Method for producing resin, method for producing active light ray-sensitive or radiation-sensitive resin composition, active light ray-sensitive or radiation-sensitive resin composition, active light ray-sensitive or radiation-sensitive film, pattern formation method, and method for manufacturing electronic device

Abstract

Provided are: a method for producing a resin, the method having (i) a step for polymerizing raw material monomers including specific monomers described in the description, in the presence of a nitroxide radical or a dithioester-based compound, wherein in step (i), a reaction solution containing a solvent, an initiator at a quantity of 80 mass% or more of the total initiator amount and a nitroxide radical or a dithioester-based compound at a quantity of 90 mass% or more of the total nitroxide radical or dithioester-based compound amount is charged in a reaction vessel, and at least some of the raw material monomers are added dropwise to the reaction solution at a temperature that is not lower than the decomposition temperature of the initiator; a method for producing an active light ray-sensitive or radiation-sensitive resin composition, which includes the method for producing a resin; an active light ray-sensitive or radiation-sensitive resin composition; an active light ray-sensitive or radiation-sensitive resin film obtained using the active light ray-sensitive or radiation-sensitive resin composition; a pattern formation method; and a method for manufacturing an electronic device.

Description

Method for producing resin, method for producing actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern forming method, and method for producing electronic device

[0001] The present invention relates to a method for producing a resin, a method for producing an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern-forming method, and a method for producing an electronic device. More specifically, the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern-forming method, and a method for producing an electronic device that can be suitably used in ultra-microlithography processes applicable to processes for producing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for producing high-density information recording media, as well as other photofabrication processes, as well as a method for producing a resin that can be used in the actinic ray- or radiation-sensitive resin composition, and a method for producing an actinic ray- or radiation-sensitive resin composition including the resin production method.

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. In recent years, with the increasing integration density of integrated circuits, there has been a demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technique for further improving resolution, the so-called immersion method, in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, various resist compositions that are effectively sensitive to various actinic rays or radiation have been developed.

[0004] Furthermore, various methods are known for producing resins used in resist compositions. For example, Patent Document 1 describes a method for producing a resin using a RAFT agent. Also, Patent Document 2 describes a method for producing a resin using a nitroxide radical.

[0005] Japanese Unexamined Patent Publication No. 2008-268875 Japanese Unexamined Patent Publication No. 10-288839

[0006] Recently, the performance required of resist compositions has been increasing. In particular, improvements in resolution, line width roughness (LWR) performance, and defect suppression performance are required when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern.

[0007] Therefore, an object of the present invention is to provide a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, and a method for producing an actinic ray-sensitive or radiation-sensitive resin composition that includes the method for producing the resin. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, an actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a method for forming a pattern using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.

[0008] The present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A method for producing a resin, comprising: (i) a step of polymerizing raw material monomers including a monomer represented by the following general formula (a) and a monomer represented by the following general formula (b) in the presence of a nitroxide radical or a dithioester compound; wherein in the step (i), a reaction solution containing a solvent, an initiator in an amount of 80% by mass or more relative to the total amount of the initiator, and a nitroxide radical or dithioester compound in an amount of 90% by mass or more relative to the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and then at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator:

[0010]

[0011] In general formula (a), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. １４ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0012]

[0013] In general formula (b), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0014] [2] The method for producing a resin according to [1], wherein in step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator relative to the total amount of the initiator, 90% by mass or more of a nitroxide radical or dithioester compound relative to the total amount of the nitroxide radical or dithioester compound, and a portion of the raw material monomers is placed in a reaction vessel, and then the remaining raw material monomers are added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator. [3] The method for producing a resin according to [2], wherein in step (i), the raw material monomers in the reaction solution are 1 to 50 mol % relative to the total amount of the raw material monomers. [4] The method for producing a resin according to any one of [1] to [3], wherein in step (i), the raw material monomers are added dropwise for 1 to 24 hours. [5] The method for producing a resin according to any one of [1] to [4], wherein in step (i), the reaction system is heated for less than 2 hours after adding the raw material monomers dropwise. [6] The method for producing a resin according to any one of [1] to [5], wherein the nitroxide radical is represented by the following general formula (N):

[0015]

[0016] In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

[0017] [7] The method for producing a resin according to any one of [1] to [6], wherein the dithioester compound is represented by the following general formula (Ra):

[0018]

[0019] In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

[0020] [8] The method for producing a resin according to any one of [1] to [7], wherein the dithioester compound is represented by the following general formula (Ra-2):

[0021]

[0022] In general formula (Ra-2), Ra １ and Ra ３ each independently represents an organic group.

[0023] [9] A method for producing a resin according to any one of [1] to [8], wherein in the general formula (a), L is a single bond.

[10] A method for producing a resin according to any one of [1] to [9], wherein in the general formula (a), Ar is a benzene ring group.

[11] A method for producing a resin according to any one of [1] to [9], wherein R in the general formula (a) is a benzene ring group. １４

[10] The method for producing a resin according to any one of [1] to

[10] , wherein

[0024]

[0025] In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

[0026]

[12] In the above general formula (b), L ２２

[13] In the general formula (b), L is an aromatic ring group having a valence of (m+1). ２１

[13] The method for producing a resin according to any one of [1] to

[12] , wherein

[0027]

[14] In the above general formula (b), R ２４ The method for producing a resin according to any one of [1] to

[13] , wherein the compound is represented by the following general formula (8):

[0028]

[0029] In general formula (8), R８１ , R ８２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８３ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８１ ~R ８３ may be linked to each other to form a ring. * indicates the bonding position to the O atom.

[0030]

[15] A method for producing an actinic ray-sensitive or radiation-sensitive resin composition, comprising the method for producing a resin according to any one of [1] to

[14] .

[0031]

[16] A polymer comprising a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B), wherein the terminal structure of the main chain is —O—N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ Each of R independently represents an organic group. Ｎ１ an actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) having a repeating unit represented by general formula (A) in a methanol-insoluble component, and a molar introduction rate (Ao) of the repeating unit represented by general formula (A) in a methanol-soluble component, and a molar introduction rate (Aw) of the repeating unit represented by general formula (A) in a methanol-soluble component, the molar introduction rate (Aw) of the repeating unit represented by general formula (A) being less than 1.75; a compound (B) that generates an acid upon irradiation with actinic rays or radiation; and a solvent (S).

[0032]

[0033] In general formula (A), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

[0034]

[0035] In general formula (B), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0036]

[17] The actinic ray-sensitive or radiation-sensitive resin composition according to

[16] , wherein in the general formula (A), L is a single bond.

[18] The actinic ray-sensitive or radiation-sensitive resin composition according to

[16] or

[17] , wherein in the general formula (A), Ar is a benzene ring group.

[19] The actinic ray-sensitive or radiation-sensitive resin composition according to

[16] or

[17] , wherein in the general formula (B), L ２２

[20] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[16] to

[18] , wherein in the general formula (B), L is an aromatic ring group having a valence of (m+1). ２１

[21] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[16] to

[19] , wherein R ２４ The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[16] to

[20] , wherein R is a substituted or unsubstituted alkyl group;

[0037]

[0038] In general formula (8), R ８１ , R ８２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.８３ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８１ ~R ８３ may be linked to each other to form a ring. * indicates the bonding position to the O atom.

[0039]

[22] The terminal structure of the main chain of the resin (A) is —S—C(═S)—S—R ａ３ (R ａ３ represents an organic group).

[23] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[16] to

[22] .

[24] A pattern forming method comprising the steps of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[16] to

[22] , exposing the actinic ray-sensitive or radiation-sensitive film to light, and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

[25] A method for producing an electronic device, comprising the pattern forming method according to

[24] .

[0040] The present invention can provide a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, and a method for producing an actinic ray-sensitive or radiation-sensitive resin composition.The present invention also can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, an actinic ray-sensitive or radiation-sensitive film that uses the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

[0041] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0042] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0043] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0044] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0045] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0046] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0047] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0048] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0049] The pKa can also be calculated by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0050] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be adopted.

[0051] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0052] [Method for Producing Resin] The present invention relates to a method for producing a resin, comprising: (i) a step of polymerizing raw material monomers including a monomer represented by the following general formula (a) and a monomer represented by the following general formula (b) in the presence of a nitroxide radical or a dithioester compound; in the step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of the initiator, and 90% by mass or more of the nitroxide radical or dithioester compound based on the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and then at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator:

[0053]

[0054] In general formula (a), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. １４ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0055]

[0056] In general formula (b), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0057] The method for producing the resin (A) described below is not particularly limited, but it can be preferably produced by the resin production method of the present invention. Note that the resin production method of the present invention can also produce resins other than the resin (A).

[0058] [Step (i) (Polymerization Step)] Step (i) in the present invention is a step of polymerizing raw material monomers including a monomer represented by the above general formula (a) and a monomer represented by the above general formula (b) in the presence of a nitroxide radical or a dithioester compound. In step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of the initiator, and 90% by mass or more of the nitroxide radical or dithioester compound based on the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

[0059] <Monomer represented by general formula (a)>

[0060]

[0061] In general formula (a), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. １４represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5.

[0062] R in general formula (a) １１ ~R １３ R each independently represents a hydrogen atom, an organic group, or a halogen atom, and preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １１ ~R １３ The alkyl group in R may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include 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. １１ ~R １３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３ The cycloalkyl group of R 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. １１ ~R １３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １１ ~R １３ The alkyl group contained in the alkoxycarbonyl group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. １３ is -CH ２ -R ａａ It is also preferable that R is a group represented by the following formula: ａａrepresents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and 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, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １３ may be bonded to L to form a ring.

[0063] R １１ , R １２ preferably represents a hydrogen atom. １３ preferably represents a hydrogen atom or a methyl group.

[0064] In the general formula (a), L represents a single bond or a divalent linking group. The divalent linking group represented by L is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R １０４ When L represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, and alkyl groups having 8 or less carbon atoms are preferred. It is preferable that L represents a single bond.

[0065] In the general formula (a), Ar represents a (k+1)-valent aromatic ring group. １２When it bonds to form a ring, it represents a (k+2)-valent aromatic ring group. When k is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent.

[0066] Specific examples of the (k+1)-valent aromatic ring group when k is an integer of 2 or greater include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (k+1)-valent aromatic ring group may further have a substituent. The substituent that the (k+1)-valent aromatic ring group may have is not particularly limited, but examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl; and halogen atoms such as fluorine atoms.

[0067] Ar preferably represents an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group, and even more preferably a benzene ring group.

[0068] R in general formula (a) １４ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or base.

[0069] R １４ Specifically, the group represented by the formula (3) that decomposes with an acid or a base to produce an —OH group is preferably a group represented by any one of the following general formulas (3) to (7). The groups represented by the general formulas (3) to (6) are base-decomposable groups, and the group represented by the general formula (7) is an acid-decomposable group.

[0070]

[0071] In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

[0072] R ３１ , R ４１ , R ５１ , and R ６１ Examples of the organic group represented by include an alkyl group, a cycloalkyl group, and an aryl group. The alkyl group is preferably 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, or a t-butyl group. The cycloalkyl group 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. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group.

[0073] R ３１ , R ４１ , R ５１ , and R ６１ The organic group represented by may further have a substituent, and the substituent is preferably a halogen atom such as a fluorine atom.

[0074] R ３１ , R ４１ , R ５１ , and R ６１ is preferably an alkyl group having 1 to 3 carbon atoms, a trifluoromethyl group, or a phenyl group.

[0075] R ７１ , R ７２ , and R ７３Examples of the organic group represented by R include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group. ７１ , R ７２ , and R ７３ The alkyl group, cycloalkyl group, and aryl group represented by R ３１ , R ４１ , R ５１ , and R ６１ Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ７１ , R ７２ , and R ７３ The heteroaryl group represented by is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having 5 to 10 membered rings, and specific examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group. ７１ , R ７２ , and R ７３ The alkenyl group represented by R is an alkenyl group having 2 to 10 carbon atoms. ７１ , R ７２ , and R ７３ The alkynyl group represented by R is an alkynyl group having 2 to 10 carbon atoms. ７１ , R ７２ , and R ７３ The above group represented by may further have a substituent.

[0076] R ７１ represents a hydrogen atom, and R ７２ , and R ７３ It is preferred that represents an alkyl group having 1 to 3 carbon atoms.

[0077] R １４ is more preferably a hydroxyl group or a group represented by formula (3), (4) or (7).

[0078] In formula (a), k represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0079] Examples of the monomer represented by formula (a) are shown below, but the invention is not limited to these.

[0080]

[0081] The amount of the monomer represented by formula (a) used is not particularly limited, but is preferably 10 to 90 mol %, more preferably 50 to 80 mol %, based on the total amount of raw material monomers. The monomer represented by formula (a) may be used alone or in combination of two or more.

[0082] <Monomer represented by formula (b)>

[0083]

[0084] In general formula (b), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0085] R in general formula (b) ２１ ~R ２３ R each independently represents a hydrogen atom, an organic group, or a halogen atom, and preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ２１ ~R ２３ The alkyl group, cycloalkyl group, halogen atom, and alkoxycarbonyl group represented by R １１ ~R １３ Examples of the alkyl group represented by the formula (I) include an alkyl group, a cycloalkyl group, a halogen atom, and an alkoxycarbonyl group.

[0086] R ２１ , R ２２preferably represents a hydrogen atom. ２３ preferably represents a hydrogen atom or a methyl group.

[0087] R ２４ Examples of the group that is decomposed and eliminated by the action of an acid and is represented by the formula (Y1) to (Y4) described below can be given. ２４ is also preferably represented by the following general formula (8).

[0088]

[0089] In general formula (8), R ８１ , R ８２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８３ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８１ ~R ８３ may be linked to each other to form a ring. * indicates the bonding position to the O atom.

[0090] R ８１ ~R ８３ The alkyl group represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Specific examples of the alkyl group include 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.

[0091] R ８１ ~R ８３ The cycloalkyl group represented by the formula (I) may be either a monocyclic or polycyclic group. ８１ ~R ８３ The number of carbon atoms in the cycloalkyl group represented by R is preferably 6 to 15, and more preferably 6 to 10. ８１ ~R ８３Specific examples of the cycloalkyl group represented by the formula (I) include 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.

[0092] R ８１ ~R ８３ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0093] R ８１ ~R ８３ The heteroaryl group represented by the formula (I) is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having a 5- to 10-membered ring. Specific examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

[0094] R ８１ ~R ８３ The alkenyl group represented by the formula (I) includes an alkenyl group having 2 to 10 carbon atoms.

[0095] R ８１ ~R ８３ The alkynyl group represented by the formula (I) includes an alkynyl group having 2 to 10 carbon atoms.

[0096] Also, R ８１ ~R ８３ may be bonded to form a ring. The ring may be either a monocyclic or polycyclic ring. The ring is preferably a cycloalkyl group, more preferably a 5- or 6-membered monocyclic cycloalkyl group. Specific examples of the ring include 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. R ８１ ~R ８３In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0097] L ２１ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R １０４ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0098] L ２１ preferably represents a single bond.

[0099] L ２２The aromatic ring group represented by represents, more specifically, an (m+1)-valent aromatic ring group. When m is 1, the divalent aromatic ring group is preferably, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent. When m is an integer of 2 or more, specific examples of the (m+1)-valent aromatic ring group include groups obtained by removing any (m-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (m+1)-valent aromatic ring group may further have a substituent. The substituent that the (m+1)-valent aromatic ring group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl.

[0100] L ２２ preferably represents an (m+1)-valent aromatic ring group, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0101] m represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.

[0102] The monomer represented by the above general formula (b) is preferably a monomer represented by the following general formula (b1).

[0103]

[0104] In general formula (b1), R ２１ ~R ２３ R each independently represents a hydrogen atom, an organic group, or a halogen atom. ２４ represents a group that is decomposed and eliminated by the action of an acid.

[0105] R in general formula (b1) ２１ ~R ２３ , and R ２４ represents R in the general formula (b). ２１ ~R ２３ , and R ２４ The same applies to preferred examples.

[0106] Examples of the monomer represented by formula (b) are shown below, but the invention is not limited to these.

[0107]

[0108] The amount of the monomer represented by formula (b) used is not particularly limited, but is preferably 10 to 90 mol %, more preferably 20 to 60 mol %, based on the total amount of raw material monomers. The monomer represented by formula (b) may be used alone or in combination of two or more.

[0109] In step (i), a monomer other than the monomer represented by general formula (a) and the monomer represented by general formula (b) may be used depending on the desired polymer structure. The amount of each monomer to be added may be determined depending on the desired polymer structure.

[0110] <Radical Polymerization Initiator> The reaction in the above step (i) uses a radical polymerization initiator. As the radical polymerization initiator, for example, azo-based initiators and peroxides are used to initiate polymerization. As the radical initiator, azo-based initiators are preferred, and azo-based initiators having an ester group, a cyano group, or a carboxyl group are preferred. Preferred initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), etc.

[0111] <Nitroxide Radical> The reaction in the above step (i) can be carried out in the presence of a nitroxide radical. The nitroxide radical is preferably represented by the following general formula (N). The nitroxide radical represented by general formula (N) that can be used in the production method of the present invention is a compound that exists stably in the form of a free radical, and is formed as a radical on an oxygen atom bonded to a nitrogen atom.

[0112]

[0113] In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

[0114] R Ｎ１ Examples of the organic group represented by R include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. Ｎ１ The organic group represented by is not particularly limited, but examples thereof include an alkyl group and an aryl group.

[0115] The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and the aryl group is preferably a phenyl group or naphthyl group having 6 to 10 carbon atoms.

[0116] R Ｎ１ The organic group represented by may further have a substituent, such as an alkyl group, an aryl group, an ester group, a hydroxyl group, a carbonyl group, a phosphate ester, or a carboxyalkyl group.

[0117] Two R's Ｎ１ may be bonded to form a ring. Ｎ１ Examples of the ring formed by bonding include a piperidine ring and a pyrrolidine ring. A methylene group forming the ring may be substituted with a carbonyl group. In a preferred embodiment, two or more nitroxide radicals represented by general formula (N) may be bonded via a single bond or a linking group.

[0118] Specific examples of nitroxide radicals include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (N-1 below), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-pyrrolidinyloxy radical (N-2 below), 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, and N,N-di-t-butylamineoxy radical. The 2,2,6,6-tetramethyl-1-piperidinyloxy radical (N-1 below) is preferably used in the present invention. Other examples include the following compounds N-3 to N-9.

[0119]

[0120] The ratio of the raw material monomer to the nitroxide radical is preferably 0.001 to 0.1 mol, more preferably 0.01 to 0.05 mol, of the nitroxide radical per 1 mol of the raw material monomer. When the ratio of the two is within the above range, the molecular weight and molecular weight distribution of the resin can be appropriately controlled, and the resin can be produced at an appropriate polymerization rate, which is preferable.

[0121] The ratio of the two to be used in combination is not particularly limited, but can be selected from the range of 0.1 to 2 moles, preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles of radical polymerization initiator per mole of nitroxide radical. It is preferable that the nitroxide radical does not also function as a polymerization initiator. Specifically, it is preferable that the nitroxide radical does not combine with the polymerization initiator and function as a polymerization initiator together.

[0122] <Dithioester Compound> The reaction in the above step (i) can be carried out in the presence of a dithioester compound. The dithioester compound is preferably represented by the following general formula (Ra). In the present invention, the dithioester compound refers to a compound having -S-C(=S)- in its structure.

[0123] In the general formula (Ra), Ra１ and Ra ２ each independently represents an organic group.

[0124] Ra １ Examples of the organic group represented by Ra include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. １ The organic group represented by is not particularly limited, but examples thereof include an alkyl group, an aryl group, and a heteroaryl group.

[0125] The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. The aryl group is preferably a phenyl group or naphthyl group having 6 to 10 carbon atoms. The heteroaryl group is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include those having 5 to 10 membered rings, such as a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, a pyrazole group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

[0126] Ra １ The organic group represented by may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, an amino group, a cyano group, a carboxy group, —CO—, —O—, and —NR １０４ - (R １０４ represents a hydrogen atom or an alkyl group), -S-, -SC(=S)-, and groups formed by combining these groups.

[0127] Ra ２ Examples of the organic group represented by Ra include organic groups having 1 to 30 carbon atoms, preferably organic groups having 1 to 20 carbon atoms, and more preferably organic groups having 1 to 10 carbon atoms. ２ The organic group represented by is not particularly limited, but examples thereof include an alkyl group, an aryl group, a heteroaryl group, an -S-alkyl group, an -S-aryl group, and an -S-heteroaryl group.

[0128] The alkyl group and the alkyl group in the -S-alkyl group are the same as those described above in Ra １The aryl group and the aryl group in the -S-aryl group include the alkyl groups represented by the above-mentioned Ra １ Examples of the heteroaryl group and the heteroaryl group in the -S-heteroaryl group include the aryl groups represented by the above-mentioned Ra １ Examples of heteroaryl groups include:

[0129] The dithioester compound represented by general formula (Ra) is preferably represented by the following general formula (Ra-2).

[0130]

[0131] In general formula (Ra-2), Ra １ and Ra ３ Each of Ra in general formula (Ra-2) independently represents an organic group. １ is Ra in the above general formula (Ra). １ The same applies to preferred examples of Ra in general formula (Ra-2). ３ The organic group represented by the general formula (Ra) is １ The preferred examples are also the same.

[0132] Examples of dithioester compounds include, but are not limited to, the following:

[0133]

[0134]

[0135] The ratio of the raw material monomer to the dithioester compound is preferably 0.001 to 0.1 mol, more preferably 0.01 to 0.05 mol, of the dithioester compound per 1 mol of the raw material monomer. When the ratio of the two is within the above range, the molecular weight and molecular weight distribution of the resin can be appropriately controlled, and the resin can be produced at an appropriate polymerization rate, which is preferable.

[0136] The ratio of the two to be used in combination is not particularly limited, but can be selected from the range of 0.1 to 2 moles, preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles of radical polymerization initiator per mole of dithioester compound.

[0137] <Solvent> The reaction in step (i) above is typically carried out in a liquid phase. That is, the reaction system above typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, but examples thereof include alcohol-based solvents, ether-based solvents, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, dialkylene glycol dialkyl ethers, cyclic lactones, linear or cyclic ketones, alkylene carbonates, alkyl carboxylates, alkyl alkoxyacetates, alkyl pyruvates, and hydrocarbon-based solvents. Other usable solvents include, for example, the solvents described in U.S. Patent Application Publication No. 2008 / 0248425 A1, paragraphs

[0244] and thereafter.

[0138] The alcohol solvent is not particularly limited as long as it contains —OH, and examples thereof include 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, and diacetone alcohol.

[0139] The ether solvent is not particularly limited as long as it contains —O—, and may be either chain or cyclic. Examples of the ether solvent include tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

[0140] Preferred 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.

[0141] Preferred examples of alkylene glycol monoalkyl ethers 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. Preferred examples of dialkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Note that alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers are included in the alcohol-based solvents.

[0142] Examples of dialkylene glycol dialkyl ethers include diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether, etc. Dialkylene glycol dialkyl ethers are included in the ether solvents.

[0143] Preferred examples of cyclic lactones 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.

[0144] Examples of chain or cyclic ketones include 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, and 2-nonane. Preferred examples of the cyclohexane-1,1-dione include cyclohexane, 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, and 3-methylcycloheptanone.

[0145] Preferred examples of alkylene carbonates include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate. Preferred examples of alkyl carboxylates include butyl acetate and acetic anhydride.

[0146] Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate. Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

[0147] Examples of hydrocarbon solvents include toluene, dichlorobenzene, and chlorobenzene.

[0148] These solvents may be used alone or in combination of two or more.

[0149] <Polymerization Reaction> The polymerization reaction in step (i) is carried out in the presence of a nitroxide radical or a dithioester compound. By carrying out radical polymerization via these compounds, the polydispersity (Mw / Mn) of the resulting polymer can be kept low.

[0150] In step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of initiators, and 90% by mass or more of a nitroxide radical or dithioester compound based on the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator. This improves the compositional uniformity of each polymer in the polymer (hereinafter referred to as polymer (X1)) obtained in step (i). This is also preferable from the viewpoints of dispersion, safety, etc.

[0151] The reaction solution may be charged into a reaction vessel and then heated to a temperature equal to or higher than the decomposition temperature of the initiator, or the heated reaction solution may be added dropwise to the reaction vessel.

[0152] From the viewpoint of uniformity of the polymer composition, the reaction solution contains 80% by mass or more of the initiator used, preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and particularly preferably 100% by mass, based on the total amount of the initiator.

[0153] From the viewpoint of uniformity of the polymer composition, the reaction solution contains 90% by mass or more of the nitroxide radical or dithioester compound used, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass, of the total amount of the nitroxide radical or dithioester compound.

[0154] It is also preferable that the reaction solution contains some of the raw material monomers. That is, in step (i), it is also preferable to place a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of initiators, 90% by mass or more of a nitroxide radical or dithioester compound based on the total amount of nitroxide radicals or dithioester compounds, and some of the raw material monomers in a reaction vessel, and then dropwise add the remaining raw material monomers to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator. The amount of raw material monomers in the reaction solution is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, and even more preferably 1 to 10 mol %, based on the total amount of raw material monomers.

[0155] The raw material monomers to be dropped into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator are typically dropped as a raw material monomer solution containing a solvent. The raw material monomer solution may contain 10% by mass or less of the initiator, 10% by mass or less of the nitroxide radical or dithioester compound, but it is preferable that the raw material monomer solution does not contain these.

[0156] When the raw material monomer is dropped into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator, it is preferable that the reaction solution is heated to at least the decomposition temperature of the initiator or higher. The upper limit of the heating temperature is, for example, 150°C.

[0157] The dropping time of the raw material monomers to be dropped into the reaction solution is preferably 1 to 24 hours. By setting the dropping time within this range, thermal decomposition of the polymer can be suppressed.

[0158] Furthermore, the time for heating the reaction system after dropping the raw material monomers into the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator is preferably less than 2 hours. By setting the heating time to less than 2 hours, the uniformity of the polymer composition can be improved. The heating time is preferably 0 to 1 hour, more preferably 0 to 30 minutes.

[0159] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and may be carried out in the presence of a chain transfer agent (e.g., alkyl mercaptan) as needed.

[0160] The monomer concentration in the reaction system is preferably 20 to 80% by mass, more preferably 25 to 70% by mass.

[0161] <Polymer (X1)> The polymer (X1) obtained by the above step (i) will be described. The polymer (X1) contains a repeating unit represented by the following general formula (AX) and a repeating unit represented by the following general formula (B), and has a nitroxide radical residue or a dithioester compound residue as a terminal structure of the main chain.

[0162]

[0163] In general formula (AX), R １１ ~R １３ , L, Ar, R １４ , and k is R in the above general formula (a). １１ ~R １３ , L, Ar, R １４ , and k have the same meanings, and preferred examples are also the same.

[0164]

[0165] In general formula (B), R ２１ ~R ２３ , L ２１ , L ２２ , R ２４ and m is R in the above general formula (b). ２１ ~R ２３ , L ２１ , L ２２ , R ２４ and m have the same meanings, and preferred examples are also the same.

[0166] The polymer (X1) may have a repeating unit other than the repeating unit represented by the general formula (A) and the repeating unit represented by the general formula (B).

[0167] The polymer (X1) has a nitroxide radical residue or a dithioester compound residue as a terminal structure of the main chain. Specifically, —O—N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１may be bonded to form a ring) (hereinafter, collectively referred to as "specific structure"). Ｎ１ represents R in the above general formula (N). Ｎ１ and preferred examples are also the same, or represent an organic group containing another polymer segment. ａ２ represents R in the above general formula (Ra). ａ２ In a preferred embodiment, the polymer (X1) has a main chain terminal structure represented by -S-C(=S)-S-R ａ３ (R ａ３ represents an organic group). ａ３ represents R in the above general formula (Ra-2). ａ３ and preferred examples thereof are also the same, or represent an organic group containing another polymer segment.

[0168] The term "terminal structure of the main chain of polymer (X1)" refers to a terminal structure other than the structure corresponding to the repeating unit of polymer (X1). The term "polymer (X1) having a nitroxide radical residue or a dithioester compound residue (specifically, the above-mentioned specific structure) at a terminal structure of the main chain" means that polymer (X1) has a nitroxide radical residue or a dithioester compound residue (specifically, the above-mentioned specific structure) at least at one terminal structure of the main chain.

[0169] The terminal structure of the main chain is １ H-NMR, １３ This can be confirmed by C-NMR or the like.

[0170] The polymer (X1) and the resin obtained by the resin production method of the present invention may be a linear polymer, a star polymer, or a branched polymer. The main chain structure of the polymer (X1) refers to the main chain structure of a polymer segment in the case of a star polymer or a branched polymer. Furthermore, at least one of the terminal structures of the main chain structures of the multiple polymer segments may have the specific structure described above. The same applies to the resin obtained by the resin production method of the present invention.

[0171] When the method for producing a resin of the present invention does not include the following step (ii) or step (iii), the polymer (X1) can become the resin (A) described below. That is, in the repeating unit represented by the general formula (AX) above, R １４ When is a hydroxyl group, it can be a repeating unit corresponding to the repeating unit represented by general formula (A) in the resin (A) described below.

[0172] The resin production method of the present invention may include steps other than the step (i) above, such as step (ii) a deprotection step and step (iii) a reprotection step.

[0173] [Step (ii) (Deprotection Step)] Step (ii) is a step of deprotecting groups that may be contained in the polymer (X1) and that generate —OH groups upon decomposition with an acid or base to form —OH groups.

[0174] <Decomposition Reaction of Base-Decomposable Group> The R １４ is a base-decomposable group, in step (ii), R １４ can be decomposed with a base to form a repeating unit represented by the following general formula (AX2).

[0175]

[0176] In general formula (AX2), R １１ ~R １３ , L, Ar, and k are R in the above general formula (a). １１ ~R １３ , L, Ar, and k, and preferred examples thereof are also the same.

[0177] (Base) Examples of the base that can be used include triethylamine, tetra-n-butylammonium fluoride, pyridine, diazabicycloundecene, etc. The amount of the base is preferably 1 to 5 molar equivalents, more preferably 1.2 to 3 molar equivalents, relative to the base-decomposable groups in the resin.

[0178] (Solvent) The base decomposition reaction is typically carried out in a liquid phase. That is, the above reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0179] These solvents may be used alone or in combination of two or more.

[0180] The reaction temperature is usually 10° C. to 100° C., preferably 20° C. to 80° C., and more preferably 40° C. to 80° C. The reaction time is usually 3 to 48 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours.

[0181] <Decomposition Reaction of Acid-Decomposable Group> The R １４ is an acid-decomposable group, in step (ii), R １４ can be decomposed with an acid to give the repeating unit represented by the above general formula (AX2).

[0182] (Acid) Examples of the acid that can be used include hydrochloric acid, p-toluenesulfonic acid, hydrobromic acid, etc. The amount of the acid is preferably 1 to 5 molar equivalents, more preferably 1.2 to 3 molar equivalents, relative to the acid-decomposable groups in the resin.

[0183] (Solvent) The acidolysis reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0184] These solvents may be used alone or in combination of two or more.

[0185] The reaction temperature is usually 10° C. to 100° C., preferably 20° C. to 80° C., and more preferably 40° C. to 80° C. The reaction time is usually 3 to 48 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours.

[0186] When the resin production method of the present invention includes the above step (ii) but does not include the following step (iii), the polymer obtained by steps (i) and (ii) (hereinafter referred to as polymer (X2)) can be the resin (A) described below. That is, the repeating unit represented by general formula (AX2) in polymer (X2) can be the repeating unit corresponding to the repeating unit represented by general formula (A) in resin (A) described below.

[0187] [Step (iii) (Reprotection Step)] The method for producing a resin of the present invention may further include a step of protecting the —OH group in the repeating unit represented by general formula (AX2) contained in the polymer (X2) obtained in step (ii).

[0188] In the step (iii), the polymer obtained in the step (ii) is reacted with a halogenated compound represented by X-Rc to reprotect the —OH group in the repeating unit represented by general formula (AX2) above, thereby converting it into a repeating unit represented by general formula (AX3) below.

[0189]

[0190] In the compound represented by X-Rc, X represents a halogen atom, preferably a chlorine atom. Rc represents a group that is eliminated by the action of an acid. Specific examples of the elimination group include the elimination groups described below.

[0191] In general formula (AX3), R １１ ~R １３ , L, Ar, and k are R in the above general formula (a). １１ ~R １３ , L, Ar, and k, and preferred examples thereof are also the same.

[0192] In this way, by the step (iii), a repeating unit having a group that is decomposed by a desired acid to generate an --OH group can be introduced into the polymer.

[0193] The amount of the compound represented by X-Rc to be added is not particularly limited, and may be adjusted appropriately depending on the desired polymer structure.

[0194] (Base) The protection reaction can be carried out in the presence of a base. Examples of the base that can be used include triethylamine, pyridine, and potassium carbonate. The amount of the base used can be, for example, 1 to 5 moles per mole of the compound represented by X-Rc.

[0195] (Solvent) The reaction is typically carried out in a liquid phase. That is, the reaction system typically further contains a solvent. The solvent is not particularly limited as long as it dissolves each component, and examples thereof include the solvents listed in step (i).

[0196] These solvents may be used alone or in combination of two or more.

[0197] The reaction temperature is usually −10° C. to 30° C., preferably −10° C. to 20° C., and more preferably 0° C. to 20° C. The reaction time is usually 1 to 6 hours, preferably 1 to 4 hours, and more preferably 1 to 2 hours.

[0198] When the resin production method of the present invention includes the above steps (ii) and (iii), the polymer obtained by steps (i) to (iii) (hereinafter referred to as polymer (X3)) can also be the resin (A) described below. That is, when a part of the repeating units represented by general formula (AX2) in polymer (X2) obtained after the deprotection step remains in polymer (X3) after the reprotection step, the repeating units represented by general formula (AX2) can be the repeating units corresponding to the repeating units represented by general formula (A) in resin (A) described below.

[0199] The resin obtained by the production method of the present invention has a low dispersity (Mw / Mn) of generally less than 1.40. The dispersity is preferably 1.35 or less, more preferably 1.30 or less, particularly preferably 1.25 or less, and most preferably 1.20 or less. The lower limit of the dispersity is more than 1.0.

[0200] Furthermore, the resin obtained by the production method of the present invention has small variations in the incorporation ratio of various raw material monomers between polymers, and therefore the variations in composition between polymers are small.

[0201] [Method for producing actinic ray-sensitive or radiation-sensitive resin composition] The present invention also relates to a method for producing an actinic ray-sensitive or radiation-sensitive resin composition, including the method for producing the resin described above.

[0202] The actinic ray-sensitive or radiation-sensitive resin composition obtained by the above-mentioned production method contains a resin (P) obtained by the above-mentioned resin production method. The resin (P) is not particularly limited as long as it is a polymer obtained via the above-mentioned step (i), and examples thereof include the above-mentioned polymers (X1) to (X3).

[0203] The weight average molecular weight (Mw) of the resin (P), as a polystyrene equivalent value measured by GPC, is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is preferably 30,000 or less, more preferably 15,000 or less.

[0204] The dispersity (molecular weight distribution, Pd, Mw / Mn) of the resin (P) is preferably less than 1.40, more preferably 1.35 or less, even more preferably 1.30 or less, particularly preferably 1.25 or less, and most preferably 1.20 or less. The lower limit of the dispersity is greater than 1.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0205] In the actinic ray-sensitive or radiation-sensitive resin composition obtained by the above production method, the content of resin (P) is preferably 40.0 to 99.9 mass%, more preferably 60.0 to 90.0 mass%, based on the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition obtained by the above production method. Resin (P) may be used alone or in combination of two or more. When two or more resins (P) are used, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0206] Components other than the resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition obtained by the above production methods include components other than the resin (A) described in the section on actinic ray-sensitive or radiation-sensitive resin compositions below (e.g., a compound (B) that generates an acid upon irradiation with actinic rays or radiation, a solvent (S), etc.). The actinic ray-sensitive or radiation-sensitive resin composition obtained by each of the above production methods can be produced by mixing the resin (P) obtained by the above-mentioned resin production method with other components as necessary. The mixing step is not particularly limited.

[0207] The present invention also relates to the following actinic ray-sensitive or radiation-sensitive resin composition.

[0208] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B), Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１ may be bonded to form a ring), and the ratio (Aw / Ao) of the molar introduction rate (Ao) of the repeating unit represented by general formula (A) in the methanol-insoluble component to the molar introduction rate (Aw) of the repeating unit represented by general formula (A) in the methanol-soluble component is less than 1.75; a compound (B) that generates an acid when irradiated with actinic rays or radiation; and a solvent (S).

[0209]

[0210] In general formula (A), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

[0211]

[0212] In general formula (B), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0213] Although the mechanism by which the above-mentioned effects are obtained by applying the resin obtained by the above-described resin production method of the present invention to an actinic ray- or radiation-sensitive resin composition, and by the composition of the present invention, is not fully understood, the present inventors speculate as follows. The resin obtained by the resin production method of the present invention is thought to have excellent resolution and roughness performance due to the small variation in composition between resins. The resin (A) contained in the composition of the present invention contains a repeating unit represented by the general formula (A) above and a repeating unit represented by the general formula (B) above, and the ratio (Aw / Ao) of the molar introduction rate (Ao) of the repeating unit represented by the general formula (A) in the methanol-insoluble component to the molar introduction rate (Aw) of the repeating unit represented by the general formula (A) in the methanol-soluble component is less than 1.75. Therefore, similarly, the small variation in composition between resins is thought to result in excellent resolution and roughness performance. Furthermore, the resin obtained by the resin production method of the present invention and the resin (A) contained in the composition of the present invention have a carbonyl group in a side chain and further have a main chain terminal group such as a nitroxide radical residue or a dithioester residue. Such a resin has high polarity and is highly compatible with a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a photoacid generator (B)) and an acid diffusion controller (particularly an onium salt compound (CD) of an acid that is relatively weaker than the acid generated from the photoacid generator (B), etc., as described below), which may be contained in the actinic ray-sensitive or radiation-sensitive resin composition, thereby making aggregation less likely to occur. This is thought to further improve roughness performance and suppress the occurrence of defects due to aggregation.

[0214] The composition of the present invention is typically a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a chemically amplified resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0215] [Resin (A)] The resin (A) contained in the composition of the present invention contains a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B), and has a main chain terminal structure represented by -O-N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１ may be bonded to form a ring), and the ratio (Aw / Ao) of the molar introduction rate (Ao) of the repeating unit represented by general formula (A) in the methanol-insoluble component to the molar introduction rate (Aw) of the repeating unit represented by general formula (A) in the methanol-soluble component is less than 1.75.

[0216] <Repeating unit represented by formula (A)>

[0217]

[0218] In general formula (A), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5.

[0219] In general formula (A), R １１ ~R １３ , L, Ar, and k are R in the above general formula (a). １１ ~R １３ , L, Ar, and k, and preferred examples thereof are also the same.

[0220] The repeating unit represented by general formula (A) contained in the resin (A) may be of one type or of two or more types.

[0221] The content ratio of the repeating unit represented by general formula (A) relative to all repeating units in resin (A) is preferably 40 to 90 mol %, more preferably 45 to 80 mol %, and even more preferably 50 to 75 mol %.

[0222] <Repeating unit represented by formula (B)>

[0223]

[0224] In general formula (B), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

[0225] In general formula (B), R ２１ ~R ２３ , L ２１ , L ２２ , R ２４ and m is R in the above general formula (b). ２１ ~R ２３ , L ２１ , L２２ , R ２４ and m have the same meanings, and preferred examples are also the same.

[0226] The repeating unit represented by formula (B) is preferably represented by the following formula (B1).

[0227]

[0228] In general formula (B1), R ２１ ~R ２３ R each independently represents a hydrogen atom, an organic group, or a halogen atom. ２４ represents a group that is decomposed and eliminated by the action of an acid.

[0229] In general formula (B1), R ２１ ~R ２３ and R ２４ represents R in the above general formula (B). ２１ ~R ２３ and R ２４ The same applies to preferred examples.

[0230] The repeating unit represented by general formula (B) contained in the resin (A) may be of one type or of two or more types.

[0231] The content ratio of the repeating unit represented by general formula (B) relative to all repeating units in resin (A) is not particularly limited, but can be, for example, 5 to 70 mol %, preferably 10 to 60 mol %, more preferably 15 to 50 mol %.

[0232] <Repeating unit having an acid-decomposable group> The resin (A) preferably has an acid-decomposable group. The resin (A) preferably contains a repeating unit having an acid-decomposable group. When the resin (A) is an acid-decomposable resin, in a pattern forming method using the composition of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0233] The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity. The acid-decomposable group is typically a group that decomposes under 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 leaves under the action of an acid (leaving group). Typically, the polarity of the resin (A) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate 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, as well as alcoholic hydroxyl groups.

[0234] Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0235] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), a heteroaryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), an alkenyl group (linear or branched), or an alkynyl group (linear or branched). １ ~Rx ３When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to each other to form a ring (which may be either a monocyclic or polycyclic ring). １ ~Rx ３ The alkyl group of Rx is preferably 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, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The heteroaryl group in Rx is preferably a heteroaryl group having 2 to 15 carbon atoms, and examples thereof include a furyl group, a thienyl group, a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group. １ ~Rx ３ The aralkyl group of Rx １ ~Rx ３ A group in which one hydrogen atom in the alkyl group is substituted with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms is preferred, and examples thereof include a benzyl group. １ ~Rx ３The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ Examples of the alkynyl group of Rx include an ethynyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining the two 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. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0236] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. 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, an aralkyl group, and an alkenyl group. ３６is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. In addition, R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0237] 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. Ar is more preferably an aryl group.

[0238] The content of the repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in the resin (A), and the content of the repeating units having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total repeating units in the resin (A).

[0239] The repeating unit having an acid-decomposable group contained in the resin (A) may be a repeating unit represented by the above-mentioned general formula (A), may be a repeating unit represented by the above-mentioned general formula (B), or may be another repeating unit. The repeating unit having an acid-decomposable group contained in the resin (A) may be one type, or two or more types. When the resin (A) contains two or more types of repeating units having an acid-decomposable group, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0240] Resin (A) may contain other repeating units in addition to the repeating units represented by the general formula (A), the repeating units represented by the general formula (B), and the repeating units having an acid-decomposable group. Regarding the other repeating units, the contents of paragraphs

[0079] to

[0172] of WO 2022 / 024928 are incorporated by reference.

[0241] The total content of the repeating units represented by the general formula (A) and the repeating units represented by the general formula (B) in the resin (A) is not particularly limited, but is preferably 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more.

[0242] <Terminal Structure of Main Chain> The resin (A) has an —O—N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ represents an organic group. Ｎ１ may be bonded to form a ring) (hereinafter, these may be collectively referred to as "specific structure"). Ｎ１ represents R in the above general formula (N). Ｎ１ and preferred examples are also the same, or represent an organic group containing another polymer segment. ａ２ represents R in the above general formula (Ra). ａ２ In a preferred embodiment, the resin (A) has a main chain terminal structure represented by -SC(=S)-SR. ａ３ (R ａ３ represents an organic group). ａ３ represents R in the above general formula (Ra-2). ａ３ and preferred examples thereof are also the same, or represent an organic group containing another polymer segment.

[0243] The term "terminal structure of the main chain of resin (A)" refers to a terminal structure other than the structure corresponding to the repeating unit described above that resin (A) has. The term "resin (A) having the specific structure at the terminal structure of the main chain" means that resin (A) has the specific structure described above at least in one of the terminal structures of the main chain.

[0244] The terminal structure of the main chain is １ H-NMR, １３ This can be confirmed by C-NMR.

[0245] The resin (A) may be a linear polymer, a star polymer, or a branched polymer. The main chain structure of the resin (A) refers to the main chain structure of a polymer segment in the case of a star polymer or a branched polymer. In addition, at least one of the terminal structures of the main chain structures of the multiple polymer segments may have the specific structure described above. The terminal structure of the main chain of the resin is as follows: １ H-NMR, １３ Identification was carried out by C-NMR.

[0246] <Molar Introduction Rate of Repeating Unit Represented by General Formula (A)> The resin (A) contained in the composition of the present invention has a ratio (Aw / Ao) of the molar introduction rate (Ao) of the repeating unit represented by general formula (A) in the methanol-insoluble component to the molar introduction rate (Aw) of the repeating unit represented by general formula (A) in the methanol-soluble component of less than 1.75.

[0247] The methanol-insoluble component of the resin (A) includes a resin with a relatively low incorporation rate of the hydrophilic component. The methanol-soluble component includes a resin with a relatively high incorporation rate of the hydrophilic component. The incorporation rate of the hydrophilic component is the incorporation rate of the repeating unit represented by the general formula (A). The smaller the ratio (Aw / Ao) of the molar incorporation rate (Ao) of the repeating unit represented by the general formula (A) in the methanol-insoluble component to the molar incorporation rate (Aw) of the repeating unit represented by the general formula (A) in the methanol-soluble component, the smaller the variation in the incorporation rate of the hydrophilic component between the resins, and the smaller the variation in the composition between the resins. The method for achieving a molar incorporation rate (Aw / Ao) of less than 1.75 is not particularly limited, but an example thereof is synthesis using the above-described method for producing the resin of the present invention.

[0248] The resin (A) has an Aw / Ao ratio of less than 1.75, preferably less than 1.50, and more preferably less than 1.30. The lower limit of Aw / Ao is, for example, more than 1.05.

[0249] Specifically, Ao and Aw can be measured as follows: 1 g of resin is dissolved in 2 g of ethyl acetate to prepare a 33% by mass resin solution. The obtained resin solution is added dropwise to a methanol solvent (20 times the mass of the resin) and stirred at 25°C for 24 hours. The resin is precipitated, filtered, and vacuum dried at 40°C to recover a methanol-insoluble component (a component having a relatively low introduction rate of the repeating unit represented by general formula (A)). The methanol solvent after filtration is concentrated and vacuum dried at 40°C to recover a methanol-soluble component (a component having a relatively high introduction rate of the repeating unit represented by general formula (A)). １ H-NMR and １３ The introduction rates of the repeating unit represented by general formula (A) in the methanol-insoluble component and the methanol-soluble component are determined by C-NMR measurement and designated as Ao and Aw, respectively. From the obtained Ao and Aw, Aw / Ao can be calculated.

[0250] The method for synthesizing the resin (A) is not particularly limited, but it is preferable to synthesize it using the above-mentioned method for producing the resin of the present invention.

[0251] The weight average molecular weight (Mw) of the resin (A), as a polystyrene equivalent value measured by the GPC method, is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more, and is preferably 30,000 or less, more preferably 15,000 or less.

[0252] The dispersity (molecular weight distribution, Pd, Mw / Mn) of the resin (A) is preferably less than 1.40, more preferably 1.35 or less, even more preferably 1.30 or less, particularly preferably 1.25 or less, and most preferably 1.20 or less. The lower limit of the dispersity is greater than 1.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0253] In the composition of the present invention, the content of resin (A) is preferably 40.0 to 99.9 mass% and more preferably 60.0 to 90.0 mass% based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more resins (A) are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0254] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention contains a compound (B) that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as photoacid generator (B)). The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. There is no particular restriction on the lower limit, but 100 or more is preferred. When the photoacid generator is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably a compound that generates an acid having a pKa of −2.0 or more upon irradiation with actinic rays or radiation, and more preferably a compound that generates an acid having a pKa of −2.0 or more and 1.0 or less.

[0255] Examples of the photoacid generator (B) include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0256] "M ＋ X －In the compound represented by the formula ", M ＋ represents an organic cation. As the organic cation, a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0257]

[0258] In formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may 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. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0259] R ２０１ , R ２０２ , and R ２０３The organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5. Examples of the alkyl group include 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. Preferred cycloalkyl groups include 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. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.

[0260] In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0261] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0262] "M ＋ X － In the compound represented by the formula "X － represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0263] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0264] 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, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0265] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0266] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or 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).

[0267] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. 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.

[0268] An example of the sulfonylimide anion is a saccharin anion.

[0269] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0270] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0271] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0272] "M ＋ X － For the compound represented by the formula "", the contents of

[0114] to

[0144] of JP-A No. 2005-2236 can be cited.

[0273] The photoacid generator (B) may be at least one selected from the group consisting of the following compounds (I) to (II):

[0274] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0275] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from an acidic site represented by the formula (I), wherein the acid dissociation constant a2 is greater than the acid dissociation constant a1. At least one of the acid dissociation constants a1 is less than 0.

[0276] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A. ２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0277] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having two HAs. １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1 described above. １ － and one HA ２ "Compound having two A １ － and A ２－ In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0278] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0279] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0280] For example, when compound (II) is an acid-generating compound having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII is "two HA １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0281] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. At least one of the acid dissociation constants a1 is less than 0. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. The two or more A １ － and two or more of the above M １ ＋ may be the same or different.

[0282] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0283]

[0284] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0285] With regard to the cation, compound (I) and compound (II), the contents of paragraphs

[0207] to

[0278] of WO 2022 / 024928 can be cited.

[0286] The content of the photoacid generator (B) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total solid content of the composition of the present invention. The content of the photoacid generator (B) is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition of the present invention. The photoacid generator (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0287] [Acid Diffusion Controller (C)] The acid diffusion controller (C) traps the acid generated from, for example, the photoacid generator (B) during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller (C) is not particularly limited, and examples thereof include a basic compound (CA), a low-molecular-weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) of an acid that is weaker in acid than the acid generated from the photoacid generator (B), and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824, and those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of the low molecular weight compound (CB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. For example, specific examples of the onium salt compound (CD) that is a weaker acid than the acid generated from the photoacid generator (B) or the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0288] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[0289] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (the total content if multiple types are present) is preferably 0.1 to 15.0 mass %, more preferably 1.0 to 15.0 mass %, based on the total solid content of the composition of the present invention. In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more types.

[0290] [Hydrophobic Resin (Resin (D))] The composition of the present invention may further contain a hydrophobic resin (also referred to as "Resin (D)") different from Resin (A). The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of the polar substance and the non-polar substance.

[0291] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0292] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% based on the total solid content of the composition of the present invention. One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0293] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and 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 surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0294] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0295] [Solvent (S)] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0296] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0297] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0298] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0299] [Other Additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0300] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0301] [Actinic ray- or radiation-sensitive film, pattern forming method] The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The present invention also relates to a pattern forming method. The pattern forming method of the present invention is preferably a pattern forming method comprising the steps of forming an actinic ray- or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention, exposing the actinic ray- or radiation-sensitive film, and developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably comprises the following steps: Step 1: Forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention; Step 2: Exposing the actinic ray- or radiation-sensitive film; Step 3: Developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of each of the above steps is described in detail below.

[0302] (Step 1: Actinic Ray- or Radiation-Sensitive Film Forming Step) Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention.

[0303] An example of a method for forming an actinic ray- or radiation-sensitive film on a substrate using the composition of the present invention is to coat the composition of the present invention on the substrate. It is preferable to filter the composition of the present invention 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 even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0304] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

[0305] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0306] The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0307] A top coat may be formed on top of the actinic ray-sensitive or radiation-sensitive film using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the actinic 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 description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the actinic ray-sensitive or radiation-sensitive film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain 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.

[0308] (Step 2: Exposure Step) Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film. Examples of the exposure method include a method of irradiating the formed actinic 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, and include far ultraviolet light with a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam are particularly preferred.

[0309] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0310] (Step 3: Development Step) Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0311] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is 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.

[0312] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0313] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0314] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially 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, even 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, based on the total amount of the developer.

[0315] The pattern forming method of the present invention is preferably a positive pattern forming method using an alkaline developer.

[0316] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0317] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0318] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0319] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0320] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0321] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of 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.

[0322] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0323] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0324] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and a content of 0 ppt by mass or more is preferred.

[0325] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0326] [Method for Manufacturing an Electronic Device] The present specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0327] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0328] [Resin Synthesis Examples] <Synthesis Example 1: Synthesis of Resin P-1>

[0329]

[0330] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-5) / (b-1) / (c-1) / (d-5) = 64 / 28 / 5 / 3. PGMEA (propylene glycol monomethyl ether acetate) was added to the mixture to give a monomer concentration of 65% by mass. A monomer solution was prepared. This solution was divided into two portions at a mass ratio of 30:70, designated as Monomer Solution A and Monomer Solution B, respectively. To Monomer Solution A, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) was added as an initiator, relative to the total amount of monomers, and 0.03 eq of 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (RA-1) was added as a dithioester compound, relative to the total amount of monomers. Under a nitrogen atmosphere, monomer solution A was added dropwise to a reaction vessel at 85°C over 1 hour, and then the mixture was heated at 80°C for an additional 1 hour. Monomer solution B (25°C) was added dropwise to the resulting solution over 3 hours, and the mixture was then allowed to react at 85°C for 1 hour. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate and n-heptane at a ratio of 1:9 (by mass), causing the resin to precipitate. The resin was then filtered, recovered, and vacuum-dried to obtain resin (P-1) in a 75% yield. The introduction ratio was (a-5) / (b-1) / (c-1) / (d-5) = 62 / 30 / 5 / 3, with an Mw of 7980 and an Mw / Mn of 1.22.

[0331] Resins PA-2, P-3, P-4, PA-5, and P-6 to P-18 were synthesized in the same manner as Resin (P-1), except that the monomers used and their ratios, solvent, monomer concentration, initiator, dithioester compound and its molar equivalent, and monomer solution B dropping time and reaction temperature were changed as shown in Table 1.

[0332] <Synthesis Example 2: Synthesis of Resin PN-3>

[0333]

[0334] Monomers (a-2), (b-3), and (d-8) were used. The monomers were mixed in a molar ratio of (a-2):(b-3):(d-8) = 71 / 26 / 3, and acetic anhydride was added to give a solution with a monomer concentration of 75% by mass to prepare a monomer solution. This solution was divided into two portions at a mass ratio of 30:70, designated as Monomer Solution A and Monomer Solution B, respectively. Monomer Solution A was added with 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) as an initiator relative to the total amount of monomers, and 0.042 eq of 2,2,6,6-tetramethylpiperidine 1-oxyl (N-1) as a nitroxide radical relative to the total amount of monomers. Monomer Solution A was added dropwise to a reaction vessel at 80°C under a nitrogen atmosphere over one hour, and then heated at 80°C for an additional hour. The liquid was heated to 130°C, the reaction temperature for polymerization, and then Monomer Solution B (room temperature, 22°C) was added dropwise over 6 hours, followed by reaction at 130°C for 1 hour. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), and the resin was precipitated. After filtration and recovery, the resin was vacuum dried to obtain Resin (PN-3) in a yield of 75%. The introduction ratio (molar ratio) of (a-2):(b-3):(d-8) = 68 / 29 / 3, the Mw was 6,880, and the Mw / Mn was 1.21.

[0335] Resins PN-4, PN-7, PN-8, PN-10, PN-11, PN-13, and PN-15 to PN-18 were synthesized in the same manner as for the above resin (PN-3), except that the monomers used and their ratios, solvent, monomer concentration, initiator, nitroxide radical source dithioester compound and its molar equivalent, and the dropwise addition time of monomer solution B and the reaction temperature at that time were changed as shown in Table 1.

[0336] The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). １３ The terminal structure of the main chain of the resin (the type of specific structure at the end of the main chain of the resin) was measured by C-NMR (nuclear magnetic resonance). １ H-NMR, １３ The resins were identified by C-NMR. The terminal structure of the main chain of the resin is shown as "Terminal Structure" in Table 1. In Table 1, PGME represents propylene glycol monomethyl ether, DAA represents diacetone alcohol, 2-methylTHF represents 2-methyltetrahydrofuran, and AC2O represents acetic anhydride. The mixing ratio of the solvents in Table 1 is a mass ratio.

[0337]

[0338] In the resins P-1, PA-2, P-3, P-4, PA-5, P-6 to P-18, and PN-3 to PN-4, PN-7 to PN-8, PN-10 to PN-11, PN-13, and PN-15 to PN-18 in Table 1, the raw material monomers are as follows: c-1 to c-9 and d-1 to d-12 are listed as repeating units derived from the raw material monomers.

[0339]

[0340]

[0341]

[0342]

[0343] The compounds used as initiators in Table 1 above are as follows: (I-1) to (I-4) have decomposition temperatures of 66°C, 65°C, 51°C, and 88°C, respectively.

[0344]

[0345] The compounds used as the nitroxide radicals or dithioester compounds in Table 1 above are as follows: (Dithioester Compounds)

[0346]

[0347] (nitroxide radical)

[0348]

[0349] In the resins P-1, PA-2, P-3, P-4, PA-5, P-6 to P-18, and PN-3 to PN-4, PN-7 to PN-8, PN-10 to PN-11, PN-13, and PN-15 to PN-18 in Table 1 above, the structures of the resin end groups are as follows:

[0350]

[0351]

[0352] <Synthesis Example 3: Synthesis of Resin PA-1> Deprotection Condition A

[0353]

[0354] To 10 g of resin (P-1), 100 ml of a 1 mol% tetra-n-butylammonium fluoride (TBAF) THF solution was added, heated to 50 ° C, and reacted for 6 hours. After cooling, 250 g of ethyl acetate and 100 g of water were added and washed with water. After removing the water layer, washing with water (100 g) was performed five times. After concentrating the obtained resin solution, it was dropped into a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration and recovery, it was vacuum dried to obtain resin (PA-1) in an 89% yield.

[0355] <Synthesis Example 4: Synthesis of Resin PA-3> Deprotection Condition B

[0356]

[0357] To 8 g of resin (P-3), 10.0 g of cyclohexanone, 15.0 g of methanol, and 4.93 g of triethylamine (48.7 mmol, 2.1 equivalents relative to the number of moles of base-decomposable protecting group unit (unit derived from a-2)) were added, heated at 60 ° C., and reacted for 12 hours. After cooling, 200 g of ethyl acetate, 80 g of water, and 2.38 g of acetic acid (39.4 mmol, 1.7 equivalents relative to the base-decomposable protecting group unit) were added for neutralization. After removing the aqueous layer, washing with water (80 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin precipitated. After filtration and recovery, it was dried under vacuum to obtain resin (PA-3) in a yield of 92%.

[0358] Synthesis Example 5: Synthesis of Resin PA-12 Deprotection Condition C

[0359]

[0360] To 8 g of resin (P-12), 50 g of THF and 10 g of acetic acid (AcOH) were added, and the mixture was heated to 50°C and reacted for 6 hours. After cooling, 200 g of ethyl acetate and 80 g of water were added, and the mixture was washed with water. After removing the aqueous layer, washing with water (80 g) was performed five times. The resulting resin solution was concentrated and then added dropwise to a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio) to precipitate the resin, which was then filtered, recovered, and vacuum dried to obtain resin (PA-12) in an 85% yield.

[0361] Resins P-3, P-4, P-8 to P-11, and P-13 to P-18 were deprotected according to deprotection condition B to give resins PA-3, PA-4, PA-8 to PA-11, and PA-13 to PA-18.

[0362] Resin P-6 was deprotected according to deprotection condition A to give resin PA-6.

[0363] Resin P-7 was deprotected according to deprotection condition C to give resin PA-7.

[0364] <Synthesis Example 6: Synthesis of Resin PNA-3>

[0365]

[0366] The resin (PN-3) obtained in Synthesis Example 2 was reacted according to deprotection conditions A to form resin (PNA-3).

[0367] Resins PN-3, PN-4, PN-8, PN-10, PN-11, PN-13, PN-15 to PN-18 were deprotected according to deprotection condition B to give resins PNA-3, PNA-4, PNA-8, PNA-10, PNA-11, PNA-13, PNA-15 to PNA-18.

[0368] Resin PN-7 was deprotected according to deprotection condition C to give resin PNA-7.

[0369] Table 2 shows the resin type before deprotection treatment, the deprotection treatment method (deprotection conditions), the resin composition (type and ratio (molar ratio) of repeating units), the terminal structure of the main chain of the resin (type of specific structure at the main chain terminal), the weight average molecular weight (Mw) of the resin, and the polydispersity (Mw / Mn) of the resin for resins PA-1 to PA-18, and PN-3, PN-4, PN-7, PN-8, PN-10, PN-11, PN-13, and PN-15 to PN-18. The terminal structure of the main chain of the resin is １ H-NMR, １３ The terminal structure of the main chain of the resin was identified by C-NMR.

[0370]

[0371] In Resins PA-1 to PA-18, and Resins PNA-3, PNA-4, PNA-8, PNA-10, PNA-11, PNA-13, and PNA-15 to PNA-18 in Table 2 above, the repeating units aa-1 to aa-3 and aa-5 to aa-7 are as follows: a-4, a-8, and b-1 to b-14 are as described above and are listed as raw material monomers; c-1 to c-9 and d-1 to d-12 are as described above.

[0372]

[0373] Comparative Synthesis Example 1: Synthesis of Resin PX-1

[0374]

[0375] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-5) / (b-1) / (c-1) / (d-5) = 62 / 30 / 5 / 3. Cyclohexanone was added so that the monomer concentration became a 30% by mass solution. 8 mol% of dimethyl 2,2'-azobis(2-methylpropionate) was added as an initiator. Under a nitrogen atmosphere, 0.1 times the mass of cyclohexanone was heated to 85 ° C., and the monomer solution was added dropwise over 4 hours, and then the reaction was continued for another 2 hours at 85 ° C. The resulting resin solution was added dropwise to a 1:9 mixed solvent of ethyl acetate and n-heptane, and the resin was precipitated. After filtration and recovery, it was dried under vacuum to obtain a resin with a yield of 75%. The resulting resin was reacted according to deprotection conditions A to obtain resin (PX-1). The introduction ratio of (aa-5) / (b-1) / (c-1) / (d-5) = 62 / 30 / 5 / 3, Mw was 7210, and Mw / Mn was 1.58.

[0376] The following radical polymerized resins PX-2 to PX-18 were synthesized in the same manner as for resin PX-1.

[0377] Comparative Synthesis Example 2: Synthesis of Resin PXX-1

[0378]

[0379] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-5) / (b-1) / (c-1) / (d-5) = 64 / 28 / 5 / 3. PGMEA (propylene glycol monomethyl ether acetate) was added to the solution to give a monomer concentration of 65% by mass. A monomer solution was prepared. To this solution, 0.030 molar equivalents of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) as an initiator, based on the total amount of monomers, and 0.03 eq of 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (RA-1) as a dithioester compound were added based on the total amount of monomers. The mixture was allowed to react at 85°C for 3 hours under a nitrogen atmosphere. The resulting resin solution was dropped into a mixed solvent of ethyl acetate and n-heptane at a ratio of 1:9 (by mass), and the resin was precipitated. The precipitate was filtered, recovered, and then vacuum-dried to obtain resin (Py-1) in a yield of 75%. The resulting resin was reacted under deprotection conditions A to obtain resin (PXX-1). The introduction ratio of (aa-5) / (b-1) / (c-1) / (d-5) was 62 / 30 / 5 / 3, with an Mw of 7180 and an Mw / Mn of 1.21.

[0380] The following resins PXX-2 to PXX-3 were synthesized in the same manner as for resin PXX-1.

[0381] Comparative Synthesis Example 3: Synthesis of Resin PXXX-1

[0382]

[0383] Monomers (a-5), (b-1), (c-1), and (d-5) were used, and the monomers were mixed in a molar ratio of (a-5) / (b-1) / (c-1) / (d-5)=64 / 28 / 5 / 3. PGMEA (propylene glycol monomethyl ether acetate) was added to the resulting solution to give a monomer concentration of 65% by mass. To this solution, 0.030 molar equivalents of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) as an initiator and 0.03 eq of 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (RA-1) as a dithioester compound were added, relative to the total amount of monomers, to prepare a monomer solution. 0.1 mass times PGMEA was heated to 85 ° C., and under a nitrogen atmosphere, a monomer solution (24 ° C.) containing (I-1) and (RA-1) was added dropwise over 4 hours, and then the mixture was allowed to react at 85 ° C. for 3 hours. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), the resin was precipitated, filtered, recovered, and then vacuum dried to obtain resin (Pz-1) in a yield of 75%. The resulting resin was reacted according to deprotection condition A to obtain resin (PXXX-1). The introduction ratio of (aa-5) / (b-1) / (c-1) / (d-5) = 62 / 30 / 5 / 3, Mw was 7260, and Mw / Mn was 1.22.

[0384] The following resins PXXX-2 to PXXX-3 were also synthesized in the same manner as for resin PXXX-1. <Comparative Synthesis Example 4: Synthesis of resin PNXX-3>

[0385]

[0386] Monomers (a-2), (b-3), and (d-8) were used, and the monomers were mixed in a molar ratio of (a-2):(b-3):(d-8) = 71 / 26 / 3. Acetic anhydride was added to the solution to give a monomer concentration of 75% by mass. A monomer solution was prepared. To this solution, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) was added as an initiator, relative to the total amount of monomers, and 0.042 eq of 2,2,6,6-tetramethylpiperidine 1-oxyl (N-1) was added as a nitroxide radical, relative to the total amount of monomers. Under a nitrogen atmosphere, 0.1 times the mass of acetic anhydride was heated to 85°C, and a monomer solution (24°C) containing (I-1) and (N-1) was added dropwise over 1 hour, followed by a reaction at 130°C for 4 hours. The resulting resin solution was dropped into a mixed solvent of ethyl acetate:n-heptane = 1:9 (mass ratio), and the resin was precipitated. After filtration and recovery, it was vacuum dried to obtain resin (PNy-3) in a 70% yield. The resulting resin was reacted according to deprotection condition A to obtain resin (PNXX-3). The introduction ratio (molar ratio) of (aa-2):(b-3):(d-8) = 69 / 28 / 3, the Mw was 6290, and the Mw / Mn was 1.22.

[0387] Comparative Synthesis Example 5: Synthesis of Resin PNXXX-3

[0388]

[0389] A monomer solution was prepared by mixing the monomers (a-2), (b-3), and (d-8) in a molar ratio of (a-2):(b-3):(d-8) = 71 / 26 / 3, and adding acetic anhydride to the solution to give a monomer concentration of 75% by mass. To this solution, 0.030 molar equivalents (0.03 eq) of dimethyl 2,2'-azobis(2-methylpropionate) (I-1) as an initiator and 0.042 eq of 2,2,6,6-tetramethylpiperidine 1-oxyl (N-1) as a nitroxide radical were added. Under a nitrogen atmosphere, 0.1 mass of PGMEA was heated to 130 ° C., and the monomer solution (24 ° C.) was added dropwise over 4 hours. The resulting resin solution was then reacted at 130 ° C. for 1 hour. The resulting resin was added dropwise to a mixed solvent of ethyl acetate: n-heptane = 1:9 (mass ratio), and the resin was precipitated. After filtration and recovery, it was vacuum dried to obtain resin (PNz-3) in a yield of 76%. The resulting resin was reacted according to deprotection condition A to obtain resin (PNXXX-3). The introduction ratio (molar ratio) of (aa-2): (b-3): (d-8) = 68 / 29 / 3, Mw was 6330, and Mw / Mn was 1.22.

[0390] The resin structures, resin compositions (types and ratios (molar ratios) of repeating units), weight average molecular weights (Mw) and dispersities (Mw / Mn) of the resins of the comparative examples are shown below. Note that the terminal structures of the resins are the same as those of P-1 for PXX-1 and PXXX-1, the same as those of PA-2 for PXX-2 and PXXX-2, and the same as those of PXX-3 and PXXX-3.

[0391]

[0392]

[0393]

[0394] <Ratio (Aw / Ao) of the molar introduction rate (Ao) of the repeating unit represented by the general formula (A) in the methanol-insoluble component to the molar introduction rate (Aw) of the repeating unit represented by the general formula (A) in the methanol-soluble component> The "Aw / Ao" in the resin (PA-1) was measured as follows.

[0395] 1 g of resin (PA-1) was dissolved in 2 g of ethyl acetate to prepare a 33% by mass resin solution. The resulting resin solution was added dropwise to a methanol solvent (20 times by mass relative to the resin) and stirred at 25°C for 24 hours. The resin was precipitated, filtered, and vacuum dried at 40°C to recover a methanol-insoluble component (a component with a relatively low introduction rate of the repeating unit represented by the general formula (A)). The methanol solvent after filtration was concentrated and vacuum dried at 40°C to recover a methanol-soluble component (a component with a relatively high introduction rate of the repeating unit represented by the general formula (A)). １ H-NMR and １３ From C-NMR measurement, the introduction rates of the repeating unit represented by the general formula (A) in the methanol-insoluble component and the methanol-soluble component were determined, and designated Ao and Aw, respectively. The same procedure was performed for resins PA-2 to PA-18, PX-1 to PX-3, PXX-1 to PXX-3, PXXX-1 to PXXX-3, PNXX-3, and PNXXX-3 to determine Ao and Aw. The compositional variation of each resin was evaluated from the ratio of the introduction rate of the repeating unit represented by the general formula (A) in the methanol-insoluble component and the methanol-soluble component of each resin, Aw / Ao. Values ​​of less than 1.50 were designated A, values ​​of 1.50 or greater but less than 1.75 were designated B, values ​​of 1.75 or greater but less than 2.00 were designated C, and values ​​of 2.00 or greater were designated D. The smaller the value, the less compositional variation between resins, which is preferable. If the value is A or B, there is essentially no problem. "Aw / Ao" is shown in Tables 2 and 3.

[0396]

[0397] [Resist Composition] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0398] <Resin (P)> As the resin (P), the resins PA-1 to PA-18, PNA-3, PNA-4, PNA-7, PNA-8, PNA-10, PNA-11, PNA-13, and PNA-15 to PNA-18 shown above were used. As comparative resins, PX-1 to PX-18, PXX-1 to PXX-3, PXXX-1 to PXXX-3, PNXX-3, and PNXXX-3 were used. Note that resins PA-1 to PA-18 also correspond to resin (A) in the composition of the present invention.

[0399] <Photoacid Generator (B)> B-1 and B-2 were used as the photoacid generator (B).

[0400]

[0401] <Acid Diffusion Controller (C)> As the acid diffusion controller (C), C-1 to C-8 were used.

[0402]

[0403] <Hydrophobic Resin> D-1 was used as the hydrophobic resin. The content ratio of the repeating unit (content relative to all repeating units in the resin) is a molar ratio.

[0404]

[0405] <Surfactant> The following surfactants W-1 to W-4 were used: W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.; fluorine and silicone-based) W-2: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based) W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

[0406] <Solvents> The solvents used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Diacetone alcohol (DAA) S-3: Propylene glycol monomethyl ether (PGME) S-4: Ethyl lactate (EL) S-5: Ethyl 3-ethoxypropionate (EEP) S-6: 2-heptanone (MAK) S-7: Methyl 3-methoxypropionate (MMP) S-8: 3-methoxybutyl acetate

[0407] <Preparation of Resist Compositions> Each component other than the solvent shown in Tables 3 and 4 was used in the amount (mass %) shown in Tables 3 and 4 and mixed with the solvent shown in Tables 3 and 4 to obtain a solution. The content of each component is the mass ratio relative to the total solids content of the resist composition. The resulting solution was filtered through a polyethylene filter with a pore size of 0.02 μm to obtain resist compositions R-1 to R-32, RX-1 to RX-18, RXX-1 to RXX-4, and RXXX-1 to RXXX-4. The solids concentration of the resist composition was adjusted to the concentration shown in Tables 3 and 4. The solids content refers to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. Tables 3 and 4 list the types of solvents used and their mass ratios.

[0408]

[0409]

[0410] <Coating of Resist Composition> The prepared resist composition was applied to a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 130°C for 300 seconds to obtain a resist film with a thickness of 100 nm. Note that similar results were obtained even if the Si wafer was replaced with a chromium substrate.

[0411] (Examples 1a to 32a, Comparative Examples 1a to 18a, and Comparative Examples 1c to 8c) <Pattern Forming Method (1): EB Exposure, Alkali Development (Positive)> A wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). The lithography was performed so as to form a 1:1 line and space pattern. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and then dried. The wafer was then rotated at 4000 rpm for 30 seconds, baked at 95°C for 60 seconds, and dried.

[0412] [Evaluation] The obtained patterns were evaluated for resolution, LWR performance, and development defects by the following methods. The results are shown in Tables 5 and 6 below.

[0413] The irradiation energy required to resolve a 1:1 line and space pattern with a line width of 50 nm was taken as the sensitivity (Eop).

[0414] <L / S Resolution> The limiting resolving power (the minimum line width at which a line and a space (line:space=1:1) are separately resolved) at the exposure dose exhibiting the above sensitivity (Eop) was taken as the resolving power (nm).

[0415] <Line Width Roughness (LWR) Performance> Line width roughness was measured at the above Eop by measuring the line width at 50 arbitrary points within 0.5 μm in the longitudinal direction of a line and space pattern (line:space=1:1) with a line width of 50 nm, determining the standard deviation, and calculating 3σ (nm). A smaller value indicates better performance.

[0416] <Development Defects> A 1:1 line and space pattern with a line width of 100 nm formed at the above sensitivity (Eop) was inspected using a defect inspection device KLA2360 (product name) manufactured by KLA Tencor Corporation. The pixel size of the defect inspection device was set to 0.16 μm and the threshold value was set to 20. The number of defects (number / cm ) extracted from the difference caused by overlaying the comparison image on a pixel-by-pixel basis was then counted. ２ ) and the number of defects per unit area (number / cm ２ After that, a defect review was performed to classify and extract development defects from all defects, and the number of development defects per unit area (number / cm ２ ) was calculated. A value of less than 0.3 was rated A, a value of 0.3 or more and less than 0.8 was rated B, and a value of 0.8 or more and less than 3.0 was rated C. The smaller the value, the better the performance.

[0417] The resist compositions used and the results are shown in Tables 5 and 6 below.

[0418]

[0419]

[0420] (Examples 1b to 32b, Comparative Examples 1b to 18b, and Comparative Examples 1d to 8d) <Pattern Forming Method (2): EUV Exposure, Alkali Development (Positive)> The same steps as in the above-mentioned pattern forming method (1) were carried out, except that an EUV exposure apparatus (Micro Exposure Tool, manufactured by Exitech, NA (Numerical Aperture) 0.3, Quadruple, Outer Sigma 0.68, Inner Sigma 0.36) was used instead of the electron beam lithography apparatus. Resolution, LWR performance, and development defects were evaluated using the same methods as described above. Tables 7 and 8 below show the resist compositions used and the results.

[0421]

[0422]

[0423] The results in Tables 5 to 8 show that the compositions obtained by the production method of the present invention are excellent in resolution, LWR performance, and development defects.

[0424] The present invention can provide a method for producing a resin that can be suitably used for an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, and a method for producing an actinic ray-sensitive or radiation-sensitive resin composition.The present invention also can provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and defect suppression performance, an actinic ray-sensitive or radiation-sensitive film that uses the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

[0425] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-058290) filed on March 29, 2024, the contents of which are incorporated herein by reference.

Claims

1. A method for producing a resin, comprising: (i) a step of polymerizing raw material monomers including a monomer represented by the following general formula (a) and a monomer represented by the following general formula (b) in the presence of a nitroxide radical or a dithioester compound; wherein in step (i), a reaction solution containing a solvent, an initiator in an amount of 80% by mass or more based on the total amount of the initiator, and a nitroxide radical or dithioester compound in an amount of 90% by mass or more based on the total amount of the nitroxide radical or dithioester compound is placed in a reaction vessel, and then at least a portion of the raw material monomers is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator. In general formula (a), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When R is bonded to form a ring, it represents a (k+2)-valent aromatic ring group. １４ represents a hydroxyl group or a group that generates an —OH group upon decomposition with an acid or a base, and k represents an integer of 1 to 5. In general formula (b), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

2. A method for producing a resin as described in claim 1, wherein in step (i), a reaction solution containing a solvent, 80% by mass or more of an initiator based on the total amount of the initiator, 90% by mass or more of a nitroxide radical or dithioester compound based on the total amount of the nitroxide radical or dithioester compound, and a portion of the raw material monomer is placed in a reaction vessel, and then the remaining raw material monomer is added dropwise to the reaction solution at a temperature equal to or higher than the decomposition temperature of the initiator.

3. The method for producing a resin according to claim 2, wherein in step (i), the raw material monomers in the reaction solution are present in an amount of 1 to 50 mol % based on the total amount of the raw material monomers.

4. The method for producing a resin according to claim 1, wherein in step (i), the raw material monomer is dropped for 1 to 24 hours.

5. The method for producing a resin according to claim 1, wherein in step (i), the reaction system is heated for less than 2 hours after the dropwise addition of the raw material monomer.

6. The method for producing a resin according to claim 1, wherein the nitroxide radical is represented by the following general formula (N): In general formula (N), R Ｎ１ Each of R independently represents an organic group. Ｎ１ may be bonded to form a ring.

7. The method for producing a resin according to claim 1, wherein the dithioester compound is represented by the following general formula (Ra): In the general formula (Ra), Ra １ and Ra ２ each independently represents an organic group.

8. The method for producing a resin according to claim 1, wherein the dithioester compound is represented by the following general formula (Ra-2): In general formula (Ra-2), Ra １ and Ra ３ each independently represents an organic group.

9. The method for producing a resin according to claim 1, wherein in general formula (a), L is a single bond.

10. The method for producing a resin according to claim 1, wherein in general formula (a), Ar is a benzene ring group.

11. R in the general formula (a) １４ is a group represented by any one of the following general formulas (3) to (7): In general formulas (3) to (7), R ３１ represents a hydrogen atom or an organic group. ４１ , R ５１ , R ６１ R each independently represents an organic group. ７１ , R ７２ R each independently represents a hydrogen atom or an organic group. ７３ represents an organic group. ７１ ~R ７３ may be linked to each other to form a ring. * indicates the bonding position to Ar.

12. In the general formula (b), L ２２ The method for producing a resin according to claim 1 , wherein is an (m+1)-valent aromatic ring group.

13. In the general formula (b), L ２１ The method for producing a resin according to claim 1 , wherein is a single bond.

14. In the general formula (b), R ２４ The method for producing a resin according to claim 1, wherein the compound is represented by the following general formula (8): In general formula (8), R ８１ , R ８２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８３ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８１ ~R ８３ may be linked to each other to form a ring. * indicates the bonding position to the O atom.

15. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition, comprising the method for producing the resin according to any one of claims 1 to 14.

16. A polymer comprising a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B), wherein the terminal structure of the main chain is -O-N(R Ｎ１ ) ２ , or -S-C(=S)-R ａ２ (R Ｎ１ and R ａ２ Each of R independently represents an organic group. Ｎ１ wherein the molar introduction rate (Ao) of the repeating unit represented by general formula (A) in the methanol-insoluble component is less than 1.75, and the molar introduction rate (Aw) of the repeating unit represented by general formula (A) in the methanol-soluble component is less than 1.75; (B) a compound that generates an acid when irradiated with actinic rays or radiation; and (S) a solvent. In general formula (A), R １１ ~R １３ each independently represents a hydrogen atom, an organic group, or a halogen atom. １２ may be bonded to Ar to form a ring, in which case R １２ represents a single bond or an alkylene group; L represents a single bond or a divalent linking group; Ar represents a (k+1)-valent aromatic ring group; R １２ When the group is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, where k represents an integer of 1 to 5. In general formula (B), R ２１ ~R ２３ each independently represents a hydrogen atom, an organic group, or a halogen atom. ２２ Is L ２２ may be bonded to form a ring, in which case R ２２ represents a single bond or an alkylene group. ２４ represents a group that is decomposed and eliminated by the action of an acid. ２１ represents a single bond or a divalent linking group. ２２ represents a single bond or an (m+1)-valent aromatic ring group, R ２２ When the group is bonded to form a ring, it represents an (m+2)-valent aromatic ring group, where m represents an integer of 1 to 5.

17. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16, wherein in general formula (A), L is a single bond.

18. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16, wherein in general formula (A), Ar is a benzene ring group.

19. In the general formula (B), L ２２ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16, wherein is an (m+1)-valent aromatic ring group.

20. In the general formula (B), L ２１ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16 , wherein is a single bond.

21. In the general formula (B), R ２４ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16, wherein the compound is represented by the following general formula (8): In general formula (8), R ８１ , R ８２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８３ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. ８１ ~R ８３ may be linked to each other to form a ring. * indicates the bonding position to the O atom.

22. The terminal structure of the main chain of the resin (A) is -S-C(=S)-S-R ａ３ (R ａ３ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 16 , wherein R 1 represents an organic group.

23. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 16 to 22.

24. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 16 to 22; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

25. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 24.

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