Resist composition, method for producing resist pattern and method for producing plated article

Abstract

To provide a resist composition capable of forming a resist pattern with sufficient resolution and exposure margin, a method for producing a resist pattern using the resist composition and a method for producing a plated article.SOLUTION: Provided is a resist composition containing a resin (A1) having acid-labile structural units, a photosensitizer (I), and a photoacid generator (B), wherein the photoacid generator (B) includes a compound whose maximum molar absorption coefficient in the wavelength range of 355 to 375 nm is 6000 (L / (mol cm)) or less, wherein the content of the photosensitizer (I) is 10% by mass or less based on the solid content of the resist composition, and when a film is formed using the resist composition at a use thickness, the minimum transmittance of radiation in the wavelength range of 355 to 375 nm in the film is 23% or more. Provided are a method for producing a resist pattern, and a method for producing a plated structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition, a method for producing a resist pattern, and a method for producing a plated object. [Background technology]

[0002] Patent Documents 1 and 2 describe resist compositions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-135507 [Patent Document 2] Special Publication No. 2023-502762 Summary of the Invention [Problem to be solved by the invention]

[0004] Resist patterns obtained using conventional resist compositions such as those described in Patent Documents 1 and 2 have room for further improvement in terms of resolution and exposure margin. Therefore, an object of the present invention is to provide a resist composition that can form a resist pattern that provides sufficient resolution and exposure margin, and a method for producing a resist pattern and a method for producing a plated product using the resist composition. [Means for solving the problem]

[0005] The present inventors have discovered that the above-mentioned problems can be solved by a resist composition that contains a resin that includes a structural unit having an acid labile group, a specific amount of a photosensitizer, and an acid generator that includes a compound that has a specific molar absorption coefficient.

[0006] The present invention provides the following inventions. [1] A resist composition comprising a resin (A1) containing a structural unit having an acid labile group, a photosensitizer (I), and an acid generator (B), the acid generator (B) contains a compound having a maximum molar absorption coefficient of 6000 (L / (mol cm)) or less in a wavelength range of 355 to 375 nm, the content of the photosensitizer (I) is 10 mass % or less of the solid content of the resist composition, When a film having a thickness to be used is formed using the resist composition, the minimum transmittance of the film to radiation in a wavelength range of 355 to 375 nm is 23% or more. Resist composition. [2] The resist composition according to [1], wherein the thickness of the resist composition when used is 4 μm or more. [3] The resist composition according to [1] or [2], wherein the photosensitizer (I) contains a compound having a quinone diazide sulfonyl group. [4] The resist composition according to any one of [1] to [3], wherein the photosensitizer (I) contains a compound having a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). TIFF2025183938000001.tif46170 [In formula (a) and formula (b), * represents a bond.] TIFF2025183938000002.tif42170 [In formula (c), * represents a bond.] [5] The resist composition according to any one of [1] to [4], wherein the acid generator (B) includes a compound having an oxime skeleton or an amide skeleton. [6] The resist composition according to any one of [1] to [5], wherein the acid generator (B) includes a compound having an oxime sulfonate group or an amido sulfonate group. [7] The resist composition according to any one of [1] to [6], wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit having a group represented by formula (10) or a group represented by formula (20). TIFF2025183938000003.tif22170[In formula (10), R a1 , R a2 and R a3each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF2025183938000004.tif24170[In formula (20), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.] [8] The resist composition according to any one of [1] to [7], wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing at least one selected from the group consisting of a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a3A), and a structural unit represented by formula (a3B). TIFF2025183938000005.tif51170[In formula (a1-1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. a4 represents a hydrogen atom or a methyl group. TIFF2025183938000006.tif52170[In formula (a1-2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. a5 represents a hydrogen atom or a methyl group. a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 may be the same or different.] TIFF2025183938000007.tif40170[In formula (a3A), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] TIFF2025183938000008.tif38170[In formula (a3B), R a1’ and R a2’each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] [9] The resist composition according to any one of [1] to [8], further comprising a quencher (C).

[10] A method for producing a resist pattern, comprising: (1) A step of applying the resist composition according to any one of [1] to [9] onto a metal surface of a substrate having a metal surface; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; and (4) Step of developing the composition layer after exposure A manufacturing method comprising:

[11] A method for manufacturing a plated object, comprising: (1) A step of applying the resist composition according to any one of [1] to [9] onto a metal surface of a substrate having a metal surface; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) developing the composition layer after exposure; (5) forming a plated object using the obtained resist pattern as a template; and (6) Step of removing the resist pattern A manufacturing method comprising: [Effects of the Invention]

[0007] By using the resist composition of the present invention, a resist pattern can be formed with high precision, and further, this resist pattern can be used to form a plated object with high precision. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, unless otherwise specified, in the description of the structural formula of a compound, the term "hydrocarbon group" means a linear or branched chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining these groups. When the number of carbon atoms in the "hydrocarbon group" is specified, the above groups may be used within the range permitted by the number of carbon atoms. When stereoisomers exist in these groups, all stereoisomers are included. In this specification, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid," and "(meth)acrylate" means "at least one of acrylate and methacrylate." In the groups described in this specification, those which can have both a straight-chain structure and a branched structure are interpreted as including both. The term "combined group" refers to a group in which two or more of the exemplified groups are bonded together, and the valence of these groups may be changed appropriately depending on the bonding form. The terms "derived from" or "derived from" refer to a polymerizable C=C bond contained in the molecule that is polymerized to a -CC- group (single bond). When stereoisomers exist, all stereoisomers are included. In each group, depending on the number of substituents, any number of hydrogen atoms in the group may be replaced with bonds at any positions. The number of carbon atoms in a substituent is not included in the number of carbon atoms of the substituted group. In this specification, the term "solids content of a resist composition" refers to the sum of all components in the resist composition excluding the solvent (D), which will be described later.

[0009] 1. Resist composition The resist composition of the present invention contains a resin containing a structural unit having an acid labile group (hereinafter, sometimes referred to as "resin (A1)"), a photosensitizer (hereinafter, sometimes referred to as "photosensitizer (I)"), and an acid generator (hereinafter, sometimes referred to as "acid generator (B)"). In addition to the resin (A1), the photosensitizer (I), and the acid generator (B), the resist composition of the present invention preferably further contains an alkali-soluble resin (hereinafter sometimes referred to as "resin (A2)"), a quencher (hereinafter sometimes referred to as "quencher (C)"), and / or a solvent (hereinafter sometimes referred to as "solvent (D)").

[0010] <Photosensitizer (I)> In the unexposed (unirradiated) areas, the photosensitizer (I) interacts with the hydrophilic groups of the resin, thereby inhibiting the resin's dissolution in a developer (alkaline aqueous solution). In the exposed (irradiated) areas, the quinone diazide groups decompose to generate carboxyl groups, which generate carboxylic acids and promote the resin's dissolution in a developer (alkaline aqueous solution). Furthermore, in the unexposed (unirradiated) areas, the resin crosslinks in the presence of the developer (alkaline aqueous solution), making it resistant to the developer (alkaline aqueous solution) and plating solution, thereby improving the accuracy of the plated object. The photosensitizer (I) primarily interacts with the alkali-soluble resin (hereinafter sometimes referred to as "resin (A2)") described below.

[0011] The photosensitizer (I) preferably contains a compound having a quinone diazide sulfonyl group (hereinafter, sometimes referred to as "compound (I-1)"). The compound (I-1) is not particularly limited as long as it has one or more quinone diazide sulfonyl groups in the molecule. The molecular weight of the compound obtained by replacing all of the quinone diazide sulfonyl groups in the molecule of compound (I-1) with hydrogen atoms is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,500 to 400.

[0012] Examples of compounds having a quinone diazide sulfonyl group include compounds having a naphthoquinone diazide sulfonyl group, compounds having a benzoquinone diazide sulfonyl group, and compounds having an anthraquinone diazide sulfonyl group, with compounds having a naphthoquinone diazide sulfonyl group and compounds having a benzoquinone diazide sulfonyl group being preferred. Compounds having a naphthoquinone diazide sulfonyl group are preferably compounds having a 1,2-naphthoquinone diazide sulfonyl group, more preferably compounds having a group represented by formula (a) or formula (b), and even more preferably compounds having a group represented by formula (a). Compounds having a benzoquinone diazide sulfonyl group are preferably compounds having a 1,2-benzoquinone diazide sulfonyl group, and more preferably compounds having a group represented by formula (c). TIFF2025183938000009.tif47170 [In formula (a) and formula (b), * represents a bond.] TIFF2025183938000010.tif43170 [In formula (c), * represents a bond.]

[0013] The compound obtained by replacing all quinone diazide sulfonyl groups present in the molecule of a compound having a quinone diazide sulfonyl group with hydrogen atoms is preferably an aromatic compound having a phenolic hydroxyl group. The compound having a quinone diazide sulfonyl group is preferably a compound obtained by converting an aromatic compound having a phenolic hydroxyl group into a quinone diazide sulfonate. The compound having a quinone diazide sulfonyl group is more preferably at least one selected from the group consisting of a compound represented by formula (II) (hereinafter sometimes referred to as "compound (II)"), a compound represented by formula (III) (hereinafter sometimes referred to as "compound (III)"), a compound represented by formula (IV) (hereinafter sometimes referred to as "compound (IV)"), and a compound represented by formula (V) (hereinafter sometimes referred to as "compound (V)"). TIFF2025183938000011.tif57170 [In formula (II), R11 ~R 14 each independently represents a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 18 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). A methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d1 - may be replaced with R d1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 15 ~R 30 each independently represents a hydrogen atom, a hydroxy group, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). R 11 ~R 30 At least one of the formulas is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). TIFF2025183938000012.tif51170 [In formula (III), R 31 ~R 39 R each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 31 ~R 39 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). P 1 ~P 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is not an oxygen atom, a carbonyl group, or -NR d2 - may be replaced by P 1 and P 2 may be bonded to each other to form a ring together with the two carbon atoms to which they are attached. 4 and P 5 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. R d2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] TIFF2025183938000013.tif30170[In formula (IV), R 40 ~R 53 R each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). 40 ~R 53 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). n a represents an integer of 1 to 5. a is an integer equal to or greater than 2, multiple R 49 ~R 52 may be the same or different from each other. TIFF2025183938000014.tif49170[In formula (V), R f1 , R f2 and R g1 ~R g8 R each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). f1 , R f2 and R g1 ~R g8 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). P 6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. P 7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms is preferably an oxygen atom, a carbonyl group, or -NR d3 - may be replaced by P 6 and P 7 may be bonded to each other to form a ring together with the carbon atoms to which they are attached. n v represents 1 or 2. R d3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0014] Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups having 1 to 18 carbon atoms (including linear or branched saturated chain hydrocarbon groups (alkyl groups) having 1 to 18 carbon atoms, and linear or branched unsaturated chain hydrocarbon groups having 2 to 18 carbon atoms (alkenyl groups, alkynyl groups)), monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms (including saturated alicyclic hydrocarbon groups having 3 to 18 carbon atoms, unsaturated alicyclic hydrocarbon groups having 3 to 18 carbon atoms), and aromatic hydrocarbon groups having 6 to 18 carbon atoms, and may be a combination of two or more of these groups. The alkyl group having 1 to 18 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t- or sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. Of these, a linear alkyl group is preferred. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof include ethenyl, propenyl, isopropenyl, methylpropenyl, methylbutenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, and examples thereof include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a nonynyl group, etc. The chain hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 16 carbon atoms, more preferably has 1 to 12 carbon atoms, still more preferably has 1 to 8 carbon atoms, still more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 carbon atoms. Examples of monocyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopropenyl and cyclobutenyl. Examples of polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms include polycyclic saturated alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl. The alicyclic hydrocarbon groups having 3 to 18 carbon atoms preferably have 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. The aromatic hydrocarbon groups having 6 to 18 carbon atoms preferably have 6 to 14 carbon atoms, and more preferably have 6 to 10 carbon atoms.

[0015] As the alkyl group having 1 to 6 carbon atoms, a group corresponding to the alkyl group having 1 to 6 carbon atoms can be selected from the alkyl groups having 1 to 18 carbon atoms mentioned above. P 6 Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group. 6 Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group and a naphthylene group.

[0016] P 1 and P 2 are bonded to each other to form a ring together with the two carbon atoms to which they are attached, and P 4 and P 5Examples of the ring formed by bonding together with the carbon atoms to which they are bonded include monocyclic or polycyclic alicyclic hydrocarbon rings each independently having 3 to 18 carbon atoms. Examples of these rings include cycloalkane rings such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; a decahydronaphthalene ring, an adamantane ring, and a norbornane ring. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0017] P 7 In the above, examples of the substituent on the hydrocarbon group having 1 to 18 carbon atoms include a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, and an acyloxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.

[0018] P 6 and P 7 Examples of the ring formed by bonding together with the carbon atoms to which they are bonded include monocyclic or polycyclic alicyclic hydrocarbon rings having 3 to 18 carbon atoms. Examples of these rings include cycloalkane rings such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; a decahydronaphthalene ring, an adamantane ring, and a norbornane ring. The alicyclic hydrocarbon ring having 3 to 18 carbon atoms preferably has 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.

[0019] Specific examples of compound (II) include compounds represented by formulae (II-1) to (II-3). TIFF2025183938000015.tif55170 where, R s2 R each independently represents a group represented by the above formula (a), a group represented by formula (b), a group represented by formula (c), or a hydroxy group. s2 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0020] Specific examples of compound (III) include compounds represented by formulae (III-1-1) to (III-3-8). TIFF2025183938000016.tif44170

[0021] TIFF2025183938000017.tif99170

[0022] TIFF2025183938000018.tif98170 where, R t1 R each independently represents a group represented by the above formula (a), a group represented by formula (b), a group represented by formula (c), or a hydroxy group. t1 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0023] Specific examples of compound (IV) include compounds represented by formulae (IV-1-1) to (IV-5-2). TIFF2025183938000019.tif120170

[0024] TIFF2025183938000020.tif66170 where, R t1 , R t3 , R t6 , R t7 , R t9 , R t10 and R t13R each independently represents a group represented by the above formula (a), a group represented by formula (b), a group represented by formula (c), or a hydroxy group. t1 , R t3 , R t6 , R t7 , R t9 , R t10 and R t13 At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0025] Specific examples of the compound (V) include compounds represented by formulae (V-1-1) to (V-3-1). TIFF2025183938000021.tif119170 where, R v R each independently represents a group represented by the above formula (a), a group represented by formula (b), a group represented by formula (c), or a hydroxy group. v At least one of the groups is a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c).

[0026] Compound (I-1) can be produced, for example, according to the descriptions in JP-A Nos. 2-84650, 3-185447, 3-191351, 5-323597, 8-245461, and 9-110762. Compound (I-1) can be produced, for example, by reacting an aromatic compound having a phenolic hydroxyl group (e.g., a compound in which all of the quinone diazide sulfonyl groups in the molecule of the above-mentioned compounds (II) to (V) have been replaced with hydrogen atoms) with a quinone diazide sulfonyl halide (e.g., a quinone diazide sulfonyl chloride such as 1,2-naphthoquinone diazide sulfonyl chloride or 1,2-benzoquinone diazide sulfonyl chloride, or a quinone diazide sulfonyl bromide such as 1,2-naphthoquinone diazide sulfonyl bromide or 1,2-benzoquinone diazide sulfonyl bromide) in the presence of a weak alkali, thereby causing complete or partial esterification. Aromatic compounds having a phenolic hydroxyl group are readily available on the market, and can be produced by known methods.

[0027] The content of the photosensitizer (I) in the solid content of the resist composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. It is also 10% by mass or less, preferably 9.9% by mass or less, and more preferably 9.8% by mass or less. Specifically, it is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 10% by mass or less, even more preferably 0.1% by mass or more and 10% by mass or less, even more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less. The content of the photosensitizer (I) in the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography. As the photosensitizer (I), the compound (III) and the compound (IV) are preferred, and the compound (III) is more preferred.

[0028] <Resin (A1)> The resin (A1) contains a structural unit having an acid labile group (hereinafter, sometimes referred to as "structural unit (a1)"). The acid labile group refers to a group containing a group that can be eliminated by contact with an acid (sometimes referred to as a leaving group). When the resin (A1) comes into contact with an acid, the leaving group is eliminated from the acid labile group, forming a hydrophilic group (for example, a hydroxy group (such as a phenolic hydroxyl group) or a carboxy group). The solubility of the resin (A1) in an alkaline aqueous solution increases upon contact with an acid. In other words, it is preferable that the resin (A1) is insoluble or slightly soluble in an alkaline aqueous solution before contact with an acid, and becomes soluble in an alkaline aqueous solution after contact with an acid. Resin (A1) may contain, in addition to a structural unit having an acid labile group, structural units known in the art, such as a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (a2)"), so long as it has the above-mentioned properties.

[0029] Examples of acids that eliminate the leaving group contained in the acid labile group include carboxylic acids, sulfonic acids, etc. In the composition of the present invention, examples of the acids that eliminate the leaving group include carboxylic acids, sulfonic acids, etc. that are generated by irradiating (exposing) the acid generator (B) described below with light in the photolithography step.

[0030] Examples of the acid labile group include a group represented by formula (10) and a group represented by formula (20). TIFF2025183938000022.tif23170[In formula (10), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.]

[0031] TIFF2025183938000023.tif25170[In formula (20), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0032] R of the group represented by formula (10) a1 ~R a3 The alkyl group having 1 to 8 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. a1 ~R a3 The alkyl group having 1 to 8 carbon atoms in R preferably has 1 to 6 carbon atoms, and more preferably has 1 to 4 carbon atoms. a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 carbon atoms may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond): TIFF2025183938000024.tif24170R a1 ~R a3 The alicyclic hydrocarbon group having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably has 3 to 16 carbon atoms, and even more preferably has 3 to 12 carbon atoms.

[0033] R a1 and R a2 -C(R a1 )(R a2 )(R a3) includes, for example, the following groups. The ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms. * represents a bond to -O-. TIFF2025183938000025.tif35170R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 and form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 and more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atoms to which they are bonded. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 and form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 and more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atoms to which they are bonded. R a3 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. ma is preferably 0. na is preferably 1.

[0034] Examples of the group represented by formula (10) include R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 3 carbon atoms (preferably a tert-butoxycarbonyl group); R a1 and R a2 are each independently an alkyl group having 1 to 3 carbon atoms, and R a3 is a cyclopentyl group or a cyclohexyl group; R a1 and R a2are bonded to each other to form a cyclopentane ring or a cyclohexane ring together with the carbon atoms to which they are attached, and R a3 is an alkyl group having 1 to 3 carbon atoms. Specific examples of the group represented by formula (10) include the following groups. TIFF2025183938000026.tif89170

[0035] R of the group represented by formula (20) a1’ ~R a3’ Examples of the hydrocarbon group having 1 to 20 carbon atoms include chain hydrocarbon groups having 1 to 20 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, as well as groups having 4 to 20 carbon atoms that are combinations of these. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group. Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 18 carbon atoms, more preferably has 1 to 16 carbon atoms, even more preferably has 1 to 12 carbon atoms, still more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 6 carbon atoms. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl. The alicyclic hydrocarbon group having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. Among the groups having 4 to 20 carbon atoms in which the above groups are combined, examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined (groups having 4 to 20 carbon atoms) include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of the group in which an alkyl group and an aromatic hydrocarbon group are combined (groups having 7 to 20 carbon atoms) include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 20 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group. Ra2’ and R a3’ When they are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-XR a3’ Examples of such heterocyclic rings include the following groups: The heterocyclic ring having 3 to 20 carbon atoms preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 3 to 12 carbon atoms. * represents a bond. TIFF2025183938000027.tif20170R a1’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom. R a2' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3’ and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R a3’ and more preferably bonded to the carbon atom to which they are bonded and X to form a heterocyclic ring having 3 to 12 carbon atoms, even more preferably a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group. R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or R a2' and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded and X, and is preferably a hydrocarbon group having 1 to 12 carbon atoms or R a2’ and more preferably bonded to form a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom to which they are bonded and X. Examples of the hydrocarbon group include alkyl groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, and groups having a combination of these having 4 to 18 carbon atoms. These groups can be arbitrarily selected from the groups listed above. X is preferably an oxygen atom. na' is preferably 0.

[0036] Specific examples of the group represented by formula (20) include the following groups. TIFF2025183938000028.tif100170

[0037] Specific examples of the group represented by formula (10) include a group represented by formula (1) and a group represented by formula (1'). TIFF2025183938000029.tif46170 [In formula (1) and formula (1'), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * represents a bond.]

[0038] Specific examples of the group represented by formula (20) include a group represented by formula (2) and a group represented by formula (2'). TIFF2025183938000030.tif53170 [In formula (2) and formula (2'), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. * represents a bond.]

[0039] <Structural Unit (a1) Having an Acid Labile Group> The resin (A1) containing the structural unit (a1) having an acid labile group can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound that leads to the structural unit (a1). The acid labile group contained in the structural unit (a1) is preferably a group represented by the above formula (10) and / or a group represented by the above formula (20). The resin (A1) may have only one type of structural unit (a1), or may have multiple types.

[0040] As the structural unit (a1), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as "structural unit (a1-1)") and a structural unit represented by formula (a1-2) (hereinafter sometimes referred to as "structural unit (a1-2)") are preferred.

[0041] TIFF2025183938000031.tif49170 [In formula (a1-1) and formula (a1-2), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. R a4 and R a5each independently represents a hydrogen atom or a methyl group. R a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a6 may be the same or different from each other.

[0042] In formula (a1-1), R a4 is preferably a methyl group. R a1 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a2 and form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a2 and more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atoms to which they are bonded. R a2 is an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R a1 and form a ring having 3 to 18 carbon atoms together with the carbon atom to which they are bonded, and is preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or R a1 and more preferably bonded to form a ring having 3 to 12 carbon atoms together with the carbon atoms to which they are bonded. R a3 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms.

[0043] In formula (a1-2), R a5 is preferably a hydrogen atom. R a1’ is preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom. Ra2' is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R a3’ and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R a3’ and more preferably bonded to form a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, further preferably a hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a methyl group or an ethyl group. R a3’ is a hydrocarbon group having 1 to 18 carbon atoms, or R a2' and form a heterocyclic ring having 3 to 18 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and is preferably a hydrocarbon group having 1 to 12 carbon atoms or R a2’ and more preferably bonded to form a heterocyclic ring having 3 to 12 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. Examples of the hydrocarbon group include alkyl groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, and groups having 4 to 18 carbon atoms, which are combinations of these. These groups can be arbitrarily selected from the above-listed groups. The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms. R a6 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. R a6Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. R a6 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. m is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. In formula (a1-2), -OC(R a1’ )(R a2’ )-OR a3’ is preferably bonded to the 3- or 4-position of the benzene ring (m- or p-position relative to the main chain bonded to the benzene ring), and more preferably bonded to the 4-position (p-position) of the benzene ring.

[0044] Examples of the structural unit (a1-1) include structural units represented by any one of formulas (a1-1-1) to (a1-1-17). TIFF2025183938000032.tif41170

[0045] TIFF2025183938000033.tif71170

[0046] Examples of the structural unit (a1-2) include structural units represented by any one of formulas (a1-2-1) to (a1-2-14). TIFF2025183938000034.tif126170In the above structural unit, R a5 A specific example of the structural unit (a1-2) is a structural unit in which the hydrogen atom corresponding to the following is replaced with a methyl group: The structural unit (a1-2) is preferably a structural unit represented by formula (a1-2-2), formula (a1-2-3), formula (a1-2-4), formula (a1-2-9), or formula (a1-2-14), and more preferably a structural unit represented by formula (a1-2-2), formula (a1-2-3), formula (a1-2-4), or formula (a1-2-9).

[0047] The resin (A1) containing a structural unit having an acid labile group is preferably a resin containing the structural unit (a1-2). When the resin (A1) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content of these structural units is preferably 3 to 80 mol %, more preferably 5 to 60 mol %, even more preferably 10 to 55 mol %, still more preferably 15 to 50 mol %, and even more preferably 20 to 45 mol %, based on all structural units in the resin (A1).

[0048] <Structural Unit (a2) Having No Acid Labile Group> Resin (A1) may contain a structural unit (a1) having an acid labile group and, if necessary, a structural unit (a2) not having an acid labile group. Resin (A1) containing the structural unit (a1) and the structural unit (a2) can be produced, for example, by polymerizing a monomer component containing an ethylenically unsaturated compound that leads to the structural unit (a1) and an ethylenically unsaturated compound that leads to the structural unit (a2). The acid labile group contained in the structural unit (a1) is preferably a group represented by the above formula (10) and / or a group represented by the above formula (20). The resin (A1) may contain only one type of structural unit (a2) that does not have an acid labile group, or may contain multiple types.

[0049] Examples of the structural unit (a2) include structural units represented by any one of formulas (a2-1) to (a2-3) (hereinafter, these may be referred to as "structural unit (a2-1)" or the like depending on the formula number). TIFF2025183938000035.tif55170 [In formula (a2-1), formula (a2-2) and formula (a2-3), R a7 , R a8 and Ra9 each independently represents a hydrogen atom or a methyl group. R a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. m' represents an integer of 0 to 4. When m' is 2 or more, multiple R a10 may be the same or different from each other. R a11 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. R a12 represents an alkyl group having 1 to 6 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. L a1 represents an alkanediyl group having 2 to 6 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. n represents an integer of 1 to 30. When n is 2 or more, a plurality of L a1 may be the same or different from each other.

[0050] R a10 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. R a10 Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. The alkoxy group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. R a11 Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include chain hydrocarbon groups having 1 to 12 carbon atoms (such as alkyl groups, alkenyl groups, and alkynyl groups), alicyclic hydrocarbon groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, and groups having 4 to 12 carbon atoms formed by combining these groups. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Examples of the alkenyl group having 2 to 12 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The chain hydrocarbon group having 1 to 12 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond): TIFF2025183938000036.tif25170 The alicyclic hydrocarbon group having 3 to 12 carbon atoms preferably has 3 to 10 carbon atoms, and more preferably has 3 to 8 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. The aromatic hydrocarbon group having 6 to 12 carbon atoms preferably has 6 to 10 carbon atoms. Examples of groups having 4 to 12 carbon atoms formed by combining the above groups, such as groups formed by combining an alkyl group with an alicyclic hydrocarbon group (groups having 4 to 12 carbon atoms), include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Examples of the group (a group having 7 to 12 carbon atoms) in which an alkyl group is combined with an aromatic hydrocarbon group include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (groups having 9 to 12 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group and a phenylcyclohexyl group.

[0051] R a12 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, etc. The alkyl group having 1 to 6 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0052] L a1 The alkanediyl group having 2 to 6 carbon atoms may be either linear or branched, and examples thereof include an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a propane-1,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. The alkanediyl group having 2 to 6 carbon atoms preferably has 2 to 4 carbon atoms, and more preferably has 2 to 3 carbon atoms.

[0053] R a7 is preferably a hydrogen atom. R a8 and Ra9 are preferably, independently of each other, a methyl group. R a10 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and is further preferably, for example, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and even more preferably a methyl group or a methoxy group. m' is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. R a11 is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms, provided that this excludes groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. L a1 is preferably an alkanediyl group having 2 to 4 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, or a butane-1,4-diyl group), more preferably an alkanediyl group having 2 to 3 carbon atoms (for example, an ethane-1,2-diyl group, a propane-1,3-diyl group, or a propane-1,2-diyl group), and even more preferably an ethane-1,2-diyl group. n is preferably an integer of 1 to 20, more preferably an integer of 1 to 16, even more preferably an integer of 1 to 14, even more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6. R a12 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, except for groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom.

[0054] The structural unit (a2-1) is preferably a structural unit represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-3), or formula (a2-1-4). Monomers from which the structural unit (a2-1) is derived are described, for example, in JP-A-2010-204634. TIFF2025183938000037.tif38170

[0055] Examples of the monomer from which the structural unit (a2-2) is derived include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; Polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; Examples thereof include aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate.

[0056] Examples of monomers that derive the structural unit (a2-3) include (meth)acrylic acid esters such as (poly)ethylene glycol monomethyl ether (meth)acrylates ((poly)alkylene glycol monoalkyl ether (meth)acrylates), such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, and octaethylene glycol monomethyl ether (meth)acrylate.

[0057] Furthermore, examples of monomers that derive the structural unit (a2) include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene.

[0058] The structural unit (a2) may be, for example, a structural unit represented by formula (a2-4). TIFF2025183938000038.tif50170[In formula (a2-4), R a13 represents a hydrogen atom or a methyl group. R a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R a15 represents a hydrocarbon group having 1 to 12 carbon atoms, excluding groups in which the carbon atom bonded to the oxygen atom is a tertiary carbon atom. A methylene group contained in the hydrocarbon group having 1 to 12 carbon atoms may be substituted with an oxygen atom or a carbonyl group, provided that a methylene group bonded to an oxygen atom and a methylene group bonded to the methylene group are not substituted with an oxygen atom. m" represents an integer of 0 to 4. When m" is 2 or more, multiple R a14 may be the same or different from each other. m''' represents an integer of 0 to 4. When m''' is 2 or more, multiple R a15 may be the same or different from each other. However, the sum of m" and m'" must be 5 or less.

[0059] R a15 The hydrocarbon group in R is a group in which the bond to the oxygen atom does not lead to a tertiary carbon atom, that is, a group in which one or more atoms other than carbon atoms, such as hydrogen atoms, are bonded to the bonded carbon. a15 Examples of the hydrocarbon group in the formula include a methylene group bonded to an oxygen atom and a group in which the methylene group bonded to the methylene group is not substituted with an oxygen atom, that is, a group not containing an acetal structure. Therefore, the structural unit represented by formula (a2-4) does not include the structural unit (a1-2).

[0060] R a14 The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms are R a10 The same groups as those shown below can be mentioned. R a15 As the hydrocarbon group having 1 to 12 carbon atoms, R a11 The same groups as those shown below can be mentioned.

[0061] R a13 is preferably a hydrogen atom. R a14is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and is further preferably, for example, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and even more preferably a methyl group or a methoxy group. R a15 is preferably a hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which a methylene group contained in these groups is replaced with an oxygen atom or a carbonyl group, and even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, a phenyl group, or a group formed by combining these and having 6 to 10 carbon atoms, or a group in which the methylene group adjacent to the oxygen atom of these groups is replaced with a carbonyl group. m" is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. m''' is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. However, the sum of m" and m'" must be 5 or less.

[0062] Examples of the structural unit (a2-4) include structural units represented by formulae (a2-4-1) to (a2-4-10). TIFF2025183938000039.tif93170

[0063] In the structural units represented by formulas (a2-4-1) to (a2-4-10), R a13 A specific example of the structural unit (a2-4) is a structural unit in which the hydrogen atom corresponding to the following is replaced with a methyl group:

[0064] When the resin (A1) contains the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and the structural unit (a2-4), the total content of these is preferably 1 to 90 mol %, more preferably 1 to 85 mol %, even more preferably 5 to 80 mol %, and particularly preferably 5 to 75 mol %, based on all structural units in the resin (A1).

[0065] When the resin (A1) contains the structural unit (a2), the content ratio of the structural unit (a1) to the structural unit (a2) [structural unit (a1):structural unit (a2)] is preferably 10:90 to 80:20, more preferably 15:85 to 60:40, and even more preferably 15:85 to 45:55, on a molar basis.

[0066] Examples of the combination of structural units contained in the resin (A1) include those represented by formulae (A1-1) to (A1-46). TIFF2025183938000040.tif254170

[0067] TIFF2025183938000041.tif234170

[0068] TIFF2025183938000042.tif83170

[0069] TIFF2025183938000043.tif126170

[0070] TIFF2025183938000044.tif251170

[0071] TIFF2025183938000045.tif242170

[0072] TIFF2025183938000046.tif238170

[0073] TIFF2025183938000047.tif167170In the above structural formula, R a5Specific examples of the structural unit include structural units in which a hydrogen atom corresponding to the following is replaced with a methyl group, or a methyl group corresponding to the following is replaced with a hydrogen atom. Furthermore, structural units having a hydrogen atom and a methyl group may coexist in one resin.

[0074] The resin (A1) is preferably a resin containing the structural unit (a1) and the structural unit (a2), and more preferably a resin containing the structural unit (a1-1) and / or the structural unit (a1-2) and the structural unit (a2).

[0075] Resin (A1) may be a resin (hereinafter sometimes referred to as "resin (A1b)") obtained by reacting a resin containing at least one group selected from a carboxy group and a phenolic hydroxyl group in a side chain with a compound containing at least two vinyloxy groups in one molecule. Resin (A1b) is preferably a resin obtained by reacting a resin containing a phenolic hydroxyl group with a compound containing two or more vinyloxy groups per molecule. Such a resin can be obtained, for example, by reacting a resin containing the structural unit (a2-1) with a compound containing two or more vinyloxy groups per molecule. Alternatively, the resin containing a phenolic hydroxyl group may be a novolak resin, as described below, and a resin obtained by reacting this novolak resin with the vinyloxy group-containing compound. Furthermore, the resin may be a resin obtained by mixing a resin containing the structural unit (a2-1) with a novolak resin and reacting the resulting resin mixture with the vinyloxy group-containing compound. Alternatively, a resin obtained by reacting a resin containing the structural unit (a2-1) with the vinyloxy group-containing compound may be used in combination with a resin obtained by reacting a novolak resin with the vinyloxy group-containing compound.

[0076] In the synthesis of the resin (A1b), the ratio of the amount of the compound containing at least two vinyloxy groups in one molecule to the amount of the carboxy group and phenolic hydroxy group [carboxy group and phenolic hydroxy group:vinyloxy group] used is preferably 60:40 to 99:1, more preferably 70:30 to 95:5, on a molar basis.

[0077] Examples of the resin (A1b) include the resins described in JP-A Nos. 2008-134515 and 2008-46594.

[0078] Examples of the compound having at least two vinyloxy groups in one molecule include 1,4-cyclohexanedimethanol divinyl ether and ethylene glycol divinyl ether.

[0079] When the resin (A1b) is a resin obtained by mixing a resin containing the structural unit (a2-1) with a novolac resin and then reacting the resulting resin mixture with a vinyloxy group-containing compound, the content of the novolac resin is 30 to 70 mass % based on the total amount of the resin (A1b).

[0080] The resin (A1) can be produced by polymerizing a monomer component containing an ethylenically unsaturated compound corresponding to the structural unit (a1) described above and, if necessary, an ethylenically unsaturated compound corresponding to the structural unit (a2) by a known polymerization method (for example, a radical polymerization method). The weight-average molecular weight of the resin (A1) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 600,000 or less, more preferably 500,000 or less. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analysis conditions for this analysis are described in the Examples of the present application.

[0081] The content of resin (A1) relative to the total amount of resins contained in the resist composition is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less, even more preferably 70 mass% or less.

[0082] Resin (A1) may be a novolak resin (hereinafter sometimes referred to as "resin (A1c)") into which acid-labile groups containing groups that can be cleaved by the action of acid have been introduced. This resin refers to a novolak resin described below in which some or all of the phenolic hydroxyl groups have been protected with acid-labile groups containing groups that can be cleaved by the action of acid, or a novolak resin described below in which some or all of the phenolic hydroxyl groups have been substituted with acid-labile groups containing groups that can be cleaved by the action of acid. This resin is also called a novolak resin having acid-labile groups (groups that contain groups that can be cleaved by contact with acid). Novolac resins are resins obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as a "phenol compound") with an aldehyde in the presence of an acid catalyst. Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, 2-methylresorcinol, 4-methylresorcinol, and 5-methylresorcinol. , 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 2-methoxyresorcinol, hydroquinone, 4-tert-butylcatechol, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid esters, α-naphthol, β-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde, etc. These may be used alone or in combination of two or more. Among these, preferred phenol compounds include, for example, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol.

[0083] Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein, and crotonaldehyde; alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanaldehyde, and furyl acrolein; aromatic aldehydes such as furfural, benzaldehyde, o-, m-, or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4-, or 3,5-dimethylbenzaldehyde, o-, m-, or p-hydroxybenzaldehyde, and o-, m-, or p-nitrobenzaldehyde; and aromatic aliphatic aldehydes such as phenylacetaldehyde and cinnamic aldehyde. These may be used alone or in combination of two or more. Among these, formaldehyde is preferred because it is easily available industrially.

[0084] Examples of catalysts used in the addition condensation reaction include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid, and p-toluenesulfonic acid, and divalent metal salts such as zinc acetate, zinc chloride, and magnesium acetate. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.01 to 1 mole per mole of aldehyde.

[0085] The condensation reaction can be carried out according to a conventional method. For example, it can be carried out at a temperature in the range of 60 to 150°C for about 2 to 30 hours. The condensation reaction may be carried out in the presence of a solvent. Examples of such solvents include ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, and acetone. After the reaction is complete, for example, a water-insoluble solvent can be added to the reaction mixture if necessary, and the reaction mixture can be washed with water and then concentrated to isolate the novolac resin. After the reaction is complete, a basic compound can be added to neutralize the acid catalyst, and the neutralized salt can be removed by washing with water.

[0086] The weight average molecular weight of the novolak resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 9,000 or less, and even more preferably 8,000 or less. In the present specification, the weight average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analysis conditions for this analysis are described in the examples of the present application.

[0087] The acid labile groups introduced into the novolak resin are not particularly limited as long as they contain a group that can be cleaved by the action of an acid, and examples thereof include known acid labile groups. The acid labile groups are introduced into some or all of the phenolic hydroxyl groups in the novolak resin obtained by condensation as described above.

[0088] Examples of the acid labile group introduced into the phenolic hydroxyl group of the novolac resin include the group represented by the above formula (10) or the group represented by formula (20). Preferred are the group represented by formula (1') or the group represented by formula (2). Specific examples of the acid labile group include a tert-butoxycarbonyloxy group, a 1-methylcyclopentan-1-yloxycarbonyloxy group, a 1-(cyclopentan-1-yl)-1-methylalkoxycarbonyloxy group, a butyloxyethoxy group, an ethoxypropyloxy group, an ethoxybutyloxy group, a tetrahydro-2-pyranyloxy group, a tetrahydro-2-furyloxy group, a methoxyethoxy group, a 1-ethoxyethoxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a propyloxy group, a butyloxyeth ... hydroxyethoxy group, cyclohexyloxyethoxy group, 1-(2-methylpropoxy)ethoxy group, 1-(2-methoxyethoxy)ethoxy group, 1-(2-acetoxyethoxy)ethoxy group, 1-[2-(1-adamantyloxy)ethoxy]ethoxy group, 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethoxy group, 3-oxocyclohexyloxy group, 4-methyltetrahydro-2-pyron-4-yloxy group, and the like. Among these, at least one selected from the group consisting of an ethoxyethoxy group, an ethoxypropyloxy group, an ethoxybutyloxy group, an isopropyloxyethoxy group, a cyclohexyloxyethoxy group, and a 1-(2-methylpropoxy)ethoxy group is preferred, at least one selected from the group consisting of an ethoxyethoxy group, an isopropyloxyethoxy group, and a cyclohexyloxyethoxy group is more preferred, and a 1-ethoxyethoxy group is even more preferred.

[0089] An example of the novolak resin (A1c) having an acid labile group is a resin containing a structural unit represented by formula (a3A) (hereinafter sometimes referred to as "structural unit (a3A)") or a structural unit represented by formula (a3B) (hereinafter sometimes referred to as "structural unit (a3B)"). TIFF2025183938000048.tif41170[In formula (a3A), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms; a1 and R a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R a3represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.] TIFF2025183938000049.tif36170[In formula (a3B), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms; a1’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. ab represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ab may be the same or different.]

[0090] R ab Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. R ab Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (R) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group. abis preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. p is preferably 0 to 2, and more preferably 0 or 1.

[0091] Examples of the combination of structural units contained in the novolak resin (A1c) having an acid labile group include those represented by formulae (A1c-1) to (A1c-12). TIFF2025183938000050.tif198170

[0092] The introduction ratio (introduction rate) of acid labile groups is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the phenolic hydroxyl groups of the novolak resin of Resin (A1c). Also, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. Furthermore, there is an optimal introduction rate depending on the acid labile group. When resin (A1) contains acid labile groups (2), the proportion of acid labile groups (2) introduced is preferably 20 mol% or more, more preferably 30 mol% or more, relative to the phenolic hydroxyl groups. When resin (A1) contains ethoxyethoxy groups as acid labile groups, the proportion is more preferably 30 to 60 mol%, when resin (A1) contains propyloxyethoxy groups, the proportion is more preferably 20 to 60 mol%, and when resin (A1) contains cyclohexyloxyethoxy groups, the proportion is more preferably 20 to 60 mol%. By adjusting the proportion within these ranges, it is possible to effectively ensure the resolution, film retention, and heat resistance after pattern formation with a resist composition using this resin. The introduction ratio of the acid labile group is, for example, 1 It can be measured by H-NMR.

[0093] The method for introducing an acid labile group into a phenolic hydroxyl group of a novolak resin includes methods known in the art. For example, when an ethoxyethoxy group is introduced as the acid labile group, a predetermined amount of ethyl vinyl ether is added to a novolak resin at room temperature in the presence of an acid catalyst, the mixture is reacted for a predetermined time in the presence of the acid catalyst, and then diethyl ether is added and the mixture is washed with water.

[0094] The weight-average molecular weight of the resin (A1c) is preferably 3,000 or more, more preferably 4,000 or more, and preferably 200,000 or less, more preferably 100,000 or less. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analysis conditions for this analysis are described in the Examples of the present application.

[0095] The content of resin (A1c) relative to the total amount of resins contained in the resist composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, and is preferably 95% by mass or less, more preferably 85% by mass or less, even more preferably 70% by mass or less.

[0096] <Resin (A2)> Resin (A2) is preferably an alkali-soluble resin. An alkali-soluble resin is a resin that has an acidic group (sometimes called a hydrophilic group) and is soluble in an alkaline developer. Examples of the acidic group include a carboxy group, a sulfo group, and a hydroxy group (such as a phenolic hydroxy group). Examples of alkali-soluble resins include those known in the resist field, such as novolak resins, resins containing the structural unit (a2-1) but not the structural unit (a1), such as resins containing a structural unit derived from hydroxystyrene, resins containing a structural unit derived from a (meth)acrylic acid ester, and polyalkylene glycols. Novolak resins are preferred. The alkali-soluble resin preferably does not have an acid labile group. That is, the alkali-soluble resin is preferably a resin containing a structural unit having an acidic group but not containing a structural unit having an acid labile group. The alkali-soluble resin preferably does not change in solubility in an aqueous alkaline solution upon contact with acid. The alkali-soluble resins may be used alone or in combination of two or more. In the resin (A2), the total content of structural units having an acidic group is preferably 3 to 100 mol%, more preferably 5 to 100 mol%, even more preferably 10 to 100 mol%, still more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%, particularly preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%, based on all structural units in the resin (A2). The resin (A2) may contain only one type of structural unit having an acidic group, or may contain multiple types.

[0097] Examples of alkali-soluble resins include resins that have a residual film ratio of 0% to 90% when developed with an alkaline developer under actual use conditions, preferably 0% to 85%, and more preferably 0% to 80%.

[0098] The remaining film ratio can be measured, for example, as follows. After dissolving the resin in an organic solvent, the solution is filtered using a filter if necessary. Then, the solution is applied to a substrate using a spin coater or the like, and heated to remove the organic solvent. The resulting organic film on the substrate is measured using a film thickness meter, developed with a 2.38% by mass alkaline aqueous solution, and the film thickness after development is measured again using the film thickness meter. The remaining film ratio can be obtained by dividing the measured film thickness after development by the film thickness before development. The development conditions are those under actual use conditions. For example, the development temperature can be 5 to 60°C, and the development time can be 5 to 600 seconds. The alkaline developer can be any of various alkaline aqueous solutions used in this field, such as aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).

[0099] The novolak resin is a resin obtained by condensing a phenol compound with an aldehyde in the presence of a catalyst, and can be selected from, for example, those described above as resin (A1c). An example of a novolac resin is a resin containing a structural unit represented by formula (a4) (hereinafter, sometimes referred to as "structural unit (a4)"). TIFF2025183938000051.tif27170[In formula (a4), R ac represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p1 represents 0, 1, 2, or 3. When p1 is 2 or 3, R ac may be the same or different. q1 represents 1, 2 or 3, provided that the sum of p1 and q1 is 4 or less. R ac The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms are R ab The same groups as those shown below can be mentioned. R acis preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, even more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and even more preferably a methyl group or a methoxy group. p1 is preferably 0 to 2, and more preferably 1 or 2. q1 is preferably 1 or 2, and more preferably 1. The weight-average molecular weight of the novolak resin is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and even more preferably 6,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 9,000 or less, and even more preferably 8,000 or less. By adjusting the weight-average molecular weight within this range, thinning and residues after development can be effectively prevented. The weight-average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. Detailed analytical conditions for this analysis are described in the Examples section of this application.

[0100] Examples of resins containing structural units derived from hydroxystyrene include resins containing structural units derived from monomers having a phenolic hydroxyl group, such as hydroxystyrenes such as hydroxystyrene (p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene) and isopropenylphenol (p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol), and specific examples include resins containing a structural unit represented by formula (a2-1).The resin containing a structural unit derived from hydroxystyrene may contain, in addition to the structural units derived from the above monomers, structural units derived from monomers exemplified below in the resin containing a structural unit derived from a (meth)acrylic acid ester. The resin containing a structural unit derived from hydroxystyrene is typically poly(vinylphenol) (poly(hydroxystyrene)), and preferably poly(p-vinylphenol) (poly(p-hydroxystyrene)). Specific examples include resins containing structural units represented by formula (a2-1). Such poly(vinylphenol) can be obtained, for example, by polymerizing the monomers described in JP 2010-204634 A.

[0101] Examples of resins containing structural units derived from (meth)acrylic acid esters include those obtained by using the following compounds as monomers and polymerizing one or more of these monomers in combination by a conventional method. That is, resins containing structural units derived from (meth)acrylic acid esters include resins containing structural units derived from the following monomers: Monomers having a carboxy group such as (meth)acrylic acid; Monomers having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Monomers having multiple ether bonds, such as polyethylene glycol monomethyl ether (meth)acrylates (polyalkylene glycol monoalkyl ether (meth)acrylates), such as diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, and nonaethylene glycol monomethyl ether (meth)acrylate.

[0102] The above-mentioned monomers may be used in combination with (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, tert-butyl (meth)acrylate, and hexyl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate; monocyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate and norbornyl (meth)acrylate; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; and ethylene glycol monoalkyl ether (meth)acrylates (alkylene glycol monoalkyl ether (meth)acrylates) such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, and ethylene glycol monobutyl ether (meth)acrylate. In addition to the above monomers, styrenes such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, and 4-isopropoxystyrene; carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and the hydroxystyrenes exemplified in the resin containing the structural unit derived from hydroxystyrene described above may also be used in combination. Examples of structural units derived from such monomers include structural units represented by formulae (a2-1) to (a2-4). Polyalkylene glycols are polymers obtained by addition polymerization of alkylene oxides to alcohols. Examples of alcohols include butanol, ethylene glycol, propylene glycol, glycerin, and pentaerythritol. Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0103] The content of resin (A2) relative to the total amount of resins contained in the resist composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0104] The resin (A2) can adjust the solubility of the resist in a developer (alkaline aqueous solution) by interacting with the photosensitizer (I), and can also provide resistance to the developer (alkaline aqueous solution) and plating solution by crosslinking with the photosensitizer (I), thereby improving the accuracy of the plated object.

[0105] The mass ratio ((A1):(A2)) of the resin (A1) and the resin (A2) contained in the resist composition is usually 20:80 to 80:20, and preferably 30:70 to 70:30. Setting the mass ratio within this range is advantageous because it can further improve the precision of the plated product.

[0106] In the resist composition of the present invention, the content of resin (A1) and resin (A2) is preferably 80% by mass or more and 99% by mass or less, based on the total amount of solids in the resist composition. The content of resin (A1) is preferably 1% by mass or more and 98% by mass or less, and more preferably 5% by mass or more and 90% by mass or less, based on the total amount of solids in the resist composition. The content of resin (A2) is preferably 1% by mass or more and 98% by mass or less, and more preferably 5% by mass or more and 90% by mass or less, based on the total amount of solids in the resist composition. The solids and the content of each component contained in the resist composition of the present invention can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0107] <Acid generator (B)> The acid generator (B) is a compound that can be decomposed by light irradiation (exposure) to generate an acid. The generated acid can eliminate a leaving group contained in the acid labile group of the resin (A1), converting the acid labile group to a hydrophilic group (e.g., a carboxy group, a hydroxy group (phenolic hydroxyl group, etc.)). In other words, by exposing a resist composition containing the resin (A1) to light, the resist can be made soluble in a developer (an alkaline aqueous solution).

[0108] The acid generator (B) essentially contains a compound (hereinafter sometimes referred to as "compound (B-1)") having a maximum molar absorption coefficient of 6000 (L / (mol·cm)) or less in the wavelength range of 355 nm to 375 nm. The molar absorption coefficient is preferably 5800 (L / (mol cm)) or less, more preferably 5500 (L / (mol cm)) or less, and even more preferably 5200 (L / (mol cm)) or less. It is also preferably 100 (L / (mol cm)) or more, more preferably 200 (L / (mol cm)) or more, even more preferably 300 (L / (mol cm)) or more, and even more preferably 500 (L / (mol cm)) or more. The molar absorption coefficient is calculated by the method described in the Examples. Regarding the molar absorption coefficient of the acid generator, under actual use conditions, specifically in the resist composition, the absorbance waveform may shift slightly to the shorter or longer wavelength side due to interactions with other components. Therefore, in the present invention, the molar absorption coefficient is evaluated in the wavelength range of 355 nm to 375 nm, which includes a wavelength of 365 nm (i-line) at the center and slightly to the shorter and longer wavelength sides.

[0109] The acid generator (B) preferably contains a compound having an oxime skeleton or an amide skeleton. In particular, the compound (B-1) is preferably a compound having an oxime skeleton or an amide skeleton. In this specification, an amide skeleton is a skeleton in which one carbonyl group (-CO-) is bonded to a nitrogen atom, and an imide skeleton is a skeleton in which two carbonyl groups (-CO-) are bonded to a nitrogen atom, and the two are different. Examples of the compound (B-1) include compounds having a group represented by the following formula (p0) or a group represented by the following formula (q0). TIFF2025183938000052.tif35170 [In formula (p0) and formula (q0), * represents a bond.] Compound (B-1) is more preferably a compound having an oxime sulfonate group or an amido sulfonate group. In this specification, an amido sulfonate group is a group in which one carbonyl group (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom, and an imido sulfonate group is a group in which two carbonyl groups (-CO-) and one sulfonyloxy group (-O-SO2-) are bonded to a nitrogen atom, and the two are different. Examples of the compound (B-1) include compounds having a group represented by the following formula (p1) or a group represented by the following formula (q1). TIFF2025183938000053.tif40170 [In formula (p1) and formula (q1), * represents a bond.] Examples of the compound (B-1) include compounds represented by formulas (b2) to (b4). The compound represented by formula (b2) or formula (b4) is preferred, and the compound represented by formula (b4) is more preferred. TIFF2025183938000054.tif100170[In formula (b2) to formula (b4), R b1 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom or a carbonyl group. R b3 , R b4 and R b5 are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b2 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms. R b6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. x2 and x3 each independently represent an integer of 0 to 5. When x2 or x3 is 2 or more, multiple R b3 or R b4 may be the same or different. x4 represents an integer of 0 to 6. When x4 is 2 or more, multiple R b5 may be the same or different.]

[0110] R b1 Examples of the hydrocarbon group having 1 to 18 carbon atoms in the hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom include linear or branched chain hydrocarbon groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, and groups having 4 to 18 carbon atoms which are combinations of these groups. As the linear or branched chain hydrocarbon group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. Among these, linear groups are preferred. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferably an aryl group having 6 to 18 carbon atoms, and examples thereof include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.

[0111] Among the groups having 4 to 18 carbon atoms formed by combining the above groups, examples of the group (group having 4 to 18 carbon atoms) formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, a 2-alkyladamantan-2-yl group, and a 1-(adamantan-1-yl)alkane-1-yl group. Examples of groups in which a chain hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 7 to 18 carbon atoms) include aralkyl groups and aromatic hydrocarbon groups having an alkyl group, and specific examples thereof include benzyl groups, phenethyl groups, phenylpropyl groups, trityl groups, naphthylmethyl groups, naphthylethyl groups, p-methylphenyl groups, p-tert-butylphenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Examples of groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (groups having 9 to 18 carbon atoms) include aromatic hydrocarbon groups having an alicyclic hydrocarbon group and alicyclic hydrocarbon groups having an aromatic hydrocarbon group, and specific examples include a p-cyclohexylphenyl group, a p-adamantylphenyl group, and a phenylcyclohexyl group. R b1 Of the hydrocarbon groups having 1 to 18 carbon atoms represented by the formula (I), an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

[0112] R b1 Examples of the group in which a methylene group contained in an alicyclic hydrocarbon group having 3 to 18 carbon atoms is substituted with an oxygen atom or a carbonyl group include groups represented by formulae (Y1) to (Y12). Preferred are groups represented by formulae (Y7) to (Y9), and more preferred is a group represented by formula (Y9). TIFF2025183938000055.tif57170

[0113] The fluorine atom-containing hydrocarbon group having 1 to 18 carbon atoms is a group in which one or more hydrogen atoms contained in the above-mentioned hydrocarbon group having 1 to 18 carbon atoms have been substituted with a fluorine atom, and specific examples include fluoroalkyl groups such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, a fluorohexyl group, a fluoroheptyl group, a fluorooctyl group, a fluorononyl group, and a fluorodecyl group; fluorocycloalkyl groups such as a fluorocyclopropyl group, a fluorocyclobutyl group, a fluorocyclopentyl group, a fluorocyclohexyl group, a fluorocycloheptyl group, a fluorocyclooctyl group, and a fluoroadamantyl group; and fluoroaryl groups such as a fluorophenyl group, a fluoronaphthyl group, and a fluoroanthryl group.

[0114] The hydrocarbon group having 1 to 18 carbon atoms and having a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, or an aromatic hydrocarbon group having 6 to 10 carbon atoms and having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0115] R b3 , R b4 , R b5 and R b6 Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferred. R b3 , R b4 and R b5 Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a methoxy group is preferred.

[0116] Ring W b2 Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring. Ring W b2Examples of the aromatic heterocyclic ring having 6 to 14 carbon atoms include rings having 6 to 14 atoms constituting the ring, and preferred examples include the following rings. TIFF2025183938000056.tif21170 Ring W b2 is preferably a naphthalene ring. x2, x3, and x4 are each independently preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

[0117] Examples of the compound represented by formula (b2) include compounds represented by the following formulas: TIFF2025183938000057.tif60170

[0118] Examples of the compound represented by formula (b3) include compounds represented by the following formulas: TIFF2025183938000058.tif18170

[0119] Examples of the compound represented by formula (b4) include compounds represented by the following formulas: TIFF2025183938000059.tif107170

[0120] The acid generator (B) may further contain other acid generators to the extent that the effects of the present invention are not adversely affected. The other acid generators may be either nonionic or ionic. Examples of nonionic acid generators include organic halides, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), and the like. Typical examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmethide anions.

[0121] Examples of other acid generators that can be used include compounds that generate acid when exposed to radiation, such as those described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, and European Patent No. 126,712. Compounds produced by known methods may also be used. These other acid generators may be used alone or in combination of two or more.

[0122] Among the other acid generators, examples of nonionic acid generators include compounds represented by formula (b1). TIFF2025183938000060.tif38170[In formula (b1), R b1 has the same meaning as above. R b2 represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Ring W b1 represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms or an aromatic heterocyclic ring having 6 to 14 carbon atoms. x represents an integer of 0 to 6. When x is 2 or more, a plurality of R b2 may be the same or different.]

[0123] The compound represented by formula (b1) is preferably a compound represented by any one of formulas (b5) to (b8), and more preferably a compound represented by formula (b5). TIFF2025183938000061.tif101170 [In formula (b5) to formula (b8), Rb1 , R b2 and x have the same meaning as above. y represents an integer of 0 to 4, and z represents an integer of 0 to 2. When y is 2 or more, a plurality of R b2 may be the same or different. When z is 2, two R b2 may be the same or different. X b1 and X b2 each independently represents -O-, -S- or -CO-.

[0124] R b2 Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferred. R b2 Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a methoxy group is preferred. Ring W b1 Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring. Ring W b1 Examples of the aromatic heterocyclic ring having 6 to 14 carbon atoms include rings having 6 to 14 atoms constituting the ring, and preferred examples include the following rings. TIFF2025183938000062.tif21170 Ring W b1 is preferably a naphthalene ring.

[0125] Examples of the compound represented by formula (b1) include compounds represented by formulas (b1-1) to (b1-17). Preferred are compounds represented by formulas (b1-6), (b1-7), (b1-10), (b1-13) and (b1-15).

[0126] TIFF2025183938000063.tif202170

[0127] Among the other acid generators, the ionic acid generator is preferably a compound represented by formula (b9) or formula (b10). TIFF2025183938000064.tif33170 [In formula (b9) and formula (b10), A b1 and A b2 represent each independently an oxygen atom or a sulfur atom. R b8 , R b9 , R b10 and R b11 are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. X1 - and X2 - represents an organic anion.

[0128] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of aromatic hydrocarbon groups having 6 to 12 carbon atoms include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R b8 , R b9 , R b10 and R b11 are each preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a phenyl group.

[0129] X1 - and X2 -Examples of the organic anion represented by formula (b11) include a sulfonate anion, a bis(alkylsulfonyl)amide anion, and a tris(alkylsulfonyl)methide anion. Of these, a sulfonate anion is preferred, and a sulfonate anion represented by formula (b11) is more preferred. TIFF2025183938000065.tif21170[In formula (b11), R b12 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom, and a methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.] R b12 As for R in formula (B1), b1 The same groups as those shown below can be mentioned.

[0130] Examples of the compound represented by formula (b9) include the following compounds. TIFF2025183938000066.tif103170

[0131] Examples of the compound represented by formula (b10) include the following compounds. TIFF2025183938000067.tif62170

[0132] In the resist composition of the present invention, the content of the acid generator (B) relative to 100 parts by mass of the resin (A) is preferably 0.1 to 40 parts by mass, more preferably 0.3 to 30 parts by mass, even more preferably 0.5 to 20 parts by mass, still more preferably 0.7 to 10 parts by mass, and even more preferably 1 to 5 parts by mass. The resist composition of the present invention may contain one type of acid generator (B) alone or multiple types. The content of the compound (B-1) in the acid generator (B) is 10 to 100 mass %, preferably 30 to 100 mass %, and more preferably 40 to 100 mass %, based on the total mass of the acid generator (B).

[0133] <Solvent (D)> The content of the solvent (D) in the resist composition is usually 35% by mass or more, preferably 40% by mass or more, and more preferably 45% by mass or more, and usually 99.9% by mass or less, preferably 99% by mass or less, and more preferably 90% by mass or less. The content of the solvent (D) can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0134] Examples of the solvent (D) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. One type of solvent (D) may be contained alone, or two or more types may be contained.

[0135] <Quencher (C)> The resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as "quencher (C)"). The quencher (C) is a compound that has the effect of capturing the acid generated from the acid generator upon exposure. Examples of the quencher (C) include basic nitrogen-containing organic compounds. Examples of the basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of the amines include aliphatic amines (including primary amines, secondary amines, and tertiary amines), aromatic amines, etc.

[0136] Examples of the amine include compounds represented by formula (C1) or formula (C2). TIFF2025183938000068.tif22170[In formula (C1), R c1 , R c2 and R c3represent each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the alkyl group having 1 to 6 carbon atoms and the alicyclic hydrocarbon group having 3 to 10 carbon atoms may have at least one group selected from the group consisting of a hydroxy group, an amino group, and an alkoxy group having 1 to 6 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms may have at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms.

[0137] Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. As the aromatic hydrocarbon group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include aryl groups such as a phenyl group and a naphthyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and preferably a methoxy group.

[0138] Examples of the compound represented by formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, ... Examples of the amine include ethyldipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, etc. Diisopropylaniline is preferred, and 2,6-diisopropylaniline is particularly preferred.

[0139] TIFF2025183938000069.tif18170[In formula (C2), Ring W 1 represents a heterocycle containing a nitrogen atom as a ring-constituting atom, or a benzene ring having a substituted or unsubstituted amino group, and the heterocycle and the benzene ring may have at least one group selected from the group consisting of a hydroxy group and an alkyl group having 1 to 4 carbon atoms. A 1 represents a phenyl group or a naphthyl group. nc represents 2 or 3, and a plurality of A 1may be the same or different.]

[0140] The substituted or unsubstituted amino group is —N(R 4 )(R 5 ) and R 4 and R 5 are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms.

[0141] A heterocycle containing a nitrogen atom as one of the atoms constituting the ring may be an aromatic ring or a non-aromatic ring, and may contain other heteroatoms (e.g., oxygen atoms, sulfur atoms) in addition to the nitrogen atom. The number of nitrogen atoms contained in the heterocycle is, for example, 1 to 3. Examples of the heterocycle include rings represented by any of formulas (Y13) to (Y28). When one of the hydrogen atoms contained in the ring is removed, A 1 It becomes a combination with. TIFF2025183938000070.tif66170

[0142] Ring W 1is preferably a heterocyclic ring containing a nitrogen atom as an atom constituting the ring, more preferably a 5- or 6-membered aromatic heterocyclic ring containing a nitrogen atom as an atom constituting the ring, and even more preferably a ring represented by any one of formulae (Y20) to (Y25).

[0143] Examples of the compound represented by formula (C2) include compounds represented by any of formulas (C2-1) to (C2-11), and preferably compounds represented by any of formulas (C2-2) to (C2-8). TIFF2025183938000071.tif98170

[0144] The content of the quencher (C) in the solid content of the resist composition is preferably from 0.0001 to 5 mass%, more preferably from 0.0001 to 4 mass%, even more preferably from 0.001 to 3 mass%, even more preferably from 0.01 to 1.0 mass%, even more preferably from 0.05 to 0.8 mass%, and even more preferably from 0.1 to 0.7 mass%.

[0145] <Adhesion improver (E)> The adhesion improver (E) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to metals, etc. used in substrates or wiring, etc. By preventing metal corrosion, it exhibits a rust-preventing effect. In addition to these effects, it can also improve adhesion between the substrate or metal, etc. and the resist composition. Examples of the adhesion improver (E) include sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds, which can be used alone or in combination of two or more.

[0146] The sulfur-containing compound may be, for example, a compound having a sulfide bond and / or a mercapto group. The sulfur-containing compound may be a chain compound or a compound having a cyclic structure. Examples of chain compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioglycolic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0147] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group, and more preferably a heterocyclic compound having a sulfide bond and a mercapto group. The heterocyclic compound is more preferably a heterocyclic compound having a sulfide bond in the ring structure. In the sulfur-containing compound, the number of sulfide bonds and mercapto groups is not particularly limited, and each may be 1 or more. The heterocyclic ring in the heterocyclic compound may be either a monocyclic ring or a polycyclic ring, and may be either a saturated or unsaturated ring. The heterocyclic ring preferably further contains a heteroatom other than a sulfur atom. Examples of the heteroatom include an oxygen atom and a nitrogen atom, and preferably a nitrogen atom. The heterocycle is preferably a heterocycle having 2 to 12 carbon atoms, more preferably a heterocycle having 2 to 6 carbon atoms. The heterocycle is preferably a monocycle. The heterocycle is preferably an unsaturated ring. The heterocycle is preferably an unsaturated monocycle.

[0148] Examples of the heterocycle include the following heterocycles: TIFF2025183938000072.tif36170

[0149] The sulfur-containing compound may be a polymer. This polymer preferably contains a structure having a sulfide bond and a mercapto group in a side chain. The structure having a sulfide bond and a mercapto group (hereinafter sometimes referred to as unit (1)) is preferably bonded to the main chain via a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond.

[0150] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, it may contain the above-mentioned structural unit (a1) having an acid labile group, structural unit (a2) not having an acid labile group, and the like. The weight average molecular weight of the homopolymer and copolymer is usually 3000 or more, preferably 5000 or more, and usually 100,000 or less, preferably 50,000 or less. The weight average molecular weight is determined by gel permeation chromatography analysis as a converted value based on standard polystyrene. When the sulfur-containing compound is a polymer, the content of the structural unit having a sulfide bond and a mercapto group is usually 0.1 to 50 mol %, preferably 0.5 to 30 mol %, and more preferably 1 to 20 mol %, based on the total structural units of the polymer of the sulfur-containing compound.

[0151] The sulfur-containing compound is preferably, for example, a compound represented by formula (IA) or a polymer having a structural unit represented by formula (IB). TIFF2025183938000073.tif24170[In formula (IA), R i11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, -SR 11 or a group represented by -NR 12 R 13 represents a group represented by the formula: R 11 , R 12 and R 13are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an acyl group having 2 to 12 carbon atoms, and these chain hydrocarbon groups, aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and acyl groups may have a hydroxy group. R i12 and R i13 represent, independently of each other, a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. A and B represent, independently of each other, a nitrogen atom or a carbon atom. n1 and m1 each independently represent 0 or 1, provided that when A is a nitrogen atom, n1 represents 0, when A is a carbon atom, n1 represents 1, when B is a nitrogen atom, m1 represents 0, and when B is a carbon atom, m1 represents 1.

[0152] Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms, such as a phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of aromatic hydrocarbon groups having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group.

[0153] R 11 is preferably a chain hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 2 to 12 carbon atoms, and R 12 and R 13 are preferably each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an acyl group having 2 to 12 carbon atoms. Examples of the acyl group having 2 to 12 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, a hexylcarbonyl group, a heptylcarbonyl group, an octylcarbonyl group, a decylcarbonyl group, a dodecylcarbonyl group, and a benzoyl group.

[0154] R i11 is more preferably a hydrogen atom or a mercapto group. R i12 and R i13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. At least one of A and B is preferably a nitrogen atom, and more preferably both are nitrogen atoms.

[0155] TIFF2025183938000074.tif49170[In formula (IB), R i21 and R i31 A each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. 1 and B 1 represent, independently of each other, a nitrogen atom or a carbon atom. n2 and m2 each independently represent 0 or 1. 1 When is a nitrogen atom, n2 represents 0, and A 1 is a carbon atom, n2 represents 1, and B 1 is a nitrogen atom, m2 represents 0, and B 1 is a carbon atom, m2 represents 1. R i4represents a hydrogen atom or a methyl group. X i1 represents a sulfur atom and an NH group. L i1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.

[0156] R i21 and R i31 Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and preferably alkyl groups having 1 to 4 carbon atoms. R i21 and R i31 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include aryl groups having 6 to 14 carbon atoms such as a phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group, and preferably an aryl group having 6 to 10 carbon atoms. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. R i21 and R i31 Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cycloalkyl groups having 3 to 18 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, and a norbornyl group, and preferably an alicyclic hydrocarbon group having 5 to 10 carbon atoms. R i21 and R i31 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0157] L i1 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as a 1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Examples of the arylene group include a phenylene group, a tolylene group, and a naphthylene group. L i1 is preferably an alkanediyl group having 2 to 14 carbon atoms containing an ester bond or a group formed by combining an arylene group having 6 to 10 carbon atoms with an alkanediyl group having 1 to 11 carbon atoms.

[0158] The structural unit represented by formula (IB) is preferably a structural unit represented by formula (IB-1) or a structural unit represented by formula (IB-2). TIFF2025183938000075.tif78170[In formula (IB-1), Ri22 and R i32 A each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. 2 and B 3 represent each independently a nitrogen atom or a carbon atom. n3 and m3 each independently represent 0 or 1. 2 is a nitrogen atom, n3 represents 0, and A 2 is a carbon atom, n3 represents 1, and B 2 is a nitrogen atom, m3 represents 0, and B 2 is a carbon atom, m3 represents 1. X i11 represents a sulfur atom and an NH group. L i2 represents a divalent hydrocarbon group having 1 to 18 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. R i5 represents a hydrogen atom or a methyl group. In formula (IB-2), R i23 and R i33 A each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. 3 and B 3 represent, independently of each other, a nitrogen atom or a carbon atom. n4 and m4 each independently represent 0 or 1. 3 is a nitrogen atom, n4 represents 0, and A 3 is a carbon atom, n4 represents 1, and B 3 is a nitrogen atom, m4 represents 0, and B 3 is a carbon atom, m4 represents 1. X i12 represents a sulfur atom and an NH group. L i3 represents a divalent hydrocarbon group having 1 to 14 carbon atoms. A methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. Ri7 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R i6 represents a hydrogen atom or a methyl group. mx represents an integer between 0 and 4.

[0159] R i22 , R i32 , R i23 and R i33 As the chain hydrocarbon group having 1 to 10 carbon atoms represented by R i21 and R i31 Examples thereof include the same chain hydrocarbon groups having 1 to 10 carbon atoms as those represented by the following formula: R i22 , R i32 , R i23 and R i33 As the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R i21 and R i31 Examples of the aromatic hydrocarbon group include the same aromatic hydrocarbon groups having 6 to 14 carbon atoms as those represented by the following formula: R i22 , R i32 , R i23 and R i33 As the alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R i21 and R i31 Examples thereof include the same alicyclic hydrocarbon groups having 3 to 18 carbon atoms as those represented by the following formula:

[0160] L i2Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1, alkanediyl groups such as a 1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group; Examples of the arylene group include a phenylene group, a tolylene group, and a naphthylene group. L i2 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms.

[0161] L i3Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, and an undecane-1,11-diyl group. alkanediyl groups such as a dodecane-1,12-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. L i3 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms. Based on the position of the phenyl group that is bonded to the main chain, L i3 is preferably bonded at the p-position.

[0162] R i7 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R i7 Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0163] Examples of sulfur-containing compounds include compounds represented by any of formulas (I-1) to (I-26). Of these, preferred are compounds represented by formulas (I-1) to (I-13), and more preferred are compounds represented by formulas (I-1), (I-4), and (I-11). TIFF2025183938000076.tif82170

[0164] TIFF2025183938000077.tif98170

[0165] Examples of the sulfur-containing compound include a homopolymer consisting of any one of the structural units represented by formulae (I-27) to (I-38) and a copolymer containing one or more of these structural units. Copolymers containing one or more of the structural units represented by formulae (I-27) to (I-36) are preferred, and copolymers containing a structural unit represented by formula (I-33) are more preferred. TIFF2025183938000078.tif145170

[0166] Examples of such copolymers include copolymers comprising structural units represented by formulae (I-39) to (I-48). Of these, polymers having structural units represented by formulae (I-39) to (I-44) are preferred.

[0167] TIFF2025183938000079.tif245170

[0168] TIFF2025183938000080.tif158170

[0169] The sulfur-containing compound may be synthesized by a known method (for example, JP 2010-79081 A) or may be a commercially available product. The polymer containing a sulfur-containing compound may be a commercially available product (for example, bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd.) or may be synthesized by a known method (for example, JP 2001-75277 A).

[0170] Examples of aromatic hydroxy compounds include phenol, cresol, xylenol, pyrocatechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid.

[0171] An example of the benzotriazole compound is a compound represented by formula (IX). TIFF2025183938000081.tif29170[In formula (IX), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a carboxy group, an amino group, a hydroxy group, a cyano group, a formyl group, a sulfonylalkyl group or a sulfo group. Q is a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group, or **-R 3X -N(R 4X )(R 5X ) and the hydrocarbon group may have an amide bond or an ester bond in the structure. R 3X represents an alkanediyl group having 1 to 6 carbon atoms. ** represents a bond to a nitrogen atom contained in the ring. R 4X and R 5X each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms.]

[0172] R 1 , R 2 The hydrocarbon group having 1 to 10 carbon atoms for Q may be either an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and may have saturated and / or unsaturated bonds. The aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a methylpentyl group, an n-hexyl group, and an n-heptyl group. The aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably an aryl group, and examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may further have a substituent, and examples of the aromatic hydrocarbon group having a substituent include an aralkyl group and an aromatic hydrocarbon group having an alkyl group, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include a hydroxyalkyl group and an alkoxyalkyl group. R 3X The alkanediyl group having 1 to 6 carbon atoms may be either linear or branched, and examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. R 4X and R 5XExamples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R 4X and R 5X Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a dihydroxyethyl group. R 4X and R 5X Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include a methoxymethyl group, a methoxyethyl group, and a dimethoxyethyl group.

[0173] When the resist composition of the present invention is applied to a substrate on which Cu is formed, Q in formula (IX) is **-R 3X -N(R 4X )(R 5X ) is preferred. 4X and R 5X When at least one of the groups is an alkyl group having 1 to 6 carbon atoms, the benzotriazole compound has poor water solubility, but is preferably used when other components capable of dissolving this compound are present.

[0174] Furthermore, when the resist composition of the present invention is applied to a substrate having an inorganic material layer (e.g., a polysilicon film, an amorphous silicon film, etc.), Q in formula (IX) preferably represents a water-soluble group. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxy group, etc. are preferred. This allows the substrate to exhibit corrosion resistance more effectively.

[0175] Examples of benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-methylbenzotriazole, 5-benzotriazolecarboxylic acid, 1-methoxybenzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethane, and 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane.

[0176] The triazine-based compound includes a compound represented by formula (II). TIFF2025183938000082.tif28170[In formula (II), R 6 , R 7 and R 8 represent each independently a halogen atom, a hydrogen atom, a hydroxy group, an amino group, a mercapto group, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or an amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same as those mentioned above. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

[0177] An example of the triazine compound is 1,3,5-triazine-2,4,6-trithiol.

[0178] An example of the silicon-containing compound is a compound represented by formula (IIA). TIFF2025183938000083.tif30170[In formula (IIA), R j1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms. R j2 ~R j4 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group, or a mercaptoalkyl group having 1 to 5 carbon atoms; R j2 ~R j4 At least one of them is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms. t i represents an integer from 1 to 10.

[0179] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group and an ethoxy group. Examples of the mercaptoalkyl group having 1 to 5 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

[0180] R j1 is preferably a methyl group, an ethyl group, or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or a mercaptopropyl group (particularly, a 3-mercaptopropyl group). R j2 ~R j4 are preferably each independently a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methyl group or a methoxy group, provided that at least one of these is preferably a mercapto group or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a mercapto group or a mercaptopropyl group. R j2 and Rj3 may be the same or different from each other, but are preferably the same from the viewpoint of productivity.

[0181] Examples of the compound of formula (IIA) include compounds represented by the following formulae (II-1) to (II-7). TIFF2025183938000084.tif188170Of these, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like are preferred.

[0182] The content of the adhesion improver (E) relative to the total amount of solids in the resist composition is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, even more preferably 0.005% by mass or more, and particularly preferably 0.008% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 4% by mass or less, still more preferably 3% by mass or less, especially preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. By setting the content within this range, a resist composition that can form a high-precision resist pattern can be obtained, and adhesion between the resist pattern and the substrate can be ensured.

[0183] <Other ingredients> The resist composition of the present invention may optionally contain components other than those described above (hereinafter, these may be referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, can be used. When other component (F) is used, the content thereof is appropriately selected depending on the type of other component (F).

[0184] 2. Preparation of Resist Composition The resist composition of the present invention can be prepared by mixing resin (A1), photosensitizer (I), acid generator (B), and, if necessary, resin (A2), resins other than resin (A1) and resin (A2), quencher (C), solvent (D), adhesion improver (E), and other components (F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing can be selected from 10 to 40°C depending on the type of resin, the solubility of the resin in the solvent (D), and other factors. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing method is also not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of about 0.003 to 50 μm.

[0185] The resist composition of the present invention has a minimum transmittance of 23% or more for radiation in the wavelength range of 355 to 375 nm under actual use conditions, specifically, when a film having a working thickness is formed using the resist composition. The transmittance is preferably 25% or more, more preferably 27% or more, even more preferably 29% or more, and even more preferably 30% or more. The transmittance is preferably 99% or less, and more preferably 98% or less. The transmittance is calculated using the method described in the Examples. Here, the term "usage film thickness of the resist composition of the present invention" refers to the film thickness of a composition layer formed from the resist composition, and also refers to the film thickness of a resist film or resist pattern produced from the resist composition. As will be described later, this can be the film thickness of a composition layer formed by applying the resist composition onto a substrate, drying, and heating (pre-baking). The thickness of the film used is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. It is usually 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. It is usually in the range of 1 to 300 μm, preferably 1 to 200 μm, more preferably 2 to 200 μm, even more preferably 3 to 150 μm, and even more preferably 4 to 150 μm.

[0186] The resist composition of the present invention contains a photosensitizer (I) and an acid generator (B). The photosensitizer (I) and the acid generator (B) may affect light transmittance, and therefore a resist pattern formed using a resist composition containing these components may not achieve sufficient resolution or exposure margin. This tendency may become particularly pronounced when the content of the above components increases or the film thickness increases. The present invention relates to a resist composition containing a specific amount of photosensitizer (I) and an acid generator (B) having a specific molar absorption coefficient, and when a film is formed using the resist composition at a working thickness, the minimum transmittance of radiation in the wavelength range of 355 to 375 nm is 23% or more, thereby enabling the formation of a resist pattern with excellent resolution and exposure margin. While the reason for this effect is not necessarily definitive, it is believed that sufficient resolution and exposure margin can be ensured in the resist pattern by adjusting the content of photosensitizer (I) in the resist composition to a specific range and selecting an acid generator (B) having a molar absorption coefficient within a specific range, thereby adjusting the transmittance of radiation in the resist film to a specific range.

[0187] 3. Resist pattern manufacturing method The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a metal surface of a substrate having a metal surface; (2) drying the applied resist composition to form a composition layer; (3) exposing the composition layer to light; and (4) A step of developing the composition layer after exposure.

[0188] The resist composition can be applied to a substrate using a commonly used device such as a spin coater. Alternatively, a photosensitive dry film formed by applying the resist composition to a base film may be laminated on the substrate. The substrate may be an inorganic substrate such as a silicon wafer, on which a semiconductor element (e.g., a transistor, a diode, etc.) may be formed in advance. When the resist composition of the present invention is used for bump formation, the substrate is preferably one on which a conductive material is further laminated. The conductive material may be at least one metal selected from the group consisting of gold, copper, nickel, tin, palladium, and silver, or an alloy containing at least one metal selected from the group, and preferably copper or an alloy containing copper. Before applying the resist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. The applied composition is dried to remove the solvent and form a composition layer. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 30 to 600 seconds. The pressure during vacuum drying is preferably 1 to 1.0 × 10 5 It is preferable that the pressure is about Pa.

[0189] After drying, the film thickness of the resulting composition is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. It is usually 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. It is usually in the range of 1 to 300 μm, preferably 1 to 200 μm, more preferably 2 to 200 μm, even more preferably 3 to 150 μm, and even more preferably 4 to 150 μm. The resulting composition layer is typically exposed using an exposure device. Examples of suitable exposure light sources include light sources emitting light with wavelengths of 345 to 436 nm (g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm)), light sources emitting ultraviolet laser light such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), and F2 excimer laser (wavelength: 157 nm), light sources that convert the wavelength of laser light from a solid-state laser light source (such as a YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, and light sources that irradiate electron beams or extreme ultraviolet light (EUV). Among these, i-line is preferred. In this specification, irradiation with these types of radiation may be collectively referred to as "exposure." During exposure, exposure is typically performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct writing without using a mask. The composition layer after exposure may be subjected to a heat treatment (so-called post-exposure bake) to promote the elimination reaction of the acid labile groups in the resin (A1). The heating temperature is usually about 50 to 200° C., preferably about 70 to 150° C. The heating time is usually 40 to 400 seconds, preferably 50 to 350 seconds.

[0190] The heated composition layer is usually developed using a developer in a developing device. Development methods include dipping, puddling, spraying, and dynamic dispensing. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 600 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced.

[0191] When a positive resist pattern is produced from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant. After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed. When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among these, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant and a small amount of water. During development, development may be stopped by replacing the organic developer with a different type of solvent. The developed resist pattern is preferably washed with a rinse solution. There are no particular limitations on the rinse solution as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0192] By exposing a resist obtained using the resist composition of the present invention, a resist pattern with a highly accurate shape can be formed.

[0193] 4. Manufacturing method for plated objects Using the resist pattern formed by the above method as a mold, an electrode material is deposited by plating, and the resist pattern is then peeled off, thereby forming plated objects such as bumps and rewirings. The method for producing a plated object of the present invention comprises the steps of: (5) forming a plated object using the resist pattern as a mold; and (6) A step of stripping the resist pattern is included.

[0194] A resist pattern formed on a substrate having a conductive layer or the like is used as a template to deposit a conductive material using a plating solution by a known method, thereby forming a plated object. Examples of the plating solution include a copper plating solution, a gold plating solution, a nickel plating solution, a solder plating solution, and a silver-tin plating solution. After the plating object is formed, the resist pattern is removed using a stripping solution by a known method. Examples of the stripping solution include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Examples of suitable esters include propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used alone or in combination of two or more. By the above method, plated objects such as bumps and rewirings can be formed. When forming a plated object, the surface of the conductive layer may be subjected to an ashing process or the like to improve adhesion between the conductive layer and the plated object. Examples of ashing methods include a method using oxygen plasma. A plated product obtained using the resist pattern of the present invention swells little in a plating bath, and therefore can be formed with high precision.

[0195] 5.Applications The resist composition of the present invention is useful for producing a thick resist film. For example, it is useful for producing a resist film with a thickness of 1 μm or more. In this case, the thickness of the resist film is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. Also, it is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. Furthermore, the resist composition of the present invention is useful for producing bumps and rewiring by a plating process. When producing bumps and rewiring using the resist composition, they can usually be formed by the following procedure. This allows the production of a resist pattern with an especially excellent pattern shape. First, a conductive material (seed metal) is deposited on a wafer on which semiconductor elements and the like are formed to form a conductive layer. Then, a resist pattern is formed on the conductive layer using the resist composition of the present invention. Next, using the resist pattern as a mold, an electrode material (e.g., Cu, Ni, solder, etc.) is deposited by plating, and the resist pattern and the conductive layer remaining below the resist pattern are removed by etching or the like to form bumps and rewiring. After removing the conductive layer, the electrode material may be melted by heat treatment, if necessary, to form bumps. [Example]

[0196] The present invention will be explained in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are by mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Apparatus: HLC-8320GPC model (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guard column (Tosoh Corporation) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0197] Synthesis Example 1 [Synthesis of Resin (A1)-1] 20 parts of poly-p-hydroxystyrene (S-4P; Maruzen Petrochemical Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone at room temperature and concentrated using an evaporator. The concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were added to a four-neck flask equipped with a reflux condenser, a stirrer, and a thermometer. While maintaining the resulting mixture at 20 to 25°C, 5.05 parts of ethyl vinyl ether was added dropwise to the resulting mixture over 10 minutes. The mixture was stirred at 20 to 25°C for 2 hours. The resulting reaction mixture was diluted with 200 parts of methyl isobutyl ketone, washed with ion-exchanged water, and separated five times. The resulting organic layer was concentrated to 45 parts using an evaporator, and then 150 parts of propylene glycol monomethyl ether acetate was added and concentrated again to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of Resin (A1)-1 (solids content: 29%). Resin (A1)-1 is a resin having the following structural unit: The weight average molecular weight of resin (A1)-1 is 1.16 × 10 4 The ratio of hydroxy groups in poly-p-hydroxystyrene that were substituted with ethoxyethoxy groups was 40.9%. TIFF2025183938000085.tif37170

[0198] Synthesis Example 2 [Synthesis of Resin (A2)-1] A four-neck flask equipped with a stirrer, reflux condenser, and thermometer was charged with 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid, and 826.9 parts of methanol. The mixture was heated to reflux and maintained at this temperature for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone was added, and 1075 parts of the solvent was distilled off at normal pressure. 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added, and the mixture was heated to 65°C. 678 parts of 37% aqueous formalin solution was added dropwise over 1.5 hours, adjusting the temperature to 87°C at the end of the addition. The resulting mixture was maintained at 87°C for 10 hours, after which 1115 parts of methyl isobutyl ketone was added. The mixture was washed three times with deionized water. 500 parts of methyl isobutyl ketone was added to the resulting mixture, and the mixture was concentrated under reduced pressure until the total volume reached 3435 parts. To the resulting mixture, 3796 parts of methyl isobutyl ketone and 4990 parts of n-heptane were added, and the mixture was heated to 60°C and stirred for 1 hour. Thereafter, the mixture was separated, and the lower layer containing the resin was removed, diluted with 3500 parts of propylene glycol monomethyl ether acetate, and concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of Resin (A2)-1 (solid content 43%). The weight-average molecular weight of novolac resin (A2)-1 is 7 × 10 3 Furthermore, the residual film ratio after development with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was 74%. The residual film ratio was measured by the method described in the section <Resin (A2)> of the Detailed Description of the Invention.

[0199] <Preparation of Resist Composition> The components shown in Table 1 were mixed and dissolved to obtain a mixture, which was then filtered through a fluororesin filter with a pore size of 0.5 μm to prepare a resist composition.

[0200] [Table 1]

[0201] <Resin> (A1)-1: Resin (A1)-1 (A2)-1: Resin (A2)-1

[0202] <Acid generator (B)> (B)-1: N-hydroxynaphthalimide triflate (NAI-105; Midori Chemical Co., Ltd.) TIFF2025183938000087.tif23170(B)-2: Compound represented by the following formula (PAG-121; manufactured by BASF) TIFF2025183938000088.tif29170(B)-3: Compound represented by the following formula (synthesized by the method described in WO2016 / 072049) TIFF2025183938000089.tif36170(B)-4: Compound represented by the following formula (synthesized in the same manner as described in WO2016 / 072049, except that (+)-10-camphorsulfonyl chloride was replaced with 1-octanesulfonyl chloride) TIFF2025183938000090.tif29170

[0203] <Photosensitizer (I)> (I)-1: Synthesized by the method described in JP-A-9-110762 In addition, R t1 , R t6 , R t7 , R t9 , R t10 For each mole of the following compound, where R is a hydroxy group, 2 moles of sulfonyl chloride reacted, and the reaction proceeded to almost 100%. t1 , R t6 , R t7 , R t9 , R t10 It was confirmed that the compound was a disubstituted compound in which the hydrogen atoms of two of the hydroxy groups had been replaced by 1,2-naphthoquinone diazide sulfonyl groups (MS: M+: 1080). TIFF2025183938000091.tif35170

[0204] <Quencher (C)> (C)-1: 2,4,5-triphenylimidazole (Tokyo Chemical Industry Co., Ltd.) (C)-2: N,N-dicyclohexylmethylamine (Aldrich)

[0205] <Solvent (D)> (D)-1: Propylene glycol monomethyl ether acetate

[0206] Examples 1 to 6, Comparative Examples 1 to 3 (Measurement of molar extinction coefficient) Acid generators (B)-1, (B)-2, (B)-3, and (B)-4 were each diluted with propylene glycol monomethyl ether acetate to 0.25 mmol / L, and the absorbance was measured in a 1 cm cell using an ultraviolet-visible spectrophotometer (Shimadzu Corporation, UV-3600i Plus). The molar extinction coefficient ε in the wavelength range of 355 to 375 nm was calculated using the following formula: n The maximum molar absorption coefficient in the wavelength range of 355 to 375 nm is shown in Table 2. ε n (L / (mol cm))=A n / (0.00025mol / L ×1cm) ε n : Molar absorption coefficient at each wavelength A n : Absorbance at each wavelength [Table 2]

[0207] (Transmittance measurement) The resist composition was spin-coated onto a quartz glass substrate so that the film thickness after baking would be 4 μm. Thereafter, the coating was pre-baked on a direct hot plate at 100° C. for 180 seconds to form a composition layer. Next, the composition layer formed on the quartz glass substrate was measured for radiation transmittance in the wavelength range of 355 to 375 nm using a spectrophotometer (V-670, manufactured by JASCO Corporation). The minimum transmittance in the wavelength range of 355 to 375 nm is shown in Table 3.

[0208] (i-line exposure evaluation of resist composition) The resist composition was spin-coated onto a 4-inch silicon wafer on which copper had been vapor-deposited, so that the film thickness after pre-baking would be 4.0 μm. Thereafter, the coating was pre-baked on a direct hot plate at 100° C. for 180 seconds to form a composition layer. Next, the composition layer formed on the wafer was exposed to light using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5) through a mask to form a 1:1 line and space pattern (line width: 0.2 to 1 μm) by gradually changing the exposure dose. After exposure, post-exposure baking was performed on a hot plate at 70° C. for 60 seconds, and then puddle development was performed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for 180 seconds to obtain a resist pattern. The resist pattern obtained after development was observed under a scanning electron microscope, and the exposure dose at which a line and space pattern with a line width of 1 μm was obtained was taken as the effective sensitivity.

[0209] <Resolution evaluation> The resist pattern obtained at the effective sensitivity was observed under a scanning electron microscope, and the minimum line width of the resolved line and space pattern was measured.

[0210] <Exposure Latitude (EL)> A line and space pattern with a line width of 1 μm was observed using a scanning electron microscope. The exposure dose at which the pattern began to appear was defined as the minimum exposure dose, and the under-exposure margin (EL u ) was calculated, and the EL was evaluated as follows: less than 35% was marked "x", 35% to less than 40% was marked "△", and 40% or more was marked "◯". EL u =(E op -E un ) / E op *100 E un :Minimum exposure required for pattern to appear E op : Effective sensitivity

[0211] <Plating resistance evaluation> A patterned wafer was prepared using the effective sensitivity obtained in the i-line exposure evaluation, and then immersed in a Cu plating solution at a bath temperature of 27° C. for 15 minutes. After immersion, the patterned wafer was observed under an optical microscope to observe a line and space pattern with a line width of 1 μm. Those in which pattern collapse occurred after immersion for 15 minutes were marked "x", and those in which pattern collapse did not occur after immersion for 15 minutes were marked "good".

[0212] [Table 3]

[0213] Examples 7 and 8, Comparative Example 4 (Transmittance measurement) The resist composition was spin-coated onto a quartz glass substrate so that the film thickness after baking would be 18 μm. Thereafter, the coating was pre-baked on a direct hot plate at 120° C. for 120 seconds to form a composition layer. Next, the composition layer formed on the quartz glass substrate was measured for radiation transmittance in the wavelength range of 355 to 375 nm using a spectrophotometer (V-670, manufactured by JASCO Corporation). The minimum transmittance in the wavelength range of 355 to 375 nm is shown in Table 4.

[0214] (i-line exposure evaluation of resist composition) The resist composition was spin-coated onto a 4-inch silicon wafer on which copper had been vapor-deposited, so that the film thickness after pre-baking would be 18.0 μm. Thereafter, the coating was pre-baked on a direct hot plate at 120° C. for 120 seconds to form a composition layer. Next, the composition layer formed on the wafer was exposed to light through a mask using an i-line stepper (NSR-2005i9C; manufactured by Nikon Corporation, NA=0.5) while gradually changing the exposure dose to form a 1:1 contact hole pattern (hole diameters: 5, 3, 2, 1 μm, pitch: 10, 6, 4, 2 μm). After exposure, post-exposure baking was performed on a hot plate at 80° C. for 30 seconds, and then puddle development was performed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for 180 seconds to obtain a resist pattern. The resist pattern obtained after development was observed under a scanning electron microscope, and the exposure dose that gave a contact hole pattern with a hole diameter of 3 μm was taken as the effective sensitivity.

[0215] <Resolution evaluation> The resist pattern obtained at the effective sensitivity was observed under a scanning electron microscope, and the minimum hole diameter of the contact hole pattern that could be resolved was measured.

[0216] <Plating resistance evaluation> A patterned wafer was prepared using the effective sensitivity obtained in the i-line exposure evaluation, and then immersed in a Cu plating solution at a bath temperature of 27° C. for 10 minutes. After immersion, the patterned wafer was observed under an optical microscope to observe the contact hole pattern with a hole diameter of 3 μm. If the resist pattern dissolved and swelled in the plating solution after 10 minutes of immersion, and a change in the shape of the resist pattern was observed, it was marked "X", and if the shape of the resist pattern did not change after 10 minutes of immersion, it was marked "O". [Table 4]

[0217] The results in Tables 3 and 4 show that the composition layers formed using the resist compositions of the present invention all had a minimum transmittance of radiation in the wavelength range of 355 to 375 nm that was equal to or greater than the specified value.The resist patterns obtained by exposing and developing the composition layers all had excellent resolution and exposure latitude (EL), and also had excellent plating resistance. [Industrial Applicability]

[0218] The resist composition of the present invention is capable of producing a resist pattern having good resolution and exposure margin, and is suitable for semiconductor microfabrication, making it extremely useful industrially.

Claims

1. A resist composition comprising a resin (A1) containing a structural unit having an acid labile group, a photosensitizer (I), and an acid generator (B), the acid generator (B) contains a compound having a maximum molar absorption coefficient of 6000 (L / (mol cm)) or less in a wavelength range of 355 to 375 nm, the content of the photosensitizer (I) is 10 mass % or less based on the solid content of the resist composition, When a film having a thickness to be used is formed using the resist composition, the minimum transmittance of the film to radiation in a wavelength range of 355 to 375 nm is 23% or more. Resist composition.

2. 2. The resist composition according to claim 1, wherein the thickness of the resist film when used is 4 [mu]m or more.

3. 3. The resist composition according to claim 1, wherein the photosensitizer (I) comprises a compound having a quinone diazide sulfonyl group.

4. 3. The resist composition according to claim 1, wherein the photosensitizer (I) comprises a compound having a group represented by formula (a), a group represented by formula (b), or a group represented by formula (c). [In formula (a) and formula (b), * represents a bond.] [In formula (c), * represents a bond.]

5. 3. The resist composition according to claim 1, wherein the acid generator (B) comprises a compound having an oxime skeleton or an amide skeleton.

6. 3. The resist composition according to claim 1, wherein the acid generator (B) comprises a compound having an oxime sulfonate group or an amido sulfonate group.

7. 3. The resist composition according to claim 1, wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing a structural unit having a group represented by formula (10) or a group represented by formula (20): [In formula (10), R ａ１ , R ａ２ and R ａ３ each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ａ１ and R ａ２ are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R ａ３ represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] [In formula (20), R ａ１’ and R ａ２’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ａ３’ represents a hydrocarbon group having 1 to 20 carbon atoms. ａ１’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ａ２’ and R ａ３’ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. A methylene group contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocycle having 3 to 20 carbon atoms may be replaced by an oxygen atom or a sulfur atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

8. 3. The resist composition according to claim 1, wherein the resin (A1) containing a structural unit having an acid labile group is a resin containing at least one selected from the group consisting of a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a3A), and a structural unit represented by formula (a3B). [In formula (a1-1), R ａ１ , R ａ２ and R ａ３ each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ａ１ and R ａ２ are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R ａ３ represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ａ４ represents a hydrogen atom or a methyl group. [In formula (a1-2), R ａ１’ and R ａ２’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ａ３’ represents a hydrocarbon group having 1 to 20 carbon atoms. ａ１’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ａ２’ and R ａ３’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. a5 represents a hydrogen atom or a methyl group. a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m represents an integer of 0 to 4. When m is 2 or more, a plurality of R a６ may be the same or different. [In formula (a3A), R ａ１ , R ａ２ and R ａ３ each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ａ１ and R ａ２ are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R ａ３ represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ａｂ represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ａｂ may be the same or different.] [In formula (a3B), R ａ１’ and R ａ２’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ａ３’ represents a hydrocarbon group having 1 to 20 carbon atoms. ａ１’ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ａ２’ and R ａ３’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene groups contained in the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic ring having 3 to 20 carbon atoms may be replaced with oxygen atoms or sulfur atoms. ａｂ represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. p represents 0, 1, 2, or 3. When p is 2 or 3, R ａｂ may be the same or different.]

9. 3. The resist composition according to claim 1, further comprising a quencher (C).

10. A method for producing a resist pattern, comprising: (1) a step of applying the resist composition according to claim 1 or 2 onto a metal surface of a substrate having a metal surface; (2) a step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; and (4) Step of developing the composition layer after exposure A manufacturing method comprising:

11. A method for manufacturing a plated object, comprising: (1) a step of applying the resist composition according to claim 1 or 2 onto a metal surface of a substrate having a metal surface; (2) a step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) developing the composition layer after exposure; (5) forming a plated object using the obtained resist pattern as a template; and (6) Step of removing the resist pattern A manufacturing method comprising:

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