx3 is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable. The cycloalkyl groups of Rx1 to Rx3 are not particularly limited, and examples thereof include cycloalkyl groups having 3 to 20 carbon atoms. Monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable. The aryl groups of Rx1 to Rx3 are not particularly limited, and examples thereof include aryl groups having 6 to 20 carbon atoms. An aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The heteroaryl groups of Rx1 to Rx3 are not particularly limited, and may be monocyclic or polycyclic. The aromatic heterocyclic ring constituting the heteroaryl group is not particularly limited, and examples thereof include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. The alkenyl groups of Rx1 to Rx3 are not particularly limited, and a vinyl group is preferable. The ring formed by bonding two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by bonding two of 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. One of the methylene groups constituting the cycloalkyl group formed by bonding two of Rx1 to Rx3 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. Further, one or more of the ethylene groups constituting the cycloalkane ring of these cycloalkyl groups may be replaced by a vinylene group. The group represented by the formula (Y1) or the formula (Y2) preferably has, for example, a mode in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group. When the composition in the method for producing the composition of the present invention is, for example, a chemically amplified radiation-sensitive or radiation-sensitive resin composition for EUV lithography, the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by bonding two of Rx1 to Rx3 preferably further have a fluorine atom or an iodine atom as a substituent.

[0212] In the formula (Y3), R 36 ~R 38 each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, and an alkenyl group. It is also preferable that R 36 is a hydrogen atom. The above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, in the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced by a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. Also, R 38 may be bonded to another substituent on the main chain of the repeating unit to form a ring. The group formed by bonding R 38 and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. When the composition in the method for producing the composition of the present invention is, for example, a chemically amplified radiation-sensitive or radiation-sensitive resin composition for EUV lithography, the monovalent organic group represented by R 36 ~R 38 and R 37 and R 38The ring formed by the combination of [groups] is further preferably having a fluorine atom or an iodine atom as a substituent.

[0213] As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

[0214] [Chemical formula]

[0215] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl 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, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced by a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It should be noted that it is preferable that 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 combining an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and an adamantyl group. In these embodiments, since the Tg (glass transition temperature) and the activation energy increase, in addition to ensuring the film strength, it is possible to suppress the fogging.

[0216] When the composition in the method for producing the composition of the present invention is, for example, a chemically amplified positive or negative resist composition for EUV exposure, the alkyl group, cycloalkyl group, aryl group, and a group combining these represented by L1 and L2 preferably further have a fluorine atom or an iodine atom as a substituent. Further, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom (that is, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups is replaced by a group containing a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group). Further, when the composition in the method for producing the composition of the present invention is, for example, a chemically amplified positive or negative resist composition for EUV exposure, in the alkyl group which may contain a hetero atom represented by Q, the cycloalkyl group which may contain a hetero atom, the aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, and a group combining these, the hetero atom is preferably a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0217] 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 be bonded to each other to form a non-aromatic ring. As Ar, an aryl group is preferable. In the method for producing the composition of the present invention, when the composition is, for example, a chemically amplified radiation-sensitive or radiation-sensitive resin composition for EUV lithography, it is also preferable that the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn each have a fluorine atom or an iodine atom as a substituent.

[0218] In formula (Y5), R 51 represents an alkyl group (linear or branched), an alkoxy group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), an aryl group (monocyclic or polycyclic), an aryloxy group, or a heteroaryl group (monocyclic or polycyclic). The above alkyl group (linear or branched), cycloalkyl group (monocyclic or polycyclic), alkenyl group (linear or branched), aryl group (monocyclic or polycyclic), or heteroaryl group (monocyclic or polycyclic) is the same as the alkyl group (linear or branched), cycloalkyl group (monocyclic or polycyclic), alkenyl group (linear or branched), aryl group (monocyclic or polycyclic), or heteroaryl group (monocyclic or polycyclic) as Rx1 to Rx3 above, and the preferred ranges are also the same.

[0219] R 51 The alkoxy group of R is not particularly limited, and examples thereof include linear or branched alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 12 carbon atoms, and more preferably alkoxy groups having 1 to 6 carbon atoms. R 51 The aryl group in the aryloxy group of R is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0220] From the viewpoint of excellent acid decomposability of the repeating unit, in the leaving group that protects the polar group, when a non-aromatic ring is directly bonded to the polar group (or its residue), it is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring does not have a halogen atom such as a fluorine atom as a substituent.

[0221] The group that is eliminated by the action of an acid may also be, for example, 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.

[0222] As the repeating unit having an acid-decomposable group, a repeating unit represented by the formula (A) is also preferable.

[0223]

Chemical formula

[0224] L1 represents a divalent linking group that may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom, and R2 represents a group that is eliminated by the action of an acid and 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. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group which may have a fluorine atom or an iodine atom (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an aromatic ring group, an aromatic heterocyclic group, etc.), and a linking group formed by linking a plurality of these. Among them, as L1, -CO-, an aromatic ring group, or - an aromatic ring group - an alkylene group having a fluorine atom or an iodine atom - is preferable, and -CO- or - an aromatic ring group - an alkylene group having a fluorine atom or an iodine atom - is more preferable. The aromatic ring group is not particularly limited, but a phenylene group is preferable. The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but 2 or more is preferable, 2 to 10 is more preferable, and 3 to 6 is still more preferable.

[0225] 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. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but 1 or more is preferable, 1 to 5 is more preferable, and 1 to 3 is still more preferable. The above alkyl group may contain a heteroatom such as an oxygen atom other than a halogen atom. The aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aryl group may contain a heteroatom such as an oxygen atom other than a halogen atom.

[0226] R2 represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. Examples of the leaving group that may have a fluorine atom or an iodine atom include groups represented by the above-described formulas (Y1) to (Y5) and that may have a fluorine atom or an iodine atom.

[0227] As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (AI) is also preferable.

[0228]

Chemical formula

[0229] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group that may have a substituent. 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 (monocyclic or polycyclic) group. However, 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. Two of Rx1 to Rx3 may combine to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0230] Examples of the alkyl group that may have a substituent represented by Xa1 include a methyl group or a group represented by -CH2-R 11 and the like. R 11represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. For example, it includes an alkyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or fewer carbon atoms which may be substituted by a halogen atom, and an alkoxy group having 5 or fewer carbon atoms which may be substituted by a halogen atom. An alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xa1, a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0231] Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and an -O-Rt- group. 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, as Rt, an alkylene group having 1 to 5 carbon atoms is preferred, and a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group is more preferred.

[0232] As the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferred. As the cycloalkyl groups of Rx1 to Rx3, monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred. As the aryl groups of Rx1 to Rx3, aryl groups having 6 to 10 carbon atoms are preferred, and examples include a phenyl group, a naphthyl group, and an anthryl group. As the alkenyl groups of Rx1 to Rx3, a vinyl group is preferred. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Also, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group is preferable. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the repeating unit represented by formula (AI), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0233] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0234] The repeating unit represented by formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

[0235] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. 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.

[0236] [ka]

[0237]

Chem.

[0238]

Chem.

[0239]

Chem.

[0240]

Chem.

[0241] The resin (A) may have, as a repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond. As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by the formula (B) is preferable.

[0242]

Chem.

[0243] In the formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. 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 Ry1 to Ry3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group, a cycloalkenyl group, etc.).

[0244] Examples of the alkyl group which may have a substituent and is represented by Xb include a methyl group or -CH2-R 11 and a group represented by the formula. R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom. An alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable. As Xb, a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.

[0245] Examples of the divalent linking group of L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. As L, a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group is preferable. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic ring group is preferable.

[0246] Examples of the alkyl group of Ry1 to Ry3 include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Examples of the cycloalkyl group of Ry1 to Ry3 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Examples of the aryl group of Ry1 to Ry3 preferably include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthryl group. Examples of the alkenyl group of Ry1 to Ry3 preferably include a vinyl group. As the alkynyl group of Ry1 to Ry3, an ethynyl group is preferred. As the cycloalkenyl group of Ry1 to Ry3, a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred. As the cycloalkyl group formed by bonding two of Ry1 to Ry3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. The cycloalkyl group or cycloalkenyl group formed by bonding two of Ry1 to Ry3 may be replaced, for example, by one of the methylene groups constituting the ring with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof. Further, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring of these cycloalkyl groups or cycloalkenyl groups may be replaced by a vinylene group. The repeating unit represented by the formula (B) is preferably, for example, a mode in which Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Rx3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0247] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0248] As the repeating unit represented by the formula (B), preferably, an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester-based repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0249] The content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more with respect to all the repeating units in the resin (A). Further, as the upper limit value, it is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less with respect to all the repeating units in the resin (A).

[0250] Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In the formula, Xb and L1 each represent any of the substituents and linking groups described above, Ar represents an aromatic group, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a substituent such as a carboxyl group, R' represents 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, Q represents a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof, and n and m each represent an integer of 0 or more.

[0251]

Chemical formula

[0252] [Chemical]

[0253] [Chemical]

[0254] [Chemical]

[0255] The resin (A) may contain, alone or in combination of two or more, a repeating unit having an acid-decomposable group.

[0256] The content of the repeating unit having an acid-decomposable group is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, based on all the repeating units in the resin (A). Further, as the upper limit value, it is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all the repeating units in the resin (A). In a preferred embodiment, the content of the repeating unit having an acid-decomposable group is preferably greater than 20 mol% based on all the repeating units of the resin (A).

[0257] The total content of the repeating unit (a1) and the repeating unit (a2) contained in the resin (A) (when there are a plurality of repeating units (a1) and repeating units (a2), the total thereof) is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol%, based on all the repeating units of the resin (A). In the case where the resin (A) has only the repeating unit (a1) and the repeating unit (a2), the total amount of the repeating unit (a1) and the repeating unit (a2) contained in the resin (A) is 100 mol%.

[0258] (Repeating unit (a3) having an acid group) Resin (A) may have a repeating unit having an acid group (also referred to as "repeating unit (a3)"). As the acid group, an acid group having a pKa of 13 or less is preferable. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and still more preferably 5 to 10. When resin (A) has an acid group having a pKa of 13 or less, the content of the acid group in resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among them, 0.8 to 6.0 mmol / g is preferable, 1.2 to 5.0 mmol / g is more preferable, and 1.6 to 4.0 mmol / g is still more preferable. If the content of the acid group is within the above range, development proceeds well, the formed pattern shape is excellent, and the resolution is also excellent. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferable. In addition, one or more (preferably 1 to 2) of the fluorine atoms of the above hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). As the acid group, -C(CF3)(OH)-CF2- thus formed is also preferable. In addition, one or more of the 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 acid group is preferably a repeating unit different from the repeating unit having a polar group protected by a leaving group that is eliminated by the action of the above acid. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0259] Examples of the repeating unit having an acid group include the following repeating units.

[0260]

Chemical formula

[0261] As the repeating unit having an acid group, a repeating unit represented by the following formula (1) is preferable.

[0262]

Chemical formula

[0263] 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 when there are a plurality of them, they may be the same or different. When having a plurality of Rs, they may jointly form a ring with each other. As R, a hydrogen atom is preferable. a represents an integer of 1 to 3. b represents an integer of 0 to (5 - a).

[0264] Hereinafter, repeating units having an acid group are exemplified below. In the formula, a represents 1 or 2.

[0265]

Chemical formula

[0266]

Chemical formula

[0267]

Chemical formula

[0268]

Chemical formula

[0269] Among the above repeating units, 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.

[0270]

Chemical formula

[0271]

Chemical formula

[0272] The content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on all the repeating units in the resin (A). Further, as the upper limit value, it is preferably 95 mol% or less, more preferably 85 mol% or less, and still more preferably 80 mol% or less, based on all the repeating units in the resin (A). In addition, when the resin (A) has only the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3), the total amount of the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3) contained in the resin (A) is 100 mol%.

[0273] In addition to the above repeating structural units, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. The resin (A) may have, for example, the repeating units described in

[0080] to

[0105] of JP-A-2020-95068, paragraphs

[0370] to

[0414] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0415] to

[0433] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0236] to

[0237] of US Patent Application Publication No. 2016 / 0026083A1, and paragraph

[0433] of US Patent Application Publication No. 2016 / 0070167A1.

[0274] As the resin (A), when the composition is used as a chemically amplified photoresist 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-based repeating units. In this case, any of those in which all of the repeating units are methacrylate-based repeating units, those in which all of the repeating units are acrylate-based repeating units, and those in which all of the repeating units are composed of methacrylate-based repeating units and acrylate-based repeating units can be used, and it is preferable that the acrylate-based repeating units are 50 mol% or less of all the repeating units.

[0275] The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). As a polystyrene equivalent value by the GPC method, the weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and further, the smoother the side wall of the resist pattern and the better the roughness property.

[0276] The present invention also relates to a resin having a repeating unit derived from a compound represented by the following general formula (P-1) and a repeating unit derived from a compound represented by any of the following formulas (A-2) to (A-5).

[0277]

Chemical formula

[0278] In the general formula (P-1), R 1 represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L1 represents a single bond or a divalent linking group. Ar p1 represents an aromatic ring group or an aromatic heterocyclic group. M + represents a lithium cation, a potassium cation, or an ammonium cation.

[0279]

Chemical formula

[0280] In formula (A-3), R b11 , and R b12 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R b2 represents an alkyl group, an aryl group, or a heteroaryl group.

[0281]

Chemical formula

[0282] In formula (A-4), R b3 represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group.

[0283]

Chemical formula

[0284] In formula (A-5), R b4 ~R b6 each independently represents an alkyl group, an aryl group, or a heteroaryl group.

[0285] The above resin is a resin corresponding to the reaction intermediate of the above resin (A). In the above resin, each group of the general formula (P-1) is the same as each group of the general formula (P-1) described in step (1) of the method for producing the resin of the present invention, and the preferred ranges are also the same. In the above resin, each group of formula (A-3) is the same as each group of formula (A-3) described in step (1) of the method for producing the resin of the present invention, and the preferred range is also the same. In the above resin, each group of formula (A-4) is the same as each group of formula (A-4) described in step (1) of the method for producing the resin of the present invention, and the preferred range is also the same. In the above resin, each group of formula (A-5) is the same as each group of formula (A-5) described in step (1) of the method for producing the resin of the present invention, and the preferred range is also the same.

[0286] The weight average molecular weight and dispersity of the above resin are the same as the weight average molecular weight and dispersity of the resin P described in step (1) of the method for producing the resin of the present invention, respectively, and the preferred ranges are also the same. The above resin can be synthesized according to a conventional method (for example, radical polymerization). The above resin can be synthesized, for example, with reference to the examples in the specification of the present application.

[0287] In the above resin, the repeating unit (also referred to as repeating unit (b1)) derived from the compound represented by the general formula (P-1) may be used alone or in combination of two or more.

[0288] In the above resin, the content of the repeating unit (b1) is preferably 0.5 to 30 mol%, more preferably 1 to 20 mol%, and even more preferably 2 to 15 mol% based on the total repeating units of the resin.

[0289] In addition, in the above resin, the repeating unit (also referred to as repeating unit (b2)) derived from the compound represented by any of formulas (A-2) to (A-5) may be used alone or in combination of two or more.

[0290] In the above resin, the content of the repeating unit (b2) is preferably 70 to 99.5 mol%, more preferably 80 to 99 mol%, and even more preferably 85 to 98 mol% based on the total repeating units of the resin.

[0291] The total content of repeating unit (b1) and repeating unit (b2) contained in the resin corresponding to the reaction intermediate of the above resin (A) (when there are a plurality of repeating units (b1) and repeating units (b2), the total thereof) is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more with respect to all the repeating units of resin (A). In addition, when the above resin has only repeating unit (b1) and repeating unit (b2), the total amount of repeating unit (b1) and repeating unit (b2) contained in the above resin is 100 mol%.

[0292] Method for producing a photosensitive or radiation-sensitive resin composition containing the above resin, including the method for producing the resin of the present invention The components that the photosensitive or radiation-sensitive resin composition (hereinafter, also referred to as "composition" or "the composition of the present invention") in the method for producing the composition of the present invention may contain will be described in detail. The above photosensitive or radiation-sensitive resin composition is typically a resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development. The above composition is typically a chemically amplified resist composition.

[0293] The above photosensitive or radiation-sensitive resin composition contains the above resin. The above resin is a resin (resin (A)) produced by the method for producing the resin of the present invention as described above. Resin (A) is as described above.

[0294] In the composition of the present invention, the content of resin (A) is preferably 50.0 to 99.9% by mass, more preferably 60.0 to 99.0% by mass, and still more preferably 70.0 to 98.0% by mass with respect to the total solid content of the composition. Resin (A) may be used alone or in combination of a plurality.

[0295] In the composition of the present invention, in a range that does not impair the effects of the present invention, in addition to the resin (A), a resin having no repeating unit (a1) (also referred to as resin (A')) may be contained. The resin (A') is not particularly limited as long as it is a resin having no repeating unit (a1). For example, in the resin (A), a resin having no repeating unit (a1) can be mentioned. When the composition of the present invention contains the resin (A'), in the composition of the present invention, the ratio of the content of the resin (A) to the content of the resin (A') is preferably 9:1 to 8:2 in terms of mass ratio.

[0296] <(B) Compound that generates an acid upon irradiation with actinic rays or radiation> The composition of the present invention may contain, within a range that does not impair the effects of the present invention, a compound that generates an acid upon irradiation with actinic rays or radiation different from the above resin (A) (also referred to as compound (B), ionic compound (B), photoacid generator, or photoacid generator (B)). A photoacid generator is a compound that generates an acid upon exposure. The photoacid generator (B) may be in the form of a low molecular weight compound or may be incorporated into a part of the polymer. Further, a combination of the form of a low molecular weight compound and the form incorporated into a part of the polymer may be used. When the photoacid generator (B) is in the form of a low molecular weight compound, its molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. In the present invention, it is preferable that the photoacid generator (B) is in the form of a low molecular weight compound.

[0297] As a preferred embodiment, the photoacid generator (B) is preferably an onium salt.

[0298] Examples of the photoacid generator (B) include a compound (onium salt) represented by "M" 21 + X - ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (such as aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acid), carboxylic acids (such as aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0299] “M 21 + X - ” in the compound represented by, M 21 + represents an organic cation. The organic cation is not particularly limited. Also, the valence of the organic cation may be 1 or 2 or more. Among them, the organic cation is not particularly limited, but the cation represented by the above formula (ZaI) (hereinafter also referred to as “cation (ZaI)”), or the cation represented by the above formula (ZaII) (hereinafter also referred to as “cation (ZaII)”) is preferred.

[0300] “M 21 + X - ” in the compound represented by, X - represents an organic anion. The organic anion is not particularly limited, and examples include monovalent or divalent or higher organic anions. As the organic anion, an anion with a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0301] Examples of the non-nucleophilic anion include sulfonate anions (such as aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions), carboxylate anions (such as aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylate anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0302] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The above alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom and may be a perfluoroalkyl group).

[0303] As the aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion, an aryl group having 6 to 14 carbon atoms is preferable, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0304] The above-mentioned alkyl group, cycloalkyl group, and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a nitro group, a halogen atom such as a fluorine atom and a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0305] As the aralkyl group in the aralkylcarboxylate anion, an aralkyl group having 7 to 14 carbon atoms is preferable. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0306] Examples of the sulfonylimide anion include a saccharin anion.

[0307] As for the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable. Further, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

[0308] Examples of the other non-nucleophilic anions include fluorinated phosphorus (e.g., PF6 - ), fluorinated boron (e.g., BF4 - ), and fluorinated antimony (e.g., SbF6 - ).

[0309] As the non-nucleophilic anion, an aliphatic sulfonate anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom is preferable. Among them, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferable, and a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferable. A plurality of non-nucleophilic anions may be bonded to each other via a linking group.

[0310] As the non-nucleophilic anion, an anion represented by the following formula (AN1) is also preferable.

[0311] [Chemical formula]

[0312] In formula (AN1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferable. Examples of the group that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. Also, as the group that is not an electron-withdrawing group, -R’, -OH, -OR’, -OCOR’, -NH2, -NR’2, -NHR’, or -NHCOR’ is preferable, each independently. R’ is a monovalent hydrocarbon group.

[0313] Examples of the monovalent hydrocarbon group represented by R’ include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; alkenyl groups such as ethenyl group, propenyl group, and butenyl group; monovalent linear or branched hydrocarbon groups such as alkynyl groups like ethynyl group, propynyl group, and butynyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups like cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group, and methylanthryl group; and monovalent aromatic hydrocarbon groups such as aralkyl groups like benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and anthrylmethyl group. Among them, R 1 and R 2is preferably, independently of each other, a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0314] L represents a divalent linking group. When a plurality of Ls are present, they may be the same or different from each other. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these. Among them, as the divalent linking group, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferable, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group- is more preferable.

[0315] As L, for example, a group represented by the following formula (AN1-1) is preferable. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0316] In formula (AN1-1), * a represents the bonding position with R 3 in formula (AN1). * b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1). X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R 2a and R 2b each independently represent a hydrogen atom or a substituent. R 2a and R2b When there are a plurality of each of them, the plurality of Rs 2a and Rs 2b may be the same or different from each other. However, when Y is 1 or more, -C(R 1 )(R 2 )- directly bonded to in formula (AN1) and the CR 2b in CR2 2b is other than a fluorine atom. 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 represents. However, when X + Y in formula (AN1-1) is 1 or more and all of Rs 2a and Rs 2b in formula (AN1-1) are all hydrogen atoms, Q is * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B 、or * A -SO2-* B represents. * A represents the bonding position on the R 3 side in formula (AN1), and * B represents the bonding position on the -SO3 - side in formula (AN1).

[0317] In formula (AN1), R 3 represents an organic group. The above-mentioned organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched-chain group (for example, a branched-chain alkyl group such as a t-butyl group), or a cyclic group. The above-mentioned organic group may or may not have a substituent. The above-mentioned organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0318] Among them, R 3 is preferably an organic group having a cyclic structure. The above-mentioned cyclic structure may be a monocyclic or polycyclic structure, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in the formula (AN1). The above-mentioned organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). The heteroatom may substitute one or more of the carbon atoms forming the cyclic structure. The above-mentioned organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, and a sultone ring group. Among them, the above-mentioned organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The above-mentioned hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may or may not have a substituent. The above-mentioned cycloalkyl group may be a monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and the number of carbon atoms is preferably 5 to 12. As the above-mentioned lactone group and sultone group, for example, in any of the structures represented by the above-mentioned formulas (LC1-1) to (LC1-21) and the structures represented by the formulas (SL1-1) to (SL1-3), a group obtained by removing one hydrogen atom from the ring member atoms constituting the lactone structure or sultone structure is preferred.

[0319] The non-nucleophilic anion may be a benzenesulfonic acid anion, and is preferably a benzenesulfonic acid anion substituted by a branched-chain alkyl group or a cycloalkyl group.

[0320] As the non-nucleophilic anion, an anion represented by the following formula (AN2) is also preferable.

[0321] [Chemical formula]

[0322] In formula (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.

[0323] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable. 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.

[0324] R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R 4 and R 5 , R 4 and R 5 may be the same or different from each other. R 4 and R 5 The alkyl group represented by has preferably 1 to 4 carbon atoms. The above alkyl group may have a substituent. As R4 and R5, a hydrogen atom is preferable.

[0325] L represents a divalent linking group. The definition of L is synonymous with L in formula (AN1).

[0326] W represents an organic group containing a cyclic structure. Among them, it is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among them, an alicyclic group having a bulky structure with 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable.

[0327] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. Among them, when it is a polycyclic heterocyclic group, the diffusion of the acid can be more suppressed. Further, the heterocyclic group may or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable.

[0328] The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spiro, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. Note that the carbon atoms (carbons contributing to ring formation) constituting the cyclic organic group may be carbonyl carbons.

[0329] As the anion represented by formula (AN2), 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 formula (AN2). q’ represents an integer from 0 to 10.

[0330] As the non-nucleophilic anion, an aromatic sulfonate anion represented by the following formula (AN3) is also preferred.

[0331]

Chemical formula

[0332] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may be further had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or more. As n, 1 to 4 is preferred, 2 to 3 is more preferred, and 3 is even more preferred.

[0333] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these.

[0334] B represents a hydrocarbon group. As B, an aliphatic hydrocarbon group is preferable, and an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group) is more preferable.

[0335] As the non-nucleophilic anion, a disulfonamide anion is also preferable. The disulfonamide anion is, for example, an anion represented by N - (SO2-R q )2. Here, R q represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable. Two Rs q may be bonded to each other to form a ring. The group formed by bonding two Rs q to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The number of carbon atoms of the above-mentioned alkylene group is preferably 2 to 4.

[0336] In addition, examples of the non-nucleophilic anion also include anions represented by the following formulas (d1-1) to (d1-4).

[0337]

Chemical formula

[0338]

Chemical formula

[0339] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0340] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). Z 2c The hydrocarbon group in may be linear, branched or may have a cyclic structure. Further, the carbon atoms in the hydrocarbon group (preferably, the carbon atoms which are 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 a substituent. The carbon atoms forming the norbornyl group may be carbonyl carbons. Further, "Z 2c -SO3 - " in formula (d1-2) is preferably different from the anions represented by the above formulas (AN1) to (AN3). For example, Z 2c is preferably other than an aryl group. Further, for example, in Z 2c , the atoms at the α-position and the β-position with respect to -SO3 - are preferably atoms other than carbon atoms having a fluorine atom as a substituent. For example, in Z 2c , the atom at the α-position and / or the atom at the β-position with respect to -SO3 - are preferably ring member atoms in a cyclic group.

[0341] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 represents a linear, branched or cyclic alkylene group, arylene group or carbonyl group, and Rf represents a hydrocarbon group.

[0342] In formula (d1-4), R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R53 and R 54 may be bonded to each other to form a ring.

[0343] The organic anion may be used alone or in combination of two or more.

[0344] The photoacid generator may be a betaine compound having a cationic part and an anionic part, and the two are linked by a covalent bond.

[0345] The content of the photoacid generator (B) in the composition of the present invention is not particularly limited, but in terms of more excellent effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more based on the total solid content of the composition. Further, the above content is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. The photoacid generator (B) may be used alone or in combination of two or more.

[0346] <Acid diffusion control agent (C)> The composition of the present invention may contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher that traps the acid generated from a photoacid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessive generated acid. The type of the acid diffusion control agent is not particularly limited, and examples thereof include a basic compound (CA), a low molecular compound (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) that is a relatively weak acid with respect to the photoacid generator, and a basic compound (CE) whose basicity is reduced or lost by irradiation with actinic rays or radiation. Further, for example, specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824. Specific examples of the basic compound (CE) whose basicity decreases or disappears upon irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824. Specific examples of the low-molecular compound (CB) having a nitrogen atom and a group that dissociates by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824. Specific examples of the onium salt compound (CE) having a nitrogen atom in the cation moiety include those described in paragraph

[0164] of International Publication No. 2020 / 066824. Further, specific examples of the onium salt compound (CD) that is a relatively weak acid with respect to the photoacid generator include those described in paragraphs

[0305] to

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

[0347] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

[0664] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of US Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of US Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of US Patent Application Publication No. 2016 / 0274458A1 can be preferably used as the acid diffusion controller.

[0348] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (when there are a plurality of types, the total thereof) is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass, based on the total solid content of the composition. In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more.

[0349] <Hydrophobic resin> The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike surfactants, it does not necessarily have to have a hydrophilic group in the molecule and does not necessarily have to contribute to the uniform mixing of polar and non-polar substances. The effects of adding the hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with respect to water, and suppressing outgassing.

[0350] From the viewpoint of uneven distribution on the film surface layer, the hydrophobic resin preferably has at least one of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin, and more preferably has two or more of them. Further, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be in the main chain of the resin or may be substituted in the side chain. Examples of the hydrophobic resin include the compounds described in paragraphs

[0275] to

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

[0351] 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, more preferably 0.1 to 15.0% by mass, based on the total solid content of the composition.

[0352] <Solvent> The composition of the present invention may contain a solvent. The solvent preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and at least one of (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Note that the solvent may further contain components other than components (M1) and (M2).

[0353] The inventors have found that when such a solvent is used in combination with the above-described resin, the coatability of the composition is improved and a pattern with a small number of development defects can be formed. Although the reason is not necessarily clear, the inventors consider that these solvents can suppress unevenness in the film thickness of the resist film and the generation of precipitates during spin coating because they have a good balance of solubility, boiling point, and viscosity of the above-described resin. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and the contents thereof are incorporated herein.

[0354] As described above, the solvent may further contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.

[0355] The content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, and more preferably determined so that the solid content concentration is 1 to 20% by mass. By doing so, the coatability of the composition of the present invention can be further improved. Note that the solid content means all components other than the solvent, and as described above, means components that form a chemically amplified photosensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the mass of components other than the solvent with respect to the total mass of the composition of the present invention. “Total solid content” refers to the total mass of components obtained by removing the solvent from the entire composition of the present invention. Also, the “solid content” is a component obtained by removing the solvent as described above, and may be solid or liquid at 25°C, for example.

[0356] <Surfactant> The composition of the present invention may contain a surfactant. When a surfactant is included, the adhesion is excellent and a pattern with fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactants include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 19395.

[0357] These surfactants may be used alone or in combination of two or more.

[0358] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and still more preferably 0.1 to 1.0% by mass based on the total solid content of the composition.

[0359] <Other Additives> The composition of the present invention may further contain a dissolution inhibitor compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0360] The composition of the present invention may further contain a dissolution inhibitor compound. Here, the "dissolution inhibitor compound" is a compound having a molecular weight of 3000 or less that decomposes by the action of an acid and has a reduced solubility in an organic developer.

[0361] The method for producing the composition of the present invention may include a step of mixing the resin contained in the above composition and other components that may be contained in the above composition as necessary.

[0362] [Use] The composition of the present invention relates to a photosensitive or radiation-sensitive resin composition that reacts upon irradiation with actinic rays or radiation and undergoes a change in properties. More specifically, the composition of the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as those for IC (Integrated Circuit), the manufacture of circuit boards such as liquid crystals or thermal heads, the production of imprint mold structures, other photolithography processes, or the manufacture of lithographic printing plates or acid-curable compositions. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, redistribution formation processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0363] 〔Pattern formation method〕 The procedure of the pattern formation method using the above resin production method is not particularly limited, but preferably has the following steps. Step 1: A step of producing the above resin by the resin production method, and Step 2: A step of forming a photosensitive or radiation-sensitive film (typically a "resist film") on a substrate using the photosensitive or radiation-sensitive resin composition containing the above resin Step 3: A step of exposing the photosensitive or radiation-sensitive film Step 4: A step of developing the exposed photosensitive or radiation-sensitive film with a developer to form a pattern Hereinafter, the procedures of the above respective steps will be described in detail.

[0364] <Step 1: Resin production step> Step 1 is a step of producing the above resin by the resin production method. The resin production method of the present invention is as described above.

[0365] <Step 2: Photosensitive or radiation-sensitive film formation step> Step 2 is a step of forming a photosensitive or radiation-sensitive film (typically a "resist film") on a substrate using the photosensitive or radiation-sensitive resin composition containing the above resin. The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition contains a resin produced by the production method of the present invention.

[0366] As a method for forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition, for example, a method of applying the actinic ray-sensitive or radiation-sensitive resin composition on the substrate can be mentioned. It is preferable to filter the actinic ray-sensitive or radiation-sensitive resin composition through a filter as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Also, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0367] The actinic ray-sensitive or radiation-sensitive resin composition can be applied onto a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the production of integrated circuit elements by an appropriate coating method such as a spinner or coater. The coating method is preferably spin coating using a spinner. The rotation speed when performing spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the actinic ray-sensitive or radiation-sensitive resin composition, the substrate may be dried to form a resist film. If necessary, various underlayer films (inorganic film, organic film, antireflection film) may be formed under the resist film.

[0368] As a drying method, for example, a method of drying by heating can be mentioned. Heating can be carried out by means provided in a normal exposure machine and / or a 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 still more preferably 80 to 130 °C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

[0369] The film thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but from the point that a more highly accurate fine pattern can be formed, it is preferably 10 to 120 nm. Among them, in the case of EUV exposure, the film thickness of the photosensitive ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. In the case of ArF immersion exposure, the film thickness of the photosensitive ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0370] Note that a top coat may be formed on the photosensitive ray-sensitive or radiation-sensitive film using a top coat composition. The top coat composition is preferably one that does not mix with the photosensitive ray-sensitive or radiation-sensitive film and can be uniformly coated on the upper layer of the photosensitive ray-sensitive or radiation-sensitive film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the descriptions in paragraphs

[0072] to

[0082] of JP-A-2014-059543. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-61648 on the photosensitive ray-sensitive or radiation-sensitive film. Specific examples of the basic compound that the top coat may contain include the basic compounds that the aforementioned photosensitive ray-sensitive or radiation-sensitive resin composition may contain. Also preferably, the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0371] <Step 3: Exposure step> Step 3 is a step of exposing the photosensitive ray-sensitive or radiation-sensitive film. Examples of the exposure method include irradiating the formed photosensitive ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, they are far ultraviolet rays with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.

[0372] It is preferable to perform baking (heating) after exposure and before development. Baking promotes the reaction in the exposed area, 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 carried out by means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. This step is also referred to as post-exposure baking.

[0373] <Process 4: Development Process> Process 4 is a process of developing the exposed radiation-sensitive or actinic ray-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-based developer).

[0374] Examples of the development method include, for example, a method of immersing the substrate in a tank filled with the developer for a certain period of time (dip method), a method of raising the developer on the substrate surface by surface tension and allowing it to stand still for a certain period of time for development (paddle method), a method of spraying the developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method). Also, after the step of performing development, a step of stopping development while substituting with another solvent may be carried out. The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0375] For the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited. Examples thereof include a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or an alkaline aqueous solution containing a cyclic amine or the like. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. Also, the pH of the alkaline developer is usually 10.0 to 15.0.

[0376] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent.

[0377] The above solvents may be mixed in plural, or may be mixed with solvents other than the above or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.

[0378] <Other processes> The above pattern forming method preferably includes a step of washing with a rinse solution after step 4.

[0379] As the rinse liquid used in the rinsing step after the development step using an alkaline developer, for example, pure water can be mentioned. In addition, a suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0380] The rinse liquid 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 resist pattern, and a solution containing a general organic solvent can be used. It is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent as the rinse liquid.

[0381] The method of the rinsing step is not particularly limited, and examples include a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time (dip method), and a method of spraying the rinse liquid onto the substrate surface (spray method). In addition, the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. By this step, the developer and the rinse liquid remaining between and inside the patterns due to baking are removed. In addition, this step also has the effect of softening 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 usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0382] In addition, the etching process of the substrate may be performed using the formed pattern as a mask. That is, the substrate (or the lower layer film and the substrate) may be processed using the pattern formed in step 4 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by performing dry etching on the substrate (or the underlying film and the substrate) using the pattern formed in Step 4 as a mask is preferred. Oxygen plasma etching is preferred for the dry etching.

[0383] The composition of the present invention and various materials used in the pattern forming method of the present invention (for example, solvents, developers, rinse liquids, compositions for forming antireflection films, compositions for forming top coats, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit is not particularly limited, and 0 mass ppt or more is preferred. Here, examples of the metal 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.

[0384] Examples of the method for removing impurities such as metals from various materials include filtration using a filter. Details of the filtration using a filter are described in paragraph

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

[0385] Examples of the method for reducing impurities such as metals contained in various materials include a method of selecting raw materials with a low metal content as raw materials constituting the various materials, a method of performing filter filtration on the raw materials constituting the various materials, and a method of performing distillation under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark), etc.

[0386] In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the above various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of metal components contained in the cleaning liquid used for cleaning the manufacturing apparatus. The content of metal components contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and still more preferably 1 mass ppt or less. The lower limit is not particularly limited, and 0 mass ppt or more is preferable.

[0387] For organic treatment liquids such as rinse liquids, a conductive compound may be added to prevent failures of chemical liquid pipes and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, and examples thereof include methanol. The addition amount is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, in terms of maintaining preferable development characteristics or rinse characteristics. The lower limit is not particularly limited, and 0.01 mass% or more is preferable. As the chemical liquid pipe, for example, various pipes coated with SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to an antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to an antistatic treatment can be used.

[0388] <Method for manufacturing an electronic device> The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method. As a preferred embodiment of the electronic device of the present invention, there is an embodiment in which it is mounted on an electric and electronic device (home appliances, OA (Office Automation), media-related devices, optical devices, communication devices, etc.).

Example

[0389] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the examples shown below. In addition, Example 1B, 1E, 2B, 3B, 9B, and 12B shall be read as Reference Example 1B, 1E, 2B, 3B, 9B, and 12B, respectively.

[0390] Examples 1A to 1E, Examples 2A to 2B, Examples 3A to 3B, Examples 4 to 6, Examples 7A to 7B, Example 8, Examples 9A to 9C, Examples 10 to 11, Examples 12A to 12B, Examples 13 to 16, Comparative Examples 1A to 1B, Comparative Examples 2 to 16 Using the monomers described in Table 1 and the solvents described in Table 1, resins P-1A to P-1E, resins P-2A to P-2B, resins P-3A to P-3B, resins P-4 to P-6, resins P-7A to P-7B, resin P-8, resins P-9A to P-9C, resins P-10 to P-11, resins P-12A to P-12B, resins P-13 to P-16, resins PC-1A to PC-1B, and resins PC-2 to PC-16 were synthesized as follows, and the allowable polymerization concentration in the synthesis of each resin was evaluated.

[0391] [Allowable polymerization concentration] The monomers were weighed at the molar ratios shown in Table 1 below so that the total mass of the monomers was 50 g, the solvents described in Table 1 were added, and after stirring for 30 minutes to dissolve, a monomer solution was prepared by passing it through a membrane filter (pore size 0.5 μm). Note that the amount of the solvent was calculated so that the "total mass of the monomers" was 40% by mass with respect to the "total mass of the monomers + total mass of the solvents (total solvent amount)", and 20% by mass of the total solvent amount was separately added to the reaction vessel, and 80% by mass of the total solvent amount was used for the above monomer solution. The initiator (dimethyl-2,2'-azobis(2-methylpropionate), 10 mol%) was dissolved in the monomer solution obtained as described above, and the monomer solution was dropped into the above reaction vessel containing 20% by mass of the solvent in the total amount of the solvent heated to 80°C over 4 hours. Then, the reaction was carried out at 80°C for 2 hours, and the reaction was stopped by allowing it to cool. For the obtained reaction solution 13 C-NMR (nuclear magnetic resonance) measurement was performed to confirm the monomer composition ratio in the resin. When the molar ratio of the repeating unit derived from monomer S in the resin was 90% or more with respect to the molar ratio at the time of charging monomer S, it was judged as polymerization acceptable. When it could not be judged as polymerization acceptable, the experiment was carried out by decreasing the monomer concentration of the reaction solution by 5% by mass each from the above 40% by mass, and the concentration at which polymerization was acceptable (acceptable polymerization concentration) was calculated. The evaluation results are shown in Table 1.

[0392]

Table 1

[0393]

Table 2

[0394] In Table 1, when the "total mass of monomers" was 40% by mass with respect to the "total mass of monomers + total mass of solvent (total solvent amount)" and it could be judged as polymerization acceptable, it was described as ">40". On the other hand, when the "total mass of monomers" was 15% by mass with respect to the "total mass of monomers + total mass of solvent (total solvent amount)" and it could not be judged as polymerization acceptable, it was described as "<15". In Table 1, the solvent ratio (mass ratio) indicates the ratio as "solvent A / solvent B".

[0395] The structure of monomer S in Table 1 is shown below.

[0396]

Chemical formula

[0397] The structures of monomers A-1 and A-2 in Table 1 are shown below.

[0398] [Chemical formula]

[0399] The solvents in Table 1 are as follows. SV-1: Methanol SV-2: Ethanol SV-3: 2-Propanol SV-4: 1-Methoxy-2-propanol (propylene glycol monomethyl ether) SV-5: Ethyl lactate SV-6: Butyl acetate SV-7: Propylene glycol monomethyl ether acetate SV-8: 2-Pentanone

[0400] As is clear from Table 1, in Examples 1A to 16, it can be seen that the polymerization allowable concentration is high for each corresponding comparative example. This is considered to indicate that the solubility of monomer S in the monomer solution is high. Therefore, according to M in the above general formula (P-1), + the amount of the solvent used in the polymerization step can be reduced, and the manufacturing cost can be reduced. Therefore, it can be seen that in the copolymerization step, by using the compound represented by the general formula (P-1), the resin can be easily manufactured.

[0401] Examples A-1 to A-3 (Synthesis of Resins PP-1 to PP-3 and PI-1) Resins PP-1 to PP-3 and PI-1 were synthesized as follows. Also shown are the composition ratios (molar% ratios; corresponding in order from the left), weight average molecular weights (Mw), and dispersities (Mw / Mn) of the repeating units in the obtained resins PP-1 to PP-3 and PI-1. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resins PP-1 to PP-3 and PI-1 were measured by GPC (solvent: dimethylformamide (DMF)). The composition ratio (molar% ratio) of the resin was measured by 13 C-NMR (nuclear magnetic resonance).

[0402] Example A-1 (Synthesis of Resin PP-1)

[0403] [Chemical formula]

[0404] Using the reaction solution obtained in Example 1A (resin P-1A) described in Table 1 above, the following synthesis was carried out. Ethyl acetate (1000 mL), water (500 mL), and triphenylsulfonium bromide (6.94 g, 20.2 mmol) were added to the obtained reaction solution, and the mixture was stirred at room temperature (23 °C) for 30 minutes. After removing the aqueous layer, water (500 mL) was added, and the operations of liquid separation and removal of the aqueous layer were repeated three times to wash the organic layer. After concentrating the obtained organic layer, 200 g of ethyl acetate was added for dilution, and then the solution was dropped into 2000 g of hexane / ethyl acetate = 8 / 2 (mass ratio) to precipitate the polymer, which was then filtered. The filtered solid was washed with 100 g of hexane / ethyl acetate = 8 / 2 (mass ratio). Thereafter, the washed solid was subjected to drying under reduced pressure to obtain 48.5 g of a resin (PI-1). The obtained resin (PI-1) (48.5 g) was dissolved in acetonitrile (450 mL), and triethylamine (15.1 g, 149 mmol) was added thereto. 1-Chloro-1-ethoxyethane (14.1 g, 130 mmol) synthesized by a conventional method was added thereto, and the mixture was reacted at room temperature for 3 hours. Water (500 mL) and ethyl acetate (1000 mL) were added to the obtained reaction solution, and liquid separation operation was performed to remove the aqueous layer. After concentrating the obtained organic layer, 200 g of ethyl acetate was added for dilution, and then the mixture was dropped into 2000 g of hexane / ethyl acetate = 9 / 1 (mass ratio) to precipitate the polymer, followed by filtration. The filtered solid was washed with 100 g of hexane / ethyl acetate = 8 / 2 (mass ratio). Thereafter, the washed solid was subjected to drying under reduced pressure to obtain 47.0 g of resin (PP-1). The Mw of the obtained resin (PP-1) was 8500, the dispersity was 1.80, and the composition ratio (molar ratio) of the repeating units was 60 / 35 / 5 in order from the left.

[0405] Example A-2 (Synthesis of Resin PI-1)

[0406]

Chemical formula

[0407] Compound (A-2) (47.3 g, 268 mmol) and compound (S-1) (2.69 g, 14.1 mmol) were weighed, and solvent SV-4 (40.5 g) and solvent SV-1 (13.5 g) were added. After stirring for 30 minutes to dissolve, a monomer solution was prepared by passing through a membrane filter (pore size 0.5 μm). Dimethyl-2,2’-azobis(2-methylpropionate) (6.50 g, 28.3 mmol) was dissolved in the obtained monomer solution to obtain a monomer solution for dropping. Solvent SV-4 (15.8 g) and solvent SV-1 (5.25 g) were added to the reaction vessel and heated to 80 °C, and the monomer solution for dropping was added thereto. The dropping was carried out over 4 hours. Then, the reaction was carried out at 80 °C for 2 hours, and the reaction was stopped by allowing to cool. 5N hydrochloric acid (11.3 mL, 56.5 mmol) was added to the obtained reaction solution, and the mixture was heated to 90 °C and reacted for 3 hours, and then the reaction was stopped by allowing to cool. Ethyl acetate (1000 mL), water (500 mL), sodium hydrogen carbonate (7.12 g, 84.8 mmol), and triphenylsulfonium bromide (4.84 g, 14.1 mmol) were added to the obtained reaction solution, and the mixture was stirred at room temperature for 30 minutes. After removing the aqueous layer, the operation of adding water (500 mL) for liquid separation and removing the aqueous layer was repeated 3 times to wash the organic layer. After concentrating the obtained organic layer, 150 g of ethyl acetate was added for dilution, and then the mixture was dropped into 1500 g of hexane / ethyl acetate = 8 / 2 (mass ratio) to precipitate the polymer, which was then filtered. The filtered solid was washed with 100 g of hexane / ethyl acetate = 8 / 2 (mass ratio). Then, the washed solid was subjected to drying under reduced pressure to obtain 32.1 g of resin (PI-1). The Mw of the obtained resin (PI-1) was 8000, the dispersity was 1.80, and the composition ratio (molar ratio) of the repeating unit was 95 / 5 in order from the left.

[0408] Example A-3 (Synthesis of Resin PP-2)

[0409]

Chemical Structure

[0410] Resin (PP-2) was synthesized in the same manner as the resin PI-1 used in the synthesis of the above resin PP-1, except that 1-chloro-1-ethoxyethane in the synthesis of resin PP-1 was changed to (2-(1-chloroethoxy)ethyl)cyclohexane, and the synthesis was carried out by the same synthesis method as resin PP-1. The Mw of the obtained resin (PP-2) was 8200, the dispersity was 1.82, and the composition ratio (molar ratio) of the repeating units was 60 / 35 / 5 in order from the left.

[0411] Example A-4 (Synthesis of Resin PP-3)

[0412]

Chemical formula

[0413] Resin (PP-3) was synthesized in the same manner as the resin PI-1 used in the synthesis of the above resin PP-1, except that 1-chloro-1-ethoxyethane in the synthesis of resin PP-1 was changed to 1-chloro-1-methoxy-2,2-dimethylpropane, and the synthesis was carried out by the same synthesis method as resin PP-1. The Mw of the obtained resin (PP-3) was 7900, the dispersity was 1.79, and the composition ratio (molar ratio) of the repeating units was 61 / 34 / 5 in order from the left.

[0414] Examples 2-1 to 2-3, Comparative Examples 2C-1 to 2C-3 [Variation in reproducibility] The variation in the composition ratio reproducibility when resins (PP-1 to PP-3) and the following resins (PP-1C to PP-3C) were repeatedly synthesized was evaluated as follows. Based on the above synthesis method, the synthesis of each resin was carried out 5 times, and the content (mol%) of the repeating unit having an acid-decomposable group with respect to all the repeating units of the resin in each run was determined, and the average value of the 5 runs was calculated. In all runs, when the above content (mol%) of the repeating unit having an acid-decomposable group was within the range of the above average value ±2 mol%, it was evaluated as A, and when it was not within the range of ±2 mol%, it was evaluated as B. In practical use, it is preferably A. The evaluation results are shown in Table 2.

[0415] As the comparative resins (PP-1C to PP-3C), resins having the same composition as the above resins (PP-1 to PP-3), synthesized by the method described below, were used.

[0416] Synthesis of Resin PP-1C

[0417]

Chemical formula

[0418] Compound (S-4) (20.2 g, 105 mmol), compound (S-1) (21.6 g, 180 mmol), compound (SR-4) (6.70 g, 15 mmol), and a polymerization initiator, dimethyl-2,2'-azobis(2-methylpropionate) (6.91 g, 30 mmol) were dissolved in a mixed solvent (155 g) having a mass ratio of propylene glycol monomethyl ether to methanol of 3 / 1. The same mixed solvent (38.8 g) was placed in a reaction vessel and dropped into the system at 80 °C over 4 hours under a nitrogen gas atmosphere. After the reaction solution was heated and stirred for 2 hours, it was allowed to cool to room temperature. The above reaction solution was diluted by adding 250 g of ethyl acetate. The diluted solution was dropped into 4000 g of hexane / ethyl acetate = 8 / 2 (mass ratio) to precipitate the polymer, which was then filtered. The filtered solid was washed with 200 g of hexane / ethyl acetate = 8 / 2 (mass ratio). Thereafter, the washed solid was subjected to drying under reduced pressure to obtain 35.5 g of resin (PP-1C). The Mw of the obtained resin (PP-1C) was 8000, the dispersity was 1.75, and the composition ratio (molar ratio) of the repeating units was 60 / 35 / 5 in order from the left.

[0419] Resins PP-2C to PP-3C were each synthesized in the same manner as resin PP-1C. As described above, the composition ratios of the respective repeating units in resins PP-2C and PP-3C are the same as the composition ratios of the respective repeating units in resins PP-2 and PP-3.

[0420]

Table 3

[0421] As is clear from Table 2, according to Examples 2-1 to 2-3, it can be seen that the resin can be produced with higher precision as compared with the comparative examples corresponding to each example.

[0422] (Examples 3-1 to 3-3, and Comparative Examples 3C-1 to 3C-2) <Preparation of Resist Composition> The components shown in Table 3 were dissolved in the solvent shown in Table 3, and this was filtered through a polyethylene filter having a pore size of 0.02 μm to prepare a resist composition. In addition, in the table, the numerical values in parentheses are the contents (parts by mass), and each abbreviation indicates the following, respectively. D-1: Tri-n-octylamine E-1: Salicylic acid SA-1: γ-Butyrolactone SA-2: Cyclohexanone SA-3: Propylene glycol monomethyl ether acetate SA-4: Propylene glycol monomethyl ether

[0423] The composition ratios (molar% ratios; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit in Resins PR-1 to PR-2 are also shown. Note that the weight average molecular weight (Mw) and dispersity (Mw / Mn) of Resins PR-1 to PR-2 were measured by GPC (solvent: dimethylformamide (DMF)). Also, the composition ratio (molar% ratio) of the resin was measured by 13 C-NMR (nuclear magnetic resonance). Resin PR-1 is a high molecular compound represented below. PR-1 was produced according to Example 1 of JP-A 2013-1715. The Mw of PR-1 was 13,400 and the dispersity was 1.57.

[0424] [Chemical formula]

[0425] Resin PR-2 is the resin shown below. Resin PR-2 was manufactured according to Example A-1. The Mw of PR-2 was 8200 and the dispersity was 1.80.

[0426] [Chemical formula]

[0427] [Table 4]

[0428] [Pattern formation method: EB exposure, alkali development (positive)] The above resist composition was uniformly applied onto a silicon substrate treated with hexamethyldisilazane using a spin coater, and heated and dried on a hot plate at 120°C for 90 seconds to form a resist film with a film thickness of 100 nm. The above resist film was pattern-irradiated using an electron beam lithography apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV). At this time, drawing was performed so that a 1:1 line and space pattern was formed. Immediately after electron beam lithography, it was heated on a hot plate at 110°C for 90 seconds, developed at 23°C for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, rinsed with pure water for 30 seconds, dried, a 1:1 line and space pattern with a line width of 50 nm was formed, and the obtained pattern was evaluated by the following method.

[0429] [Performance evaluation] [Roughness performance] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.). The exposure dose (electron beam irradiation dose) when resolving a 1:1 line and space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). For any 30 points in the 10-μm length direction of a 100-nm line pattern (a 1:1 line-and-space pattern with a line width of 50 nm) at the irradiation dose showing the above sensitivity, the distance from the reference line where there should be an edge was measured using a scanning electron microscope (S-9220 manufactured by Hitachi, Ltd.), the standard deviation was obtained, and 3σ (nm) was calculated.

[0430] [Etching resistance performance] Using the above resist composition, a resist film with a thickness of 200 nm was formed on a silicon wafer, and then, using an Ar / C4F6 / O2 gas (a mixed gas with a volume ratio of 100 / 4 / 2), the silicon wafer was subjected to a dry etching treatment for 60 seconds under the condition of a temperature of 23°C using a dry etching apparatus (HITACHI U-621 manufactured by Hitachi, Ltd.). The cross-sectional shape of each pattern was observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.), the remaining film amount was obtained, and the etching rate was calculated. (Judgment criteria) A: When the etching rate is less than 15 Å / sec B: When the etching rate is 15 Å / sec or more In practical use, it is preferably A.

[0431] The obtained evaluation results are shown in Table 3.

[0432] As shown in Table 3 above, it can be seen that a pattern excellent in roughness performance and etching resistance performance can be formed by the resist composition containing the resin obtained by the production method of the present invention. On the other hand, according to the comparative example, these performances were insufficient.

Claims

1. A method for producing a resin having a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid, the method including a step of polymerizing a compound represented by the following general formula (P-1) and a copolymerizable monomer compound. 【Chemical Formula 1】 In the general formula (P-1), R １ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L １ represents a single bond or a divalent linking group. Ar ｐ１ represents an aromatic ring group or an aromatic heterocyclic group. M ＋ represents a lithium cation or a potassium cation.

2. The method for producing a resin according to claim 1, wherein at least one of the copolymerizable monomer compounds is a compound represented by the following general formula (A-1). 【Chemical Formula 2】 In the general formula (A-1), R ２ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Ar ａ１ represents an (n + 1)-valent aromatic ring group or an (n + 1)-valent aromatic heterocyclic group. n represents an integer from 1 to 4. Y １ represents a hydrogen atom or a substituent. When n represents an integer from 2 to 4, a plurality of Y １ may be the same or different.

3. The method for producing a resin according to claim 2, wherein Y １ in the general formula (A-1) is a hydrogen atom or a group represented by any one of the following formulas (AY-1) to (AY-3). 【Chemical Formula 3】 In formula (AY-1), R ａ１１ and R ａ１２Each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R ａ２ represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position. [Chemical Formula 4] In formula (AY-2), R ａ３ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group. * represents the bonding position. [Chemical Formula 5] In formula (AY-3), R ａ４ to R ａ６ each independently represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

4. The method for producing a resin according to claim 2 or 3, wherein the compound represented by the general formula (A-1) is a compound represented by any one of the following formulas (A-2) to (A-5). [Chemical Formula 6] In formula (A-3), R ｂ１１ , and R ｂ１２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R ｂ２ represents an alkyl group, an aryl group, or a heteroaryl group. [Chemical Formula 7] In formula (A-4), R ｂ３ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group. [Chemical Formula 8] In formula (A-5), R ｂ４ to R ｂ６ each independently represents an alkyl group, an aryl group, or a heteroaryl group.

5. The compound represented by the general formula (A-1) is a compound represented by any one of the formulas (A-3) to (A-5), and the method for producing a resin according to claim 4 includes a step of converting a repeating unit derived from the compound represented by the general formula (A-1) after the polymerization step into a repeating unit represented by the following formula (AP-1). 【Chemical Formula 9】

6. The method for producing a resin according to claim 5 includes a step of converting at least a part of the repeating unit represented by the formula (AP-1) into a repeating unit represented by the following formula (AP-2). 【Chemical Formula 10】 In the formula (AP-2), Y ２ represents a group that is eliminated by the action of an acid.

7. The compound represented by the general formula (A-1) is a compound represented by the formula (A-2), and the method for producing a resin according to claim 4 includes a step of converting at least a part of the repeating unit represented by the general formula (A-2) after the polymerization step into a repeating unit represented by the following formula (AP-2). 【Chemical Formula 11】 In the formula (AP-2), Y ２ represents a group that is eliminated by the action of an acid.

8. In the formula (AP-2), Y ２ is a group represented by the following formula (AY-4), and the method for producing a resin according to claim 6 or 7 is provided. 【Chemical Formula 12】 In the formula (AY-4), R ｃ１１ , and R ｃ１２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R ｃ２ represents an alkyl group, an aryl group, or a heteroaryl group. * represents the bonding position.

9. The compound represented by the above general formula (P-1) is a compound represented by the following general formula (P-2), and the method for producing a resin according to any one of claims 1 to 8 is provided. [Chemical Formula 13] In the general formula (P-2), M ＋ is synonymous with M in the general formula (P-1) above. ＋

10. A method for producing a resin according to any one of claims 1 to 9, wherein a solvent is used in the polymerization step, and the content of the alcohol-based solvent is 20% by mass or more based on the total amount of the solvent.

11. A method for producing a resin according to claim 10, wherein the content of the alcohol-based solvent is 50% by mass or more based on the total amount of the solvent.

12. The method for producing a resin according to claim 10 or 11, wherein the alcohol-based solvent is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 1-methoxy-2-propanol, methyl lactate, ethyl lactate, and diacetone alcohol.

13. A method for producing a resin according to any one of claims 1 to 12, wherein before carrying out the polymerization step, a solution containing the compound represented by the general formula (P-1) is passed through a filter having a pore size of 0.05 to 5 μm, and then the polymerization step is carried out.

14. After the polymerization step, a step of exchanging the cation M ＋ in the repeating unit derived from the compound represented by the general formula (P-1) with an organic cation is included. A method for producing a resin according to any one of claims 1 to 13.

15. A method for producing a resin according to any one of claims 1 to 14, wherein the resin is a resin having a repeating unit having an acid-decomposable group.

16. A method for producing a photosensitive or radiation-sensitive resin composition containing the resin, which includes the method for producing a resin according to any one of claims 1 to 15.

17. A step of producing the resin by the method for producing a resin according to any one of claims 1 to 15, A step of forming a radiation-sensitive or radiation-sensitive resin film on a substrate using the radiation-sensitive or radiation-sensitive resin composition containing the resin, A step of exposing the radiation-sensitive or radiation-sensitive resin film, A step of developing the exposed radiation-sensitive or radiation-sensitive resin film with a developer to form a pattern, which is a pattern forming method.

18. A resin having a repeating unit derived from a compound represented by the following general formula (P-1) and a repeating unit derived from a compound represented by any one of the following formulas (A-2) to (A-5). [Chemical Formula 14] In the general formula (P-1), R １ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. L １ represents a single bond or a divalent linking group. Ar ｐ１ represents an aromatic ring group or an aromatic heterocyclic group. M ＋ represents a lithium cation or a potassium cation. [Chemical Formula 15] In the formula (A-3), R ｂ１１ , and R ｂ１２ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. R ｂ２ represents an alkyl group, an aryl group, or a heteroaryl group. [Chemical Formula 16] In the formula (A-4), R ｂ３ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heteroaryl group. [Chemical Formula 17] In the formula (A-5), R ｂ４ to R ｂ６Each independently represents an alkyl group, an aryl group, or a heteroaryl group.

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