Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern formation method, and manufacturing method for electronic device

Abstract

Provided are: an actinic-ray-sensitive or radiation-sensitive resin composition which contains a resin (A) that contains a repeating unit having a group that is decomposed by the action of an acid and that has increased polarity, and a compound (B) that has a specific structure and a molecular weight of 350 or more; an actinic-ray-sensitive or radiation-sensitive film that uses the actinic-ray-sensitive or radiation-sensitive composition; a pattern formation method; and a method for manufacturing an electronic device.

Description

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

[0001] 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 manufacturing 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 manufacturing an electronic device that can be suitably used in an ultra-microlithography process applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes.

[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, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] Patent Documents 1 to 3 describe resist compositions containing various components such as a resin that becomes alkali-soluble in the presence of an acid.

[0005] Japanese Patent Application Publication No. 10-83079 Japanese Patent Application Publication No. 2012-181510 Japanese Patent Application Publication No. 2000-10270

[0006] Recently, the performance required of resist compositions has become increasingly high, and further improvements in, for example, resolution and process margin are expected. The process margin refers to the tolerance range (margin) within which a desired result can be obtained even if various conditions (e.g., heating temperature, etc.) in the pattern formation process using a resist composition vary, and the wider this tolerance range, the better the process margin. In pattern formation using a resist composition, a resist film formed from the resist composition may be exposed and then baked (heated) before development. The post-exposure baking is also called PEB (Post Exposure Bake). The process margin with respect to the PEB temperature is also called "PEB temperature dependency." The smaller the PEB temperature dependency, the smaller the change in performance with respect to PEB temperature change, and the better.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent resolution and little PEB temperature dependency. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) containing a repeating unit having a group that decomposes under the action of an acid and exhibits increased polarity; and a compound (B) represented by the following formula (N1) and having a molecular weight of 350 or more:

[0010]

[0011] In formula (N1), R ｂ１ represents a hydrogen atom or a substituent, R ｂ２ represents a substituent. ｂ１ and R ｂ２does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ１ and R ｂ２ may be bonded to form a ring. １ teeth* １ -(C=O)O-* ２ , -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ Represents. １ indicates the bonding position with the nitrogen atom, * ２ is X １ represents the bonding position with １ but* １ -(C=O)O-* ２ When expressing １ represents an aryl group, a heteroaryl group, a group represented by the following formula (X-1) or a group represented by the following formula (X-2). １ -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ When expressing １ is an aryl group, a heteroaryl group, -CR Ｘ１ =CR Ｘ２ R Ｘ３ , -C≡CR Ｘ４ , a group represented by the following formula (X-1), a group represented by the following formula (X-2), or a group represented by the following formula (X-3). Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent.

[0012]

[0013] In formula (X-1), R Ｘ５ ~R Ｘ８ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R representsＸ５ and R Ｘ６ does not represent an aryl group or a heteroaryl group. Ｘ９ represents a substituent. Ｘ１ represents an aromatic ring group having 4 to 20 ring members. m1 represents an integer of 0 to 8. When m1 represents an integer of 2 or more, a plurality of R Ｘ９ may be the same or different, and multiple R Ｘ９ may be bonded to form a ring. * indicates the bonding position.

[0014]

[0015] In formula (X-2), R Ｘ１０ and R Ｘ１１ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ１０ and R Ｘ１１ does not represent an aryl group or a heteroaryl group. Ｘ１２ represents a substituent. Ｘ２ represents an aromatic ring group having 4 to 20 ring members. m2 represents an integer of 0 to 8. When m2 represents an integer of 2 or more, a plurality of R Ｘ１２ may be the same or different, and multiple R Ｘ１２ may be bonded to form a ring. * indicates the bonding position.

[0016]

[0017] In formula (X-3), L Ｘ１ is an aryl group, a heteroaryl group, -CR Ｘ１５ =CR Ｘ１６ R Ｘ１７ or -C≡CR Ｘ１８ Represents R Ｘ１３ ~R Ｘ１８ Each independently represents a hydrogen atom or a substituent. * represents a bonding position. [2] A in the above formula (N1) １ but* １ -(C=O)O-* ２ When R in the above formulas (X-1) and (X-2) represents Ｘ５ , R Ｘ６ , RＸ１０ and R Ｘ１１ [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein A in the formula (N1) each independently represents a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, a cycloalkylsulfonyl group, an aryloxy group, an arylthio group, or an arylsulfonyl group. １ but* １ -(C=O)O-* ２ or -(S(=O) ２ [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the compound (B) is represented by the following formula (N2) or (N3):

[0018]

[0019] In formula (N2), R ｂ３ and R ｂ４ each independently represents a substituent. ｂ３ and R ｂ４ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ３ and R ｂ４ may be bonded to form a ring. Ｘ１９ represents a substituent. Ｘ３ represents an aromatic ring group having 4 to 20 ring members. m3 represents an integer of 0 to 8. When m3 represents an integer of 2 or more, a plurality of R Ｘ１９ may be the same or different, and multiple R Ｘ１９ may be bonded to form a ring.

[0020]

[0021] In formula (N3), R ｂ５ represents a hydrogen atom or a substituent. ｂ６ represents a substituent. ｂ５ and R ｂ６ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom.ｂ５ and R ｂ６ may be bonded to form a ring. Ｘ２０ and R Ｘ２１ each independently represents a hydrogen atom or a substituent. Ｘ２０ and R Ｘ２１ does not represent an aryl group or a heteroaryl group. Ｘ２２ represents a substituent. Ｘ４ represents an aromatic ring group having 4 to 20 ring members. m4 represents an integer of 0 to 8. When m4 represents an integer of 2 or more, a plurality of R Ｘ２２ may be the same or different, and multiple R Ｘ２２ may be bonded to form a ring. [5] A in the above formula (N1) １ -(S(=O) ２ )-, X １ represents an aryl group, a heteroaryl group, a group represented by formula (X-2) above, or a group represented by formula (X-4) below.

[0022]

[0023] In formula (X-4), R Ｘ２３ and R Ｘ２４ R each independently represents a hydrogen atom or a substituent. Ｘ２５ represents a substituent. Ｘ５ represents an aryl group or a heteroaryl group. m5 represents an integer of 0 to 8. When m5 represents an integer of 2 or more, a plurality of R Ｘ２５ may be the same or different, and multiple R Ｘ２５ may be bonded to form a ring. * represents the bonding position. [6] R in the above formula (N1) ｂ１ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the following formula (GN1), and R ｂ２ represents an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the following formula (GN1), and R ｂ１ and R ｂ２ may be bonded to form a ring.

[0024]

[0025] In formula (GN1), R ｎ１ ~R ｎ３ each independently represents a hydrogen atom or a substituent. ｎ１ ~R ｎ３ At least one of R represents a substituent. ｎ１ ~R ｎ３ at least two of these may be bonded to form a ring. * represents a bonding position. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound (B) has a molecular weight of 400 or more. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (A) contains a repeating unit represented by the following formula (Pa1):

[0026]

[0027] In formula (Pa1), R １１ , R １２ and R １３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １２ is Ar １ may be bonded to form a ring, in which case R １２ represents a single bond or an alkylene group. １１ is a single bond, —COO— or —CONR １４ - represents. １４ represents a hydrogen atom or an alkyl group. １１ represents a single bond or an alkylene group. １ represents a (k+1)-valent aromatic ring group, R １２ and a repeating unit represented by the formula (Ga1) below: [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin (A) contains a repeating unit represented by the formula (Ga1):

[0028]

[0029] In formula (Ga1), R ａ１ , R ａ２ and Rａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ represents a single bond or a divalent linking group. ａ１ represents an aromatic ring group. ａ２ represents -O- or -C(=O)O-. １ represents a group represented by the following formula (G-1) or (G-2).

[0030]

[0031] In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ５ and R ａ６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ４ and R ａ５ may be bonded to form a ring. １ is a group represented by formula (G-1), Ar ａ１ is R ａ３ or R ａ４ may bond to form a ring. * indicates the bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ７ , R ａ８ and R ａ９two of the groups may be bonded to form a ring. * indicates a bonding position.

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], further comprising a compound (C) that generates an acid upon irradiation with actinic rays or radiation.

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , further comprising an acid diffusion controller (D).

[12] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] .

[13] A pattern-forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] ; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern.

[14] A method for manufacturing an electronic device, comprising the pattern forming method according to

[13] .

[0032] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution and little PEB temperature dependency. The present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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).

[0037] 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:

[0038] (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, an acryloyl group, a methacrylate group, a methyl ... Examples of the substituent T include acyl groups such as thiazolyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl 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 (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0039] 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".

[0040] 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).

[0041] 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.

[0042] 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.

[0043] In this specification, the term "solid content" refers to components contained in the actinic ray-sensitive or radiation-sensitive resin composition and that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component contained in the actinic ray-sensitive or radiation-sensitive resin composition and 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.

[0044] <Actinic ray-sensitive or radiation-sensitive resin composition> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) including a repeating unit having a group that decomposes under the action of an acid and exhibits increased polarity, and a compound (B) represented by the following formula (N1) and having a molecular weight of 350 or more.

[0045]

[0046] In formula (N1), R ｂ１ represents a hydrogen atom or a substituent, R ｂ２ represents a substituent. ｂ１ and R ｂ２ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ１ and R ｂ２ may be bonded to form a ring. １ teeth* １ -(C=O)O-* ２ , -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ Represents. １ indicates the bonding position with the nitrogen atom, * ２ is X １ represents the bonding position with １ but* １ -(C=O)O-* ２ When expressing １represents an aryl group, a heteroaryl group, a group represented by the following formula (X-1) or a group represented by the following formula (X-2). １ -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ When expressing １ is an aryl group, a heteroaryl group, -CR Ｘ１ =CR Ｘ２ R Ｘ３ , -C≡CR Ｘ４ , a group represented by the following formula (X-1), a group represented by the following formula (X-2), or a group represented by the following formula (X-3). Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent.

[0047]

[0048] In formula (X-1), R Ｘ５ ~R Ｘ８ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ does not represent an aryl group or a heteroaryl group. Ｘ９ represents a substituent. Ｘ１ represents an aromatic ring group having 4 to 20 ring members. m1 represents an integer of 0 to 8. When m1 represents an integer of 2 or more, a plurality of R Ｘ９ may be the same or different, and multiple R Ｘ９ may be bonded to form a ring. * indicates the bonding position.

[0049]

[0050] In formula (X-2), R Ｘ１０ and R Ｘ１１ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２When R represents Ｘ１０ and R Ｘ１１ does not represent an aryl group or a heteroaryl group. Ｘ１２ represents a substituent. Ｘ２ represents an aromatic ring group having 4 to 20 ring members. m2 represents an integer of 0 to 8. When m2 represents an integer of 2 or more, a plurality of R Ｘ１２ may be the same or different, and multiple R Ｘ１２ may be bonded to form a ring. * indicates the bonding position.

[0051]

[0052] In formula (X-3), L Ｘ１ is an aryl group, a heteroaryl group, -CR Ｘ１５ =CR Ｘ１６ R Ｘ１７ or -C≡CR Ｘ１８ Represents R Ｘ１３ ~R Ｘ１８ Each of the symbols independently represents a hydrogen atom or a substituent. * represents a bonding position.

[0053] The composition of the present invention is preferably 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 preferably 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 preferably a resist film.

[0054] [Resin (A) containing a repeating unit having a group that decomposes under the action of an acid and increases polarity] The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") that contains a repeating unit that decomposes under the action of an acid and has a group that increases polarity.

[0055] (Repeating unit having acid-decomposable group) The resin (A) preferably has a repeating unit having an acid-decomposable group. 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 alkaline developers and decreasing its solubility in organic solvents. 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.

[0056] 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)

[0057] In formula (Y1) and formula (Y2), Rx １ ~Rx ３Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl 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 ３ When 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 in Rx may be either linear or branched. As the alkyl group, an alkyl group having 1 to 10 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, is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. １ ~Rx ３ The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. １ ~Rx ３ The cycloalkyl group may be 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. In the cycloalkyl group, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the ring may be replaced with a vinylene group. １ ~Rx ３The aryl group in Rx is preferably an aryl group having 6 to 20 carbon atoms, more 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 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 ３ Examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms, and alkenyl groups having 2 to 10 carbon atoms are preferred, such as vinyl and allyl groups. １ ~Rx ３ Examples of the alkynyl group include alkynyl groups having 2 to 20 carbon atoms, preferably alkynyl groups having 2 to 10 carbon atoms, and for example, an ethynyl group is preferred. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkane ring. １ ~Rx ３ The cycloalkane ring formed by bonding these two may be a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkane ring formed by bonding these two, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the ring may be replaced with a vinylene group. １ ~Rx ３ The ring formed by bonding these two may have a substituent. The group represented by formula (Y1) or formula (Y2) may be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３and are bonded to form a cycloalkane ring.

[0058] 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. ３６ is 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.

[0059] 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.

[0060] The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (Ga1): The resin (A) preferably has a repeating unit represented by the following formula (Ga1).

[0061]

[0062] In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１represents a single bond or a divalent linking group. ａ１ represents an aromatic ring group. ａ２ represents -O- or -C(=O)O-. １ represents a group represented by the following formula (G-1) or (G-2).

[0063]

[0064] In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ５ and R ａ６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ４ and R ａ５ may be bonded to form a ring. １ is a group represented by formula (G-1), Ar ａ１ is R ａ３ or R ａ４ may bond to form a ring. * indicates the bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ７ , R ａ８ and R ａ９ Two of the groups may be bonded to form a ring. * indicates the bonding position.

[0065] R in formula (Ga1) ａ１ , R ａ２ and R ａ３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ , R ａ２ and R ａ３The 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. ａ１ , R ａ２ and R ａ３ 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. ａ１ , R ａ２ and R ａ３ The cycloalkyl group may be 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. ａ１ , R ａ２ and R ａ３ 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. ａ１ , R ａ２ and R ａ３ 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.

[0066] R ａ１ , R ａ２ and R ａ３ Preferably, each independently represents a hydrogen atom or an alkyl group.

[0067] L in formula (Ga1) ａ１ represents a single bond or a divalent linking group. ａ１ The divalent linking group represented by is not particularly limited, but examples thereof include -O-, -CO-, -COO-, and -CONR ａ１０ -, an alkylene group, a cycloalkylene group, and a group formed by combining two or more of these groups. ａ１０ represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom or an alkyl group.ａ１ The alkylene group represented by may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited. The alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene, are preferred. L ａ１ The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. ａ１０ The alkyl group represented by may be either linear or branched, and examples thereof include alkyl groups having 1 to 20 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 an alkyl group having 1 to 8 carbon atoms is preferred.

[0068] Ar in formula (Ga1) ａ１ represents an aromatic ring group, specifically a divalent aromatic ring group. The divalent aromatic ring group may be, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, an anthrylene group, or a biphenylene group. The divalent aromatic ring group may also be, for example, a divalent aromatic ring group containing a heterocycle containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, 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. Ar ａ１ preferably represents an arylene group having 6 to 12 carbon atoms, more preferably a phenylene group or a naphthylene group.

[0069] L in formula (Ga1) ａ２ represents —O— or —C(═O)O—. １represents a group represented by formula (G-1) or (G-2). ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. The alkyl group, the cycloalkyl group, the aryl group, the heteroaryl group, the aralkyl group, and the alkenyl group may have a substituent. R ａ４ The alkyl group in R may be either linear or branched. As the alkyl group, an alkyl group having 1 to 10 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, is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred. ａ４ The number of carbon atoms in the cycloalkyl group is preferably 3 to 20, and more preferably 4 to 15. The cycloalkyl group may be 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. In the cycloalkyl group, 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. R ａ４ The aryl group in R is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. ａ４ The heteroaryl group in the formula (I) is preferably a heteroaryl group having 3 to 19 carbon atoms, more preferably a heteroaryl group having 4 to 14 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 as a ring member. The number of ring atoms in the heteroaryl group is preferably 4 to 20, more preferably 5 to 15. Examples of heteroaryl groups include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. R ａ４ The aralkyl group of Rａ４ 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. ａ４ The alkenyl group includes alkenyl groups having 2 to 20 carbon atoms, and is preferably an alkenyl group having 2 to 10 carbon atoms, such as a vinyl group or an allyl group.

[0070] R ａ４ preferably represents a hydrogen atom, an alkyl group or a cycloalkyl group.

[0071] R in formula (G-1) ａ５ and R ａ６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ５ and R ａ６ The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group and alkenyl group represented by R ａ４ It is the same as in R ａ５ and R ａ６ Preferably, each independently represents an alkyl group or a cycloalkyl group.

[0072] R in formula (G-1) ａ４ and R ａ５ may be bonded to form a ring. ａ４ and R ａ５ The ring formed by bonding is preferably a cycloalkane ring. The cycloalkane ring may be a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring or an adamantane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a nitrogen atom or a sulfur atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the ring may be replaced with a vinylene group. ａ４ and R ａ５The ring formed by bonding may have a substituent.

[0073] G in formula (Ga1) １ is a group represented by formula (G-1), Ar ａ１ is R ａ３ or R ａ４ Ar may be bonded to form a ring. ａ１ and R ａ３ or R ａ４ The explanation, specific examples and preferred ranges of the ring formed by bonding with R ａ４ and R ａ５ are bonded to form a ring.

[0074] R in formula (G-2) ａ７ , R ａ８ and R ａ９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ７ , R ａ８ and R ａ９ The explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group, heteroaryl group, aralkyl group and alkenyl group represented by R ａ４ It is the same as in R ａ７ , R ａ８ and R ａ９ Preferably, each independently represents an alkyl group or a cycloalkyl group.

[0075] R in formula (G-2) ａ７ , R ａ８ and R ａ９ Two of the R may be bonded to form a ring. ａ７ , R ａ８ and R ａ９ The explanation, specific examples and preferred ranges of the ring formed by combining two of the above are as described above for R ａ４ and R ａ５ are bonded to form a ring.

[0076] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited to these. ３ , C.F. ３ or CH２ represents OH. Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. p represents an integer of 0 or greater. Z represents a substituent. When multiple Zs are present, the multiple Zs may be the same or different. Me represents a methyl group.

[0077]

[0078]

[0079]

[0080]

[0081] The content of the repeating unit 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). The content of the repeating unit 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). 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 preferred content range.

[0082] (Repeating unit having a phenolic hydroxyl group) The resin (A) contains a repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit different from the repeating unit having an acid-decomposable group described above. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following formula (Pa1). The resin (A) preferably has a repeating unit represented by the following formula (Pa1).

[0083]

[0084] In formula (Pa1), R １１ , R １２ and R １３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.１２ is Ar １ may be bonded to form a ring, in which case R １２ represents a single bond or an alkylene group. １１ is a single bond, —COO— or —CONR １４ - represents. １４ represents a hydrogen atom or an alkyl group. １１ represents a single bond or an alkylene group. １ 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.

[0085] R in formula (Pa1) １１ , R １２ and R １３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １１ , R １２ and R １３ The explanation, specific examples and preferred ranges of R in the above formula (Ga1) are ａ１ , R ａ２ and R ａ３ It is similar to that in

[0086] X in formula (Pa1) １１ is a single bond, —COO— or —CONR １４ - represents. １４ represents a hydrogen atom or an alkyl group. １４ The alkyl group represented by may be either linear or branched, and examples thereof include alkyl groups having 1 to 20 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 an alkyl group having 1 to 8 carbon atoms is preferred.

[0087] L in formula (Pa1) １１ represents a single bond or an alkylene group. １１The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited. The alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene, are preferred.

[0088] Ar in formula (Pa1) １ represents a (k+1)-valent aromatic ring group, R １２ When Ar is bonded to form a ring, it represents a (k+2)-valent aromatic ring group, and k represents an integer of 1 to 5. When k is 1, Ar １ represents a divalent aromatic ring group. The divalent aromatic ring group may be, for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, an anthrylene group, or a biphenylene group. The divalent aromatic ring group may also be, for example, a divalent aromatic ring group containing a heterocycle containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, 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. Specific examples of (k+1)-valent aromatic ring groups when k is an integer of 2 or more include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of divalent aromatic ring groups. 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, 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. １ preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0089] The repeating unit represented by formula (Pa1) preferably has a hydroxystyrene structure. １ preferably represents a benzene ring group. k preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0090] Specific examples of repeating units having a phenolic hydroxyl group are shown below, but the present invention is not limited to these. １ and G ２ each independently represents a hydrogen atom, a methyl group, a cyano group, a hydroxy group, or a hydroxymethyl group, and f1 represents an integer of 1 to 3.

[0091]

[0092] When the resin (A) has a repeating unit having a phenolic hydroxyl group, the content of the repeating unit having a phenolic hydroxyl group in the resin (A) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (A). Furthermore, the content of the repeating unit having a phenolic hydroxyl group is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (A). The repeating unit having a phenolic hydroxyl 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 a phenolic hydroxyl group, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0093] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit having a lactone group, a sultone group, or a carbonate group (hereinafter also referred to as "unit Y"). It is also preferable that unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0094] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Of these, a 5- to 7-membered lactone structure to which another ring structure is fused, forming a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused, forming a bicyclo or spiro structure, is more preferred. The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0095] Resin (A) preferably has a repeating unit having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2), and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of Resin (A). The lactone group, sultone group, and carbonate group may have a substituent.

[0096] R in the following structural formula Ｌ represents a substituent. Ｌ If there are multiple R Ｌ may be the same or different. Ｌ Examples of R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple R Ｌ may be the same or different, and multiple R ＬThey may be bonded to each other to form a ring.

[0097]

[0098] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0099]

[0100] In formula (AI-2), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ The alkyl group of Rb may have a substituent. ０ Examples of the substituent that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０ Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group formed by combining these. Among these, Ab is preferably a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any of formulas (CC1-1) to (CC1-2).

[0101] When the resin (A) contains the unit Y, the content of the unit Y may be 1 mol% or more, or 10 mol% or more, based on all repeating units in the resin (A). The content of the unit Y may be 80 mol% or less, or 70 mol% or less, based on all repeating units in the resin (A). It is also preferred that the resin (A) does not contain the unit Y.

[0102] (Repeating unit having a photoacid generating group) The resin (A) may have a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0103]

[0104] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０ represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0105] L ４１ represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).

[0106] L ４２ represents an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —S—, —SO—, —SO ２Preferably, the linking group is at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but preferably 3 to 20, more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but preferably 6 to 20, more preferably 6 to 10. The alkylene group, cycloalkylene group, and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0107] R ４０ is preferably a group represented by the following formula (S4-1).

[0108]

[0109] In formula (S4-1), Q － represents an acid residue, M ＋ represents a cation. * represents L ４１ The bond position of the acid residue is a group formed by dissociating a proton from an acid. － is a carboxylate anion group (COO － ), sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１ represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ) is preferred, and a sulfonate anion group is more preferred. M ＋ The explanation, specific examples and preferred ranges of M in the explanation of the photoacid generator to be described later ＋ is the same as

[0110] Specific examples of repeating units having a photoacid generating group include the repeating units described in

[0094] to

[0105] of JP 2014-041327 A, the repeating unit described in

[0094] of WO 2018 / 193954 A, and the repeating unit described in

[0138] of WO 2022 / 024928 A. The above descriptions are incorporated herein by reference.

[0111] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A and the repeating unit described in paragraph

[0094] of WO 2018 / 193954 A.

[0112] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, based on the total repeating units in the resin (A).Furthermore, the content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (A).It is also preferable that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0113] (Repeating unit represented by formula (V-1) or formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or formula (V-2). It is also preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the above-mentioned respective repeating units.

[0114]

[0115] In formulas (V-1) and (V-2), R ６ and R ７each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0116] (Repeating Unit for Reducing Mobility of Main Chain) Resin (A) may have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg may be greater than 90°C, greater than 100°C, greater than 110°C, or greater than 125°C. In order to achieve an excellent dissolution rate in a developer, the Tg may be 400°C or less or 350°C or less. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​is used to determine the Tg (°C) of the polymer. The Bicerano method is described in "Prediction of Polymer Properties," Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0117] For the repeating units for reducing the mobility of the main chain, the contents of paragraphs

[0144] to

[0160] of WO 2022 / 024928 are incorporated herein by reference.

[0118] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>.

[0119] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0120] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, resolution is improved, particularly in contact hole applications. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0121] (Repeating Unit Having an Alicyclic Hydrocarbon Structure and Not Exhibiting Acid Decomposability) Resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, and cyclohexyl(meth)acrylate.

[0122] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0123]

[0124] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP-A 2014-098921.

[0125] (Other repeating units) Furthermore, the resin (A) may have other repeating units other than the repeating units described above. The resin (A) may have a repeating unit selected from the group consisting of, for example, a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units include those described in

[0170] of WO 2022 / 024928.

[0126] Regarding the resin (A), the contents of

[0112] to

[0118] and

[0171] to

[0172] of WO 2022 / 024928 can be further cited.

[0127] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Pd, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. 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.

[0128] The content of resin (A) in the composition of the present invention 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.

[0129] [Compound (B) represented by formula (N1) and having a molecular weight of 350 or more] The composition of the present invention contains a compound (B) (also simply referred to as "compound (B)") represented by the following formula (N1) and having a molecular weight of 350 or more.

[0130]

[0131] In formula (N1), R ｂ１ represents a hydrogen atom or a substituent, R ｂ２ represents a substituent. ｂ１ and R ｂ２ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ１ and R ｂ２ may be bonded to form a ring. １ teeth* １ -(C=O)O-*２ , -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ Represents. １ indicates the bonding position with the nitrogen atom, * ２ is X １ represents the bonding position with １ but* １ -(C=O)O-* ２ When expressing １ represents an aryl group, a heteroaryl group, a group represented by the following formula (X-1) or a group represented by the following formula (X-2). １ -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ When expressing １ is an aryl group, a heteroaryl group, -CR Ｘ１ =CR Ｘ２ R Ｘ３ , -C≡CR Ｘ４ , a group represented by the following formula (X-1), a group represented by the following formula (X-2), or a group represented by the following formula (X-3). Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent.

[0132]

[0133] In formula (X-1), R Ｘ５ ~R Ｘ８ Each independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ does not represent an aryl group or a heteroaryl group. Ｘ９ represents a substituent. Ｘ１represents an aromatic ring group having 4 to 20 ring members. m1 represents an integer of 0 to 8. When m1 represents an integer of 2 or more, a plurality of R Ｘ９ may be the same or different, and multiple R Ｘ９ may be bonded to form a ring. * indicates the bonding position.

[0134]

[0135] In formula (X-2), R Ｘ１０ and R Ｘ１１ Each independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ１０ and R Ｘ１１ does not represent an aryl group or a heteroaryl group. Ｘ１２ represents a substituent. Ｘ２ represents an aromatic ring group having 4 to 20 ring members. m2 represents an integer of 0 to 8. When m2 represents an integer of 2 or more, a plurality of R Ｘ１２ may be the same or different, and multiple R Ｘ１２ may be bonded to form a ring. * indicates the bonding position.

[0136]

[0137] In formula (X-3), L Ｘ１ is an aryl group, a heteroaryl group, -CR Ｘ１５ =CR Ｘ１６ R Ｘ１７ or -C≡CR Ｘ１８ Represents R Ｘ１３ ~R Ｘ１８ Each of the symbols independently represents a hydrogen atom or a substituent. * represents a bonding position.

[0138] It is believed that compound (B) has a molecular weight of 350 or more, which makes it less likely to volatilize upon heating, thereby reducing the PEB temperature dependency of the composition of the present invention. However, the present invention is not limited in any way by the above-mentioned assumed mechanism. The molecular weight of compound (B) is 350 or more, preferably 400 or more. Furthermore, the molecular weight of compound (B) is preferably 1500 or less, more preferably 1000 or less, and particularly preferably 800 or less.

[0139] The compound (B) is preferably a compound different from the resin (A) described above.

[0140] R in formula (N1) ｂ１ represents a hydrogen atom or a substituent, R ｂ２ represents a substituent. ｂ１ and R ｂ２ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ１ and R ｂ２ may be bonded to form a ring.

[0141] R ｂ１ and R ｂ２ The substituent represented by is an adjacent nitrogen atom (R ｂ１ and R ｂ２ There are no restrictions on the structure other than that the nitrogen atom to which R is bonded does not contain a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded. ｂ１ and R ｂ２ The substituent represented by R is preferably an organic group, more preferably an organic group having 1 to 30 carbon atoms. ｂ１ and R ｂ２ The substituent represented by is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group. These groups may further have one or more substituents. Examples of groups having further substituents include a fluoroalkyl group, a fluoroalkyloxy group, etc.

[0142] R ｂ１ and R ｂ２The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may have a substituent. The alkyl group may also contain an ether bond (-O-) in the chain. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0143] R ｂ１ and R ｂ２ The explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy group and alkylthio group represented by are the same as those described above for R ｂ１ and R ｂ２ is the same as that in the alkyl group represented by

[0144] R ｂ１ and R ｂ２ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, and is, for example, preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. The cycloalkyl group may have a substituent. In the cycloalkyl group, 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. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0145] R ｂ１ and R ｂ２ The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxy group and cycloalkylthio group represented by are the same as those of the Rｂ１ and R ｂ２ is the same as that in the cycloalkyl group represented by

[0146] R ｂ１ and R ｂ２ The number of carbon atoms in the aryl group represented by is not particularly limited, and for example, is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aryl group may have a substituent. The aryl group may be a monocyclic group or a polycyclic group. The aryl group is an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene), a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane, which may have one or more carbonyl groups as a ring-constituting group), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene, which may have one or more carbonyl groups as a ring-constituting group), a non-aromatic heterocyclic compound (for example, pyrrolidine, pyridine), Five-membered non-aromatic heterocyclic compounds such as chloroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring may have at least one group selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group as a group constituting the ring. The aryl group may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure fused with at least one group selected from the group consisting of aryl groups. Examples of aryl groups include a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a phenanthryl group.

[0147] R ｂ１ and R ｂ２ The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group and the arylthio group represented by are the same as those of the above-mentioned R ｂ１ and R ｂ２ The same applies to the aryl group represented by the formula (I).

[0148] R ｂ１ and R ｂ２The heteroaryl group (aromatic heterocyclic group) represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have a substituent. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The heteroaryl group may be any of the five-membered aromatic heterocyclic compounds and six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), non-aromatic heterocyclic compounds (e.g., pyrrolidine, pyrroline, 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.), or a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of: five-membered ring non-aromatic heterocyclic compounds such as benzophenone, tetrahydrofuran, and tetrahydrothiophene; and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran.

[0149] R ｂ１ and R ｂ２ It is also preferable that represents a group represented by the following formula (GN1).

[0150]

[0151] In formula (GN1), R ｎ１ ~R ｎ３ each independently represents a hydrogen atom or a substituent. ｎ１ ~R ｎ３ At least one of R represents a substituent. ｎ１ ~R ｎ３ At least two of the groups may be bonded to form a ring. * indicates the bonding position.

[0152] R in formula (GN1) ｎ１ ~R ｎ３ R each independently represents a hydrogen atom or a substituent. ｎ１ ~R ｎ３ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. The substituent represented by is preferably an organic group, and more preferably an alkyl group, an aryl group, a heteroaryl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

[0153] R ｎ１ ~R ｎ３ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may have a substituent. The alkyl group may also contain an ether bond (-O-) in the chain. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0154] R ｎ１~R ｎ３ The alkyl group contained in the substituent represented by ｎ１ ~R ｎ３ The explanation, specific examples and preferred ranges of the alkyl group contained in the alkoxy group, alkylcarbonyloxy group, alkylsulfonyl group and alkoxycarbonyl group represented by R ｎ１ ~R ｎ３ is the same as that in the alkyl group represented by

[0155] R ｎ１ ~R ｎ３ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, and is, for example, preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. The cycloalkyl group may have a substituent. In the cycloalkyl group, 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. In addition, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0156] R ｎ１ ~R ｎ３ The cycloalkyl group contained in the substituent represented by (for example, R ｎ１ ~R ｎ３ The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxycarbonyl group represented by R ｎ１ ~R ｎ３ is the same as that in the cycloalkyl group represented by

[0157] R ｎ１ ~R ｎ３The number of carbon atoms in the aryl group represented by is not particularly limited, and for example, is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aryl group may have a substituent. The aryl group may be a monocyclic group or a polycyclic group. The aryl group is an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene), a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane, which may have one or more carbonyl groups as a ring-constituting group), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene, which may have one or more carbonyl groups as a ring-constituting group), a non-aromatic heterocyclic compound (for example, pyrrolidine, pyridine), Five-membered non-aromatic heterocyclic compounds such as chloroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring may have at least one group selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group as a group constituting the ring. The aryl group may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure fused with at least one group selected from the group consisting of aryl groups. Examples of aryl groups include a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a phenanthryl group.

[0158] R ｎ１ ~R ｎ３ The aryl group contained in the substituent represented by ｎ１ ~R ｎ３ The explanation, specific examples and preferred ranges of the aryl group represented by R ｎ１ ~R ｎ３ The same applies to the aryl group represented by the formula (I).

[0159] R ｎ１ ~R ｎ３The heteroaryl group (aromatic heterocyclic group) represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have a substituent. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The heteroaryl group may be any of the five-membered aromatic heterocyclic compounds and six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), non-aromatic heterocyclic compounds (e.g., pyrrolidine, pyrroline, 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.), or a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of: five-membered ring non-aromatic heterocyclic compounds such as benzophenone, tetrahydrofuran, and tetrahydrothiophene; and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran.

[0160] R ｎ１ ~R ｎ３ At least two of R may be bonded to form a ring. ｎ１ ~R ｎ３ The ring formed by combining at least two of the above (also referred to as "ring X") may be a non-aromatic nitrogen-containing heterocycle or an aromatic nitrogen-containing heterocycle.

[0161] The case where ring X is a non-aromatic nitrogen-containing heterocycle will be described below. The non-aromatic nitrogen-containing heterocycle may be saturated or unsaturated. The number of ring members in the non-aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms in the non-aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The non-aromatic nitrogen-containing heterocycle may be monocyclic or polycyclic. The non-aromatic nitrogen-containing heterocycle contains at least one nitrogen atom as a heteroatom and may further contain at least one atom selected from the group consisting of a sulfur atom and an oxygen atom as a ring member. Examples of non-aromatic nitrogen-containing heterocycles include five-membered non-aromatic nitrogen-containing heterocycles such as pyrrolidine, pyrroline, and 2-oxazolidone, and six-membered non-aromatic nitrogen-containing heterocycles such as morpholine, piperidine, and piperazine. The non-aromatic nitrogen-containing heterocycle may be a fused ring having a structure in which the five-membered non-aromatic nitrogen-containing heterocycle or the six-membered non-aromatic nitrogen-containing heterocycle is fused with at least one selected from the group consisting of a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms such as cyclopentane or cyclohexane), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), the five-membered non-aromatic nitrogen-containing heterocycle, and the six-membered non-aromatic nitrogen-containing heterocycle. The non-aromatic nitrogen-containing heterocycle may have a substituent. One or more of the methylene groups constituting the ring of the non-aromatic nitrogen-containing heterocycle may be fused with a carbonyl bond, an ester bond, an amide bond, or a sulfone bond (-SO ２-), When the bond between adjacent atoms contained in the non-aromatic nitrogen-containing heterocycle is a single bond, the single bond may be replaced with a multiple bond (for example, a double bond).

[0162] The case where ring X is an aromatic nitrogen-containing heterocycle will be described below. The number of ring members in the aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 3 to 30, and more preferably 4 to 20. The number of carbon atoms in the aromatic nitrogen-containing heterocycle is not particularly limited, but is preferably 2 to 20, and more preferably 3 to 15. The aromatic nitrogen-containing heterocycle may be monocyclic or polycyclic. The aromatic nitrogen-containing heterocycle contains at least one nitrogen atom as a heteroatom and may further contain at least one ring member selected from the group consisting of a sulfur atom and an oxygen atom. Examples of aromatic nitrogen-containing heterocycles include five-membered aromatic nitrogen-containing heterocycles such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic nitrogen-containing heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. Furthermore, the aromatic nitrogen-containing heterocycle may be a fused ring (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic nitrogen-containing heterocycle or the six-membered aromatic nitrogen-containing heterocycle is fused with at least one selected from the group consisting of the five-membered aromatic nitrogen-containing heterocycle, the six-membered aromatic nitrogen-containing heterocycle, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), and non-aromatic nitrogen-containing heterocycles (e.g., the five-membered non-aromatic nitrogen-containing heterocycle, the six-membered non-aromatic nitrogen-containing heterocycle, etc.). The aromatic nitrogen-containing heterocycle may have a substituent.

[0163] R ｂ１ R preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or a group represented by formula (GN1). ｂ２ preferably represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or a group represented by formula (GN1).

[0164] R in formula (N1) ｂ１ and R ｂ２ may be bonded to form a ring. ｂ１ and R ｂ２ The description, specific examples, and preferred ranges of the ring formed by bonding R are the same as those for ring X described above. ｂ１ and R ｂ２ The ring formed by bonding is preferably a non-aromatic nitrogen-containing heterocycle.

[0165] R in formula (N1) ｂ１ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group represented by formula (GN1), and R ｂ２ represents an alkyl group, a cycloalkyl group, an aryl group, or a group represented by formula (GN1), and R ｂ１ and R ｂ２ In a preferred embodiment of the compound (B), may be bonded to form a ring.

[0166] A in formula (N1) １ teeth* １ -(C=O)O-* ２ , -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ Represents. １ indicates the bonding position with the nitrogen atom, * ２ is X １ represents the bonding position with １ teeth* １ -(C=O)O-* ２ or -(S(=O) ２ )- is preferably represented.

[0167] A１ but* １ -(C=O)O-* ２ When expressing １ represents an aryl group, a heteroaryl group, a group represented by the above formula (X-1) or a group represented by the above formula (X-2). １ The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by R in the above formula (GN1) are respectively ｎ１ ~R ｎ３ It is the same as in

[0168] R in formula (X-1) Ｘ５ ~R Ｘ８ R each independently represents a hydrogen atom or a substituent. Ｘ５ ~R Ｘ８ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. When it is an organic group, it is preferably an organic group having 1 to 30 carbon atoms, and more preferably an organic group having 1 to 20 carbon atoms. Ｘ５ ~R Ｘ８ The substituent represented by is preferably a cyano group, a hydroxy group, a halogen atom, a nitro group, a carboxy group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. These groups may further have one or more substituents. Examples of groups having a substituent include a fluoroalkyl group in which a fluorine atom is substituted on an alkyl group, and an aralkyl group in which an aryl group is substituted on an alkyl group. R Ｘ５ ~R Ｘ８ The explanations, specific examples and preferred ranges of the alkyl group, alkoxy group, alkylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, heteroaryl group, aryloxy group, arylthio group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group represented by R in the above-mentioned formula (GN1) are as follows.ｎ１ ~R ｎ３ It is similar to that in

[0169] However, A in formula (N1) １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ does not represent an aryl group or a heteroaryl group. １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ A in formula (N1) preferably represents a hydrogen atom, an alkyl group, or a cycloalkyl group. １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ The alkyl group and cycloalkyl group represented by may have a substituent, and may have an aryl group or a heteroaryl group as a substituent.

[0170] R in formula (X-1) Ｘ９ represents a substituent. Ｘ９ The explanation, specific examples and preferred ranges of the substituents represented by R Ｘ５ ~R Ｘ８ It is the same as in

[0171] Ar in formula (X-1) Ｘ１ represents an aromatic ring group having 4 to 20 ring members, and preferably represents an aromatic ring group having 4 to 13 ring members. Ｘ１The aromatic ring group represented by may be an aromatic carbocyclic group or an aromatic heterocyclic group. The aromatic carbocyclic group may be a monocyclic group or a polycyclic group. The aromatic carbocyclic group is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 20 carbon atoms (preferably 6 to 13 carbon atoms), such as benzene, naphthalene, or fluorene). The aromatic carbocyclic group may also be a group obtained by removing one or more hydrogen atoms from a fused ring compound having a structure in which an aromatic hydrocarbon is fused with at least one selected from the group consisting of cycloalkanes (for example, monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (for example, monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), and non-aromatic heterocyclic compounds (for example, five-membered non-aromatic heterocyclic compounds, such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds, such as morpholine, piperidine, piperazine, and tetrahydropyran).

[0172] The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include groups obtained by removing one or more hydrogen atoms from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The aromatic heterocyclic group may be any of the five-membered aromatic heterocyclic compounds or six-membered aromatic heterocyclic compounds, the five-membered aromatic heterocyclic compounds, the six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (for example, monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (for example, monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms such as cyclopentane and cyclohexane), cycloalkenes (for example, monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), It may also be a group obtained by removing one or more hydrogen atoms from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of non-aromatic heterocyclic compounds (e.g., the above-mentioned five-membered ring non-aromatic heterocyclic compounds, the above-mentioned six-membered ring non-aromatic heterocyclic compounds, etc.).

[0173] In formula (X-1), m1 represents an integer of 0 to 8. When m1 represents an integer of 2 or more, a plurality of R Ｘ９ may be the same or different, and multiple R Ｘ９ may be bonded to form a ring, provided that the upper limit of m1 is Ｘ１ For example, Ar Ｘ１ When the aromatic ring group represented by is a benzene ring group, the upper limit of m1 is 5.

[0174] R in formula (X-2) Ｘ１０ and R Ｘ１１ R each independently represents a hydrogen atom or a substituent. Ｘ１０ and R Ｘ１１ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. When it is an organic group, it is preferably an organic group having 1 to 30 carbon atoms, and more preferably an organic group having 1 to 20 carbon atoms. Ｘ１０ and R Ｘ１１ The substituent represented by is preferably a cyano group, a hydroxy group, a halogen atom, a nitro group, a carboxy group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. These groups may further have one or more substituents. Examples of groups having a substituent include a fluoroalkyl group in which a fluorine atom is substituted on an alkyl group, and an aralkyl group in which an aryl group is substituted on an alkyl group. R Ｘ１０ and R Ｘ１１ The explanations, specific examples and preferred ranges of the alkyl group, alkoxy group, alkylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, heteroaryl group, aryloxy group, arylthio group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group represented by R in the above-mentioned formula (GN1) are as follows. ｎ１ ~R ｎ３ It is similar to that in

[0175] However, A in formula (N1) １ but* １ -(C=O)O-* ２ When R represents Ｘ１０ and R Ｘ１１ does not represent an aryl group or a heteroaryl group. １ but* １ -(C=O)O-*２ When R represents Ｘ１０ and R Ｘ１１ A in formula (N1) preferably represents a hydrogen atom, an alkyl group, or a cycloalkyl group. １ but* １ -(C=O)O-* ２ When R represents Ｘ１０ and R Ｘ１１ The alkyl group and cycloalkyl group represented by may have a substituent, and may have an aryl group or a heteroaryl group as a substituent.

[0176] R in formula (X-2) Ｘ１２ represents a substituent. Ｘ１２ The explanation, specific examples and preferred ranges of the substituents represented by R Ｘ１０ and R Ｘ１１ It is the same as in

[0177] Ar in formula (X-2) Ｘ２ represents an aromatic ring group having 4 to 20 ring members, and preferably represents an aromatic ring group having 4 to 13 ring members. Ｘ２ The description, specific examples and preferred range of the aromatic ring group represented by Ar in the above formula (X-1) are as follows. Ｘ１ It is the same as in

[0178] In formula (X-2), m2 represents an integer of 0 to 8. When m2 represents an integer of 2 or more, a plurality of R Ｘ１２ may be the same or different, and multiple R Ｘ１２ may be bonded to form a ring, provided that the upper limit of m2 is Ｘ２ For example, Ar Ｘ２ When the aromatic ring group represented by is a benzene ring group, the upper limit of m2 is 5.

[0179] A １ -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ When expressing １ is an aryl group, a heteroaryl group, -CR Ｘ１ =CR Ｘ２R Ｘ３ , -C≡CR Ｘ４ , a group represented by the above formula (X-1), a group represented by the above formula (X-2), or a group represented by the above formula (X-3). Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent. １ The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by R in the above formula (GN1) are respectively ｎ１ ~R ｎ３ It is the same as in R Ｘ１ ~R Ｘ４ The explanation, specific examples and preferred ranges of the substituents represented by R in formula (GN1) are as follows: ｎ１ ~R ｎ３ It is the same as in R Ｘ１ and R Ｘ２ R preferably each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group. Ｘ３ and R Ｘ４ preferably each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group, and more preferably represent an aryl group or a heteroaryl group.

[0180] L in formula (X-3) Ｘ１ is an aryl group, a heteroaryl group, -CR Ｘ１５ =CR Ｘ１６ R Ｘ１７ or -C≡CR Ｘ１８ Represents L Ｘ１ The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by R in the above formula (GN1) are respectively ｎ１ ~R ｎ３ It is the same as in R Ｘ１３ ~R Ｘ１８ The explanation, specific examples and preferred ranges of the substituents represented by R in formula (GN1) are as follows: ｎ１ ~R ｎ３It is the same as in R Ｘ１３ and R Ｘ１４ R preferably each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group. Ｘ１５ and R Ｘ１６ R preferably each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group. Ｘ１７ and R Ｘ１８ preferably each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group, and more preferably represent an aryl group or a heteroaryl group.

[0181] The group represented by formula (X-3) is preferably a group represented by the following formula (X-4).

[0182]

[0183] In formula (X-4), R Ｘ２３ and R Ｘ２４ R each independently represents a hydrogen atom or a substituent. Ｘ２５ represents a substituent. Ｘ５ represents an aryl group or a heteroaryl group. m5 represents an integer of 0 to 8. When m5 represents an integer of 2 or more, a plurality of R Ｘ２５ may be the same or different, and multiple R Ｘ２５ may be bonded to form a ring. * indicates the bonding position.

[0184] R in formula (X-4) Ｘ２３ and R Ｘ２４ R each independently represents a hydrogen atom or a substituent. Ｘ２３ and R Ｘ２４ The explanation, specific examples and preferred ranges of the substituents represented by R in formula (GN1) are as follows: ｎ１ ~Rｎ３ It is the same as in R Ｘ２３ and R Ｘ２４ Preferably, each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group.

[0185] R in formula (X-4) Ｘ２５ represents a substituent. Ｘ２５ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. When it is an organic group, it is preferably an organic group having 1 to 30 carbon atoms, and more preferably an organic group having 1 to 20 carbon atoms. Ｘ２５ The substituent represented by is preferably a cyano group, a hydroxy group, a halogen atom, a nitro group, a carboxy group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. These groups may further have one or more substituents. Examples of groups having a substituent include a fluoroalkyl group in which a fluorine atom is substituted on an alkyl group, and an aralkyl group in which an aryl group is substituted on an alkyl group. R Ｘ２５ The explanations, specific examples and preferred ranges of the alkyl group, alkoxy group, alkylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, heteroaryl group, aryloxy group, arylthio group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group represented by R in the above-mentioned formula (GN1) are as follows. ｎ１ ~R ｎ３ It is similar to that in

[0186] Ar in formula (X-4) Ｘ５ represents an aryl group or a heteroaryl group. Ｘ５The explanation, specific examples and preferred ranges of the aryl group and heteroaryl group represented by R in the above formula (GN1) are respectively ｎ１ ~R ｎ３ It is the same as in

[0187] In formula (X-4), m5 represents an integer of 0 to 8. When m5 represents an integer of 2 or more, a plurality of R Ｘ２５ may be the same or different, and multiple R Ｘ２５ may be bonded to form a ring, provided that the upper limit of m5 is Ｘ５ For example, Ar Ｘ５ When the aromatic ring group represented by is a benzene ring group, the upper limit of m5 is 5.

[0188] A in formula (N1) １ but* １ -(C=O)O-* ２ When R in formula (X-1) and (X-2) represents Ｘ５ , R Ｘ６ , R Ｘ１０ and R Ｘ１１ In a preferred embodiment of compound (B), each independently represents a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, a cycloalkylsulfonyl group, an aryloxy group, an arylthio group, or an arylsulfonyl group.

[0189] The compound (B) is also preferably represented by the following formula (N2) or (N3).

[0190]

[0191] In formula (N2), R ｂ３ and R ｂ４ each independently represents a substituent. ｂ３ and R ｂ４ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ３ and R ｂ４ may be bonded to form a ring. Ｘ１９ represents a substituent. Ｘ３represents an aromatic ring group having 4 to 20 ring members. m3 represents an integer of 0 to 8. When m3 represents an integer of 2 or more, a plurality of R Ｘ１９ may be the same or different, and multiple R Ｘ１９ may be bonded to form a ring.

[0192]

[0193] In formula (N3), R ｂ５ represents a hydrogen atom or a substituent. ｂ６ represents a substituent. ｂ５ and R ｂ６ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ５ and R ｂ６ may be bonded to form a ring. Ｘ２０ and R Ｘ２１ each independently represents a hydrogen atom or a substituent. Ｘ２０ and R Ｘ２１ does not represent an aryl group or a heteroaryl group. Ｘ２２ represents a substituent. Ｘ４ represents an aromatic ring group having 4 to 20 ring members. m4 represents an integer of 0 to 8. When m4 represents an integer of 2 or more, a plurality of R Ｘ２２ may be the same or different, and multiple R Ｘ２２ may be bonded to form a ring.

[0194] R in formula (N2) ｂ３ and R ｂ４ each independently represents a substituent. ｂ３ and R ｂ４ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ３ The explanation, specific examples and preferred ranges of R in the above formula (N1) are ｂ１ R in formula (N2) is the same as ｂ４ The explanation, specific examples and preferred ranges of R in the above formula (N1) are ｂ２ It is the same as in R ｂ３ and R ｂ４ may be bonded to form a ring.ｂ３ and R ｂ４ The description, specific examples, and preferred ranges of the ring formed by bonding R are the same as those for ring X described above. ｂ３ and R ｂ４ The ring formed by bonding is preferably a non-aromatic nitrogen-containing heterocycle.

[0195] R in formula (N2) Ｘ１９ represents a substituent. Ｘ１９ The explanation, specific examples and preferred ranges of the substituents represented by R in formula (X-1) are as follows: Ｘ７ and R Ｘ８ It is the same as in

[0196] Ar in formula (N2) Ｘ３ represents an aromatic ring group having 4 to 20 ring members, and preferably represents an aromatic ring group having 4 to 13 ring members. Ｘ３ The description, specific examples and preferred range of the aromatic ring group represented by Ar in the above formula (X-1) are as follows. Ｘ１ It is the same as in

[0197] In formula (N2), m3 represents an integer of 0 to 8. When m3 represents an integer of 2 or more, a plurality of R Ｘ１９ may be the same or different, and multiple R Ｘ１９ may be bonded to form a ring. However, the upper limit of m3 is Ｘ３ For example, Ar Ｘ３ When the aromatic ring group represented by is a benzene ring group, the upper limit of m3 is 5.

[0198] R in formula (N3) ｂ５ represents a hydrogen atom or a substituent. ｂ６ represents a substituent. ｂ５ and R ｂ６ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ５ The explanation, specific examples and preferred ranges of R in the above formula (N1) are ｂ１ R in formula (N3) is the same as ｂ６ The explanation, specific examples and preferred ranges of R in the above formula (N1) are ｂ２ It is the same as in Rｂ５ and R ｂ６ may be bonded to form a ring. ｂ５ and R ｂ６ The description, specific examples, and preferred ranges of the ring formed by bonding R are the same as those for ring X described above. ｂ５ and R ｂ６ The ring formed by bonding is preferably a non-aromatic nitrogen-containing heterocycle.

[0199] R in formula (N3) Ｘ２０ and R Ｘ２１ each independently represents a hydrogen atom or a substituent. Ｘ２０ and R Ｘ２１ does not represent an aryl group or a heteroaryl group. Ｘ２０ and R Ｘ２１ The substituent represented by is not particularly limited as long as it is other than an aryl group or a heteroaryl group, and examples thereof include the aforementioned substituent T (excluding aryl groups and heteroaryl groups), and are preferably a cyano group, a hydroxy group, a halogen atom, a nitro group, a carboxy group, an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. These groups may further have one or more substituents. Examples of groups having a substituent include a fluoroalkyl group in which a fluorine atom is substituted on an alkyl group, and an aralkyl group in which an aryl group is substituted on an alkyl group. R Ｘ２０ and R Ｘ２１ The explanations, specific examples and preferred ranges of the alkyl group, alkoxy group, alkylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryloxy group, arylthio group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group represented by R in the above-mentioned formula (GN1) are as follows. ｎ１ ~R ｎ３ It is similar to that in

[0200] R in formula (N3) Ｘ２２ represents a substituent. Ｘ２２ The explanation, specific examples and preferred ranges of the substituents represented by R in formula (X-1) are as follows: Ｘ７ and R Ｘ８ It is the same as in

[0201] Ar in formula (N3) Ｘ４ represents an aromatic ring group having 4 to 20 ring members, and preferably represents an aromatic ring group having 4 to 13 ring members. Ｘ４ The description, specific examples and preferred range of the aromatic ring group represented by Ar in the above formula (X-1) are as follows. Ｘ１ It is the same as in

[0202] In formula (N3), m4 represents an integer of 0 to 8. When m4 represents an integer of 2 or more, a plurality of R Ｘ２２ may be the same or different, and multiple R Ｘ２２ may be bonded to form a ring. However, the upper limit of m4 is Ｘ４ For example, Ar Ｘ４ When the aromatic ring group represented by is a benzene ring group, the upper limit of m4 is 5.

[0203] A in formula (N1) １ -(S(=O) ２ )-, X １ In a preferred embodiment of the compound (B), represents an aryl group, a heteroaryl group, a group represented by the above formula (X-2) or a group represented by the above formula (X-4).

[0204] Specific examples of compound (B) are shown below together with their molecular weights. However, the present invention is not limited to these specific examples. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

[0205]

[0206]

[0207]

[0208] The compound (B) can be synthesized based on a known method.

[0209] The content of compound (B) in the composition of the present invention is preferably 1.0 mass% or more, more preferably 2.0 mass% or more, and even more preferably 3.0 mass% or more, based on the total solid content of the composition of the present invention. The content of compound (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. Only one type of compound (B) may be used, or two or more types may be used. When two or more types of compound (B) are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0210] [Compound (C) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention preferably further contains a compound (C) (also referred to as a "photoacid generator") that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator is preferably a compound different from compound (B). The photoacid generator is preferably a compound that generates an acid having a pKa of less than 0 upon irradiation with actinic rays or radiation. The pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is preferably -0.1 or less, more preferably -0.2 or less. Furthermore, the pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is preferably -1.5 or more, more preferably -1.0 or more.

[0211] The photoacid generator may be in the form of a low molecular weight compound or may be incorporated into a polymer. Furthermore, both the low molecular weight compound and the 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 not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000. When the photoacid generator is incorporated into a polymer, it may be incorporated into the resin (A) or into a resin different from the resin (A). When the resin (A) does not have the repeating unit having the photoacid-generating group described above, the composition of the present invention preferably contains a photoacid generator that is a compound different from the resin (A). When the resin (A) contains a repeating unit having a photoacid-generating group, the composition of the present invention may or may not contain a separate photoacid generator. The photoacid generator is preferably in the form of a low molecular weight compound.

[0212] Examples of the photoacid generator 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.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0213] "M ＋ X － In the compound represented by the formula ", M ＋ represents an organic cation. The organic cation is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. Among them, the organic cation is preferably 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)").

[0214]

[0215] In the above 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 represented by R 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 listed.

[0216] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0217] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R 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 ２０３Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0218] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group optionally contained in the arylsulfonium cation is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0219] R ２０１ ~R ２０３Preferred 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 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents if possible, and it is also preferred that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents form an acid-decomposable group in any combination. Note that the acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and is preferably a structure in which the polar group is protected with a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0220] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0221] R ２０１ ~R ２０３Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0222] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0223]

[0224] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0225] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0226] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0227] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙThe ring formed by bonding together may have a substituent.

[0228] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0229]

[0230] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxyl group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0231] In formula (ZaI-4b), R １３ , R１４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0232] Next, formula (ZaII) will be described. 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 ２０５ The 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).

[0233] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５Examples 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.

[0234] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0235]

[0236]

[0237] "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.

[0238] 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.

[0239] 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).

[0240] 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.

[0241] 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).

[0242] 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.

[0243] An example of the sulfonylimide anion is a saccharin anion.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0248]

[0249] In formula (AN1), R１ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0250] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0251] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0252] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR ２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0253] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0254] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0255] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring member atom constituting the lactone structure or sultone structure in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) is preferred.

[0256] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0257] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0258]

[0259] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0260] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0261] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple R ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0262] L represents a divalent linking group, and is defined the same as L in formula (AN1).

[0263] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0264] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0265] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0266] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0267] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0268]

[0269] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0270] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0271] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0272] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0273] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0274]

[0275] In formula (d1-1), R ５１represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0276] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃ The hydrocarbon group in the formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. ２ｃ -SO ３ － " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z ２ｃ is preferably other than an aryl group. For example, Z ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ － The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0277] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0278] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４may be bonded to each other to form a ring.

[0279] The organic anions may be used alone or in combination of two or more.

[0280] It is also preferable that the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).

[0281] (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:

[0282] 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 ２and an acid dissociation constant a2 derived from the acidic site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0283] 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.

[0284] 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. 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.

[0285] 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 the 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.

[0286] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0287] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0288] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0289] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ －Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any of formulas (BB-1) to (BB-6), and even more preferably any of formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. Ａ The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0290]

[0291]

[0292] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge. ＋ Examples of the organic cation include those represented by the following formula:

[0293] (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

[0294] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in compound (I) and A １ － and M １ ＋ The definition and preferred embodiments are also the same.

[0295] In the compound (II), the cation moiety M in the structural moiety X １＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (I) is the same as the acid dissociation constant a1 in the compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound that generates an acid having two HAs. 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.

[0296] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the 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. １ － and two or more of the above M １ ＋ may be the same or different.

[0297] 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:

[0298]

[0299] 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.

[0300] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0301]

[0302]

[0303] When the composition of the present invention contains a photoacid generator, the content of the photoacid generator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the photoacid generator is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention. Only one photoacid generator may be used, or two or more may be used. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0304] [Acid Diffusion Controller (D)] The composition of the present invention may further contain an acid diffusion controller (D) (also referred to as "compound (D)"). The compound (D) can act as a quencher that traps acid generated, for example, from a photoacid generator during exposure, and suppresses reaction of the resin (A) in unexposed areas due to excess generated acid. The type of compound (D) is not particularly limited, and examples thereof include a basic compound (DA), a low-molecular-weight compound (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (DC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of the compound (DC) include an onium salt compound (DD) of an acid that is weaker in acid than the acid generated from the photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.

[0305] (Basic Compound (DA)) As the basic compound (DA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0306]

[0307] In formulas (A) and (E), R ２００ , R ２０１ and R ２０２ may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). ２０１ and R ２０２ may be bonded to each other to form a ring. ２０３ , R ２０４ , R ２０５ and R ２０６ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms. In formulas (B), (C), (D), and (E), * represents a bonding position.

[0308] R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６The alkyl group or cycloalkyl group represented by may have a substituent or may be unsubstituted. With regard to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by is more preferably unsubstituted.

[0309] Examples of the basic compound (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (DA) may be a compound having at least one structure selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (DA) may be an alkylamine derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond.

[0310] The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (DA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator used, but is, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0311] (Onium Salt Compound (DD) of an Acid that is Relatively Weaker than the Acid Generated from a Photoacid Generator) The compound (DD) may be a compound that generates an acid upon irradiation with actinic rays or radiation. The compound (DD) is preferably a compound that generates an acid that has a pKa that is 1.00 or more higher than that of the acid generated from the photoacid generator. The difference between the pKa of the acid generated from the compound (DD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from the compound (DD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. The pKa of the acid generated from compound (DD) varies depending on the type of photoacid generator used, but is preferably, for example, 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0312] Compound (DD) is preferably an onium salt compound consisting of an anion and a cation. Examples of compound (DD) include "M ＋ X － Examples of compounds include compounds (onium salts) represented by the formula "M ＋ represents an organic cation, and X － represents an organic anion. ＋ As the photoacid generator, M ＋ The same as above can be mentioned. － Examples of the anion include the anions represented by formulas (d1-1) to (d1-4) described in the description of the photoacid generator, and the anion represented by formula (d1-1) or the anion represented by formula (d1-2) is preferred.

[0313] Specific examples of the basic compound (DA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (DE) 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, and specific examples of the low molecular weight compound (DB) 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. Specific examples of the onium salt compound (DD) that is a weaker acid than the acid generated from a photoacid generator or the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0314] 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.

[0315] The molecular weight of the compound (D) is not particularly limited, but is preferably from 100 to 3,000, more preferably from 150 to 2,500, and even more preferably from 200 to 2,000.

[0316] It is also preferable that the compound (D) is a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0317] When the composition of the present invention contains compound (D), the content of compound (D) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total solid content of the composition of the present invention.In addition, the content of compound (D) is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, and even more preferably 30.0 mass% or less, based on the total solid content of the composition of the present invention.Only one type of compound (D) may be used, or two or more types may be used.When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0318] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed 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.

[0319] 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.

[0320] 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. Only one hydrophobic resin may be used, or two or more hydrophobic resins may be used. When two or more hydrophobic resins are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0321] [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.

[0322] 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.

[0323] [Solvent] 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).

[0324] 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 can therefore 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.

[0325] 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.

[0326] 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.

[0327] [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). The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less that decomposes under the action of an acid and thereby reduces its solubility in an organic developer.

[0328] The content of the other additives is not particularly limited, but may be 20.0 mass% or less, 10.0 mass% or less, or 5.0 mass% or less, based on the total solid content of the composition of the present invention. Only one type of the other additives may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0329] [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 a resist film on a substrate using the composition of the present invention; Step 2: Exposing the resist film; Step 3: Developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0330] (Step 1: Resist Film Forming Step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0331] A method for forming a resist film on a substrate using the composition of the present invention includes, for example, applying the composition of the present invention to a substrate. It is preferable to filter the composition of the present invention before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0332] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate 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 a resist film. If necessary, various underlayer films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0333] 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.

[0334] The thickness of the resist 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 resist 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.

[0335] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist 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 resist 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.

[0336] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film. Examples of exposure methods include a method in which the formed resist film is irradiated 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 preferably have a wavelength of 250 nm or less, more preferably 220 nm or less, and far ultraviolet light having a wavelength of 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.

[0337] 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. Heating after exposure is also called PEB (Post Exposure Bake). The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a normal 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 bake.

[0338] (Step 3: Development Step) Step 3 is a step of developing the exposed resist 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).

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0344] 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.

[0345] 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.

[0346] 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).

[0347] 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.

[0348] 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.

[0349] 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.

[0350] 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).

[0351] 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.

[0352] 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.

[0353] [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).

[0354] 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.

[0355] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0356] <Resin (A)> Resins A-1 to A-10 were used as resins (A). A-1 to A-10 contain the repeating units shown in Table 1 below in the amounts shown in Table 1 below. Table 1 also lists the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each resin. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units contained in each resin. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resins were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of each repeating unit is １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0357]

[0358] The structural formula of the repeating unit is shown below.

[0359]

[0360] <Compound (B)> B-1 to B-21 were used as compound (B). BR-1 to BR-4 were also used as compounds other than compound (B). However, in Table 3 below, BR-1 to BR-4 are listed in the "Compound (B)" column for convenience. The structural formulas and molecular weights of B-1 to B-21 and BR-1 to BR-4 are shown below. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

[0361]

[0362]

[0363]

[0364]

[0365] <Photoacid Generator> Photoacid generators C-1 and C-2 were used. The structural formulas of C-1 and C-2 are shown below.

[0366]

[0367] <Acid Diffusion Controller (D)> D-1 and D-2 were used as the acid diffusion controller (D). The structural formulae of D-1 and D-2 are shown below.

[0368]

[0369] <Hydrophobic Resin> T-1 was used as the hydrophobic resin. The structural formula of T-1, the content (mol %) of each repeating unit, the weight average molecular weight (Mw), and the dispersity (Mw / Mn) are shown below. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units.

[0370]

[0371] <Solvents> The solvents used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: γ-butyrolactone

[0372] <Preparation of Resist Compositions> The components shown in Tables 2 and 3 below were dissolved in the solvents shown in Tables 2 and 3 to prepare solutions with a solids concentration of 3.0% by mass. These were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions (R-1 to R-26, XR-1 to XR-4). In Tables 2 and 3, the "mass %" column indicates the content (mass %) of each component relative to the total solids in the resist composition. The solids refer to components other than the solvent. Tables 2 and 3 also list the type of solvent used and its mixing ratio (mass ratio). In the tables below, when two or more types of each component were used, the type and amount of each component are separated by a " / ". The order in which the types and amounts separated by a " / " are listed corresponds to each other.

[0373]

[0374]

[0375] Examples 1-1 to 1-26, Comparative Examples X1-1 to X1-4 Pattern Formation Method (1): EB Exposure, Alkali Development (Positive) The resist compositions shown in Table 4 below were applied to 6-inch Si wafers that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater. The wafers were then dried on a hot plate at 100°C for 60 seconds to obtain resist films with a thickness of 100 nm. Similar results were obtained even when the Si wafers were replaced with chromium substrates. The wafers coated with the resist films obtained above were subjected to pattern irradiation using an electron beam lithography system (HL750, Hitachi, Ltd., accelerating voltage 50 keV). The lithography was performed so as to form a 1:1 line-and-space pattern. After electron beam lithography, the wafers were heated on a hot plate at 110°C for 60 seconds as post-exposure bake (PEB), developed with a 2.38% by mass aqueous tetramethylammonium hydroxide solution for 30 seconds, and rinsed with pure water. The wafer was then rotated at 4000 rpm for 30 seconds and heated at 95° C. for 60 seconds to obtain a 1:1 line and space resist pattern with a line width of 50 nm. The PEB temperature dependency was evaluated for patterns formed under the conditions described below.

[0376] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line and space resist pattern with a line width of 50 nm was taken as sensitivity (Eop). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose that exhibited the above sensitivity (Eop) was taken as resolution (nm). The smaller this value, the higher the resolution.

[0377] [PEB Temperature Dependence] A pattern was formed in the same manner as above, except that the post-exposure bake (PEB) was changed to 110°C for 90 seconds. The optimal exposure dose was the exposure dose required to reproduce a 1:1 line-and-space pattern with a width of 50 nm. Next, after irradiation at the optimal exposure dose, the pattern was heated at two temperatures, +2°C and -2°C (i.e., 112°C and 108°C) relative to the post-exposure bake temperature. The resulting line-and-space patterns were measured to determine their line widths L1 and L2. PEB temperature dependence was defined as the change in line width per 1°C change in PEB temperature and calculated using the following formula: PEB temperature dependence (nm / °C) = |L1 - L2| / 4. A smaller PEB temperature dependence value indicates a smaller change in performance with temperature change and is therefore more favorable. PEB temperature dependence was evaluated using the following criteria. A: PEB temperature dependency is less than 1.0 nm / °C. B: PEB temperature dependency is 1.0 nm / °C or more and less than 2.0 nm / °C. C: PEB temperature dependency is 2.0 nm / °C or more.

[0378] Table 4 below shows the resist compositions used in each of the Examples and Comparative Examples, as well as the evaluation results of each of the Examples and Comparative Examples.

[0379]

[0380] Examples 2-1 to 2-26, Comparative Examples X2-1 to X2-4 Pattern Formation Method (2): EUV Exposure, Alkali Development (Positive) The resist compositions shown in Table 5 below were applied to 6-inch Si wafers that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and then dried on a hot plate at 100°C for 60 seconds to obtain resist films with a thickness of 100 nm. Note that similar results were obtained even when the Si wafer was replaced with a chrome substrate. The wafers coated with the resist films obtained above were subjected to pattern exposure using an EUV exposure system (Micro Exposure Tool, Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After the exposure, the wafer was subjected to post-exposure baking (PEB) by heating on a hot plate at 110°C for 60 seconds, followed by development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds and rinsing with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds and heated at 95°C for 60 seconds to obtain a 1:1 line and space resist pattern with a line width of 50 nm.

[0381] <Performance Evaluation> The resolution and PEB temperature dependency were evaluated in the same manner as described in the explanation of Examples 1-1 to 1-26 and Comparative Examples X1-1 to X1-4. The obtained evaluation results are shown in Table 5.

[0382]

[0383] The results in Tables 4 and 5 show that the resist compositions used in the examples have excellent resolution and little PEB temperature dependency.

[0384] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition having excellent resolution and little PEB temperature dependency. The present invention also provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0385] 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. 2024-046414) filed on March 22, 2024, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray- or radiation-sensitive resin composition containing: (A) a resin containing a repeating unit having a group that decomposes under the action of an acid and increases its polarity; and (B) a compound represented by the following formula (N1) and having a molecular weight of 350 or more. In formula (N1), R ｂ１ represents a hydrogen atom or a substituent, R ｂ２ represents a substituent. ｂ１ and R ｂ２ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ１ and R ｂ２ may be bonded to form a ring. １ teeth* １ -(C=O)O-* ２ , -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ Represents. １ indicates the bonding position with the nitrogen atom, * ２ is X １ represents the bonding position with １ but* １ -(C=O)O-* ２ When expressing １ represents an aryl group, a heteroaryl group, a group represented by the following formula (X-1) or a group represented by the following formula (X-2). １ -(S(=O) ２ ) -, * １ -(S(=O) ２ ) O-* ２ , -(S=O)- or * １ -(S=O)O-* ２ When expressing １ is an aryl group, a heteroaryl group, -CR Ｘ１ =CR Ｘ２ R Ｘ３ , -C≡CR Ｘ４ , a group represented by the following formula (X-1), a group represented by the following formula (X-2), or a group represented by the following formula (X-3). Ｘ１ ~R Ｘ４ each independently represents a hydrogen atom or a substituent. In formula (X-1), R Ｘ５ ~R Ｘ８ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ５ and R Ｘ６ does not represent an aryl group or a heteroaryl group. Ｘ９ represents a substituent. Ｘ１ represents an aromatic ring group having 4 to 20 ring members. m1 represents an integer of 0 to 8. When m1 represents an integer of 2 or more, a plurality of R Ｘ９ may be the same or different, and multiple R Ｘ９ may be bonded to form a ring. * indicates the bonding position. In formula (X-2), R Ｘ１０ and R Ｘ１１ Each of A in the formula (N1) independently represents a hydrogen atom or a substituent. １ but* １ -(C=O)O-* ２ When R represents Ｘ１０ and R Ｘ１１ does not represent an aryl group or a heteroaryl group. Ｘ１２ represents a substituent. Ｘ２ represents an aromatic ring group having 4 to 20 ring members. m2 represents an integer of 0 to 8. When m2 represents an integer of 2 or more, a plurality of R Ｘ１２ may be the same or different, and multiple R Ｘ１２ may be bonded to form a ring. * indicates the bonding position. In formula (X-3), L Ｘ１ is an aryl group, a heteroaryl group, -CR Ｘ１５ =CR Ｘ１６ R Ｘ１７ or -C≡CR Ｘ１８ Represents R Ｘ１３ ~R Ｘ１８ Each of the symbols independently represents a hydrogen atom or a substituent. * represents a bonding position.

2. A in the formula (N1) １ but* １ -(C=O)O-* ２ When R in the formulas (X-1) and (X-2) represents Ｘ５ , R Ｘ６ , R Ｘ１０ and R Ｘ１１ each independently represent a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, a cycloalkylsulfonyl group, an aryloxy group, an arylthio group, or an arylsulfonyl group.

3. A in the formula (N1) １ but* １ -(C=O)O-* ２ or -(S(=O) ２ 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein 4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (B) is represented by the following formula (N2) or (N3): In formula (N2), R ｂ３ and R ｂ４ each independently represents a substituent. ｂ３ and R ｂ４ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ３ and R ｂ４ may be bonded to form a ring. Ｘ１９ represents a substituent. Ｘ３ represents an aromatic ring group having 4 to 20 ring members. m3 represents an integer of 0 to 8. When m3 represents an integer of 2 or more, a plurality of R Ｘ１９ may be the same or different, and multiple R Ｘ１９ may be bonded to form a ring. In formula (N3), R ｂ５ represents a hydrogen atom or a substituent. ｂ６ represents a substituent. ｂ５ and R ｂ６ does not include a structure in which a group selected from the group consisting of a carbonyl group and a sulfonyl group is bonded to the adjacent nitrogen atom. ｂ５ and R ｂ６ may be bonded to form a ring. Ｘ２０ and R Ｘ２１ each independently represents a hydrogen atom or a substituent. Ｘ２０ and R Ｘ２１ does not represent an aryl group or a heteroaryl group. Ｘ２２ represents a substituent. Ｘ４ represents an aromatic ring group having 4 to 20 ring members. m4 represents an integer of 0 to 8. When m4 represents an integer of 2 or more, a plurality of R Ｘ２２ may be the same or different, and multiple R Ｘ２２ may be bonded to form a ring.

5. A in the formula (N1) １ -(S(=O) ２ )-, X １ represents an aryl group, a heteroaryl group, a group represented by formula (X-2) or a group represented by formula (X-4): In formula (X-4), R Ｘ２３ and R Ｘ２４ R each independently represents a hydrogen atom or a substituent. Ｘ２５ represents a substituent. Ｘ５ represents an aryl group or a heteroaryl group. m5 represents an integer of 0 to 8. When m5 represents an integer of 2 or more, a plurality of R Ｘ２５ may be the same or different, and multiple R Ｘ２５ may be bonded to form a ring. * indicates the bonding position.

6. R in the formula (N1) ｂ１ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the following formula (GN1), and R ｂ２ represents an alkyl group, a cycloalkyl group, an aryl group, or a group represented by the following formula (GN1), and R ｂ１ and R ｂ２ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein: may be bonded to form a ring. In formula (GN1), R ｎ１ ~R ｎ３ each independently represents a hydrogen atom or a substituent. ｎ１ ~R ｎ３ At least one of R represents a substituent. ｎ１ ~R ｎ３ At least two of the groups may be bonded to form a ring. * indicates the bonding position.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (B) has a molecular weight of 400 or more.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit represented by the following formula (Pa1): In formula (Pa1), R １１ , R １２ and R １３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １２ is Ar １ may be bonded to form a ring, in which case R １２ represents a single bond or an alkylene group. １１ is a single bond, —COO— or —CONR １４ - represents. １４ represents a hydrogen atom or an alkyl group. １１ represents a single bond or an alkylene group. １ 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.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit represented by the following formula (Ga1): In formula (Ga1), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ represents a single bond or a divalent linking group. ａ１ represents an aromatic ring group. ａ２ represents -O- or -C(=O)O-. １ represents a group represented by the following formula (G-1) or (G-2). In formula (G-1), R ａ４ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ５ and R ａ６ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ４ and R ａ５ may be bonded to form a ring. １ is a group represented by formula (G-1), Ar ａ１ is R ａ３ or R ａ４ may bond to form a ring. * indicates the bonding position. In formula (G-2), R ａ７ , R ａ８ and R ａ９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an aralkyl group, or an alkenyl group. ａ７ , R ａ８ and R ａ９ Two of the groups may be bonded to form a ring. * indicates the bonding position.

10. The actinic ray- or radiation-sensitive resin composition according to claim 1, further comprising a compound (C) that generates an acid upon exposure to actinic rays or radiation.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising an acid diffusion controller (D).

12. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11.

13. 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 1 to 11; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern.

14. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 13.

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