Resist composition, method for producing a resist pattern, and carboxylate salt

Abstract

There is a need for technology that can manufacture resist patterns with good line edge roughness (LER). [Solution] A resist composition containing a carboxylate salt represented by formula (I). JPEG2026093366000204.jpg19170

Description

[Technical Field]

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

[0002] Patent Document 1 describes a resist composition containing a carboxylate salt represented by the following formula.

[0003] [ka] [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-156044 [Overview of the project] [Problems that the invention aims to solve]

[0005] There is a need for technology that can manufacture resist patterns with good line edge roughness (LER). [Means for solving the problem]

[0006] This invention includes the following inventions. [Invention 1] A resist composition containing a carboxylate salt represented by formula (I).

[0007] [ka]

[0008] [In formula (I), L 1represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -SO2- or -NR 7 -.

[0009] R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X 1 represents a single bond, -O-, -S-, -CO-, -SO-, -SO2-, -NR 7 -, or a divalent hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -SO2- or -NR 7 -.

[0010] Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent, and the substituents of Ar 1 and Ar 2 may together form a ring which may contain a hetero atom.

[0011] Z + represents an organic cation.] [Invention 2] -Ar 1 -X 1 -Ar 2 The resist composition according to [Invention 1], wherein -Ar

[0012] [Chemical formula] <00所01390>

[0013] [[ID=5所]] [In formulas (I-A) and (I-B), X 1 represents the same meaning as described above. R 3 and R 4Each of these independently represents a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 - may be replaced with R 3 and R 4 These may come together to form a ring that may contain heteroatoms.

[0014] R 7 This expresses the same meaning as above. X 2 These are single bonds, -O-, -S-, -CO-, -SO-, -SO2-, -NR 7 -or represents a divalent hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -SO2- or -NR 7 It may be replaced by this.

[0015] nn1 and nn2 each independently represent either 0 or 1. m3 represents an integer between 0 and (4 + nn1 × 2), and when m3 in equation (IA) or (m3-1) in equation (IB) is 2 or greater, multiple R 3 They may be identical or different from one another.

[0016] m4 represents an integer between 0 and (5 + nn2 × 2), and when m4 in equation (IA) or (m4-1) in equation (IB) is 2 or greater, multiple R 4 They may be identical or different from one another.

[0017] * is L 1 or COO - This is a bonding site with the carbon atoms that make up the molecule. [Invention 3] The resist composition according to [Invention 1] or [Invention 2], wherein the carboxylate salt represented by formula (I) is the carboxylate salt represented by formula (I1).

[0018] [ka]

[0019] [In formula (I1), L 1 represents a hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 - may be replaced with this.

[0020] R 7 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar 1 and Ar 2 Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar 1 and Ar 2 The substituents may come together to form a ring that may contain heteroatoms.

[0021] R 5 and R 6 Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have a halogen atom or substituents, and the -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -NR 7 -, -SO-, or -SO2- may be used as replacements.

[0022] m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R 5 They may be identical or different from one another. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R 6 They may be identical or different from one another.

[0023] Z + Each of these independently represents an organic cation. [Invention 4] L 1 However, a chain hydrocarbon group having 1 to 12 carbon atoms may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -NR 7-or may be replaced by -CO-.) A group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group and the cyclic hydrocarbon group are -O-, -NR 7 A resist composition according to any one of [Invention 1] to [Invention 3], wherein - or -CO- may be replaced.

[0024] [Invention 5] A resist composition according to any one of [Invention 1] to [Invention 4], further comprising a resin containing a structural unit represented by formula (a2-A).

[0025] [ka]

[0026] [In formula (a2-A), R a2 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom.

[0027] R a27 This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group.

[0028] A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a28 - may be replaced with this.

[0029] R a28 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a2This represents a single bond or a carbonyl group. nA2 represents an integer from 1 to 5, and when nA2 is 2 or greater, the bases within the parentheses may be the same or different from each other.

[0030] na21 represents an integer from 0 to 4, and when na21 is 2 or greater, multiple R a27 They may be the same or different from one another. mc represents an integer between 0 and 2. [Invention 6] The resin further comprises structural units having acid-unstable groups, The resist composition according to [Invention 5], wherein the structural unit having the acid-unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a1-4), a structural unit represented by formula (a1-5), and a structural unit represented by formula (a1-6).

[0031] [ka]

[0032] [In equations (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents a bond, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-.

[0033] R a01 , R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a02 , R a03 and R a04Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have halogen atoms.

[0034] R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination thereof, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have halogen atoms.

[0035] m1' represents an integer between 0 and 14. n1 represents an integer between 0 and 14. n1' represents an integer between 0 and 3.

[0036] [ka]

[0037] [In formula (a1-4), R a1 This represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom.

[0038] R a17 This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group.

[0039] A a11represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a18 - may be replaced with this.

[0040] R a18 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a1 This represents a single bond or a carbonyl group. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a34 R represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and a35 and R a36 These groups bond to each other, forming a divalent heterocyclic group having 3 to 20 carbon atoms with the -CO- groups to which they are bonded. The -CH2- groups contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with -O- or -S- groups.

[0041] na1 represents an integer between 1 and 5, and when na1 is 2 or greater, the bases within the parentheses may be the same or different from each other. na11 represents an integer from 0 to 4, and when na11 is 2 or greater, multiple R a17 They may be the same or different from one another.

[0042] mc represents an integer between 0 and 2.

[0043] [ka]

[0044] [In formula (a1-5), R a8 This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom.

[0045] Z a1is a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding site with L 51 L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-.

[0046] s1 represents an integer of any one of 1 to 3. s1′ represents an integer of any one of 0 to 3.]

[0047] [In formula (a1-6),

[0048] R represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. a61

[0049] R a62 , R a63 and R a64 each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, or R a64 represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and R a62 and R a63 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.

[0050] X a61 represents a single bond, -CO-O-* or -CO-NR a65 -*, * represents the bonding site with Ar, and R a65 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a62 represents a single bond, *-O-L a61 - or *-CO-O-L a62 ​​- represents the bonding site with Ar, and * represents the bonding site with L. a61 and L a62 Each of these independently represents an alkanediyl group with 1 to 4 carbon atoms.

[0051] Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. [Invention 7] Furthermore, the resist composition according to any one of Inventions 1 to 6, wherein the acid generator contains an acid generator comprising a salt represented by formula (B1), a salt represented by formula (B2), or a salt represented by formula (B4).

[0052] [ka]

[0053] [In formula (B1), L b1 represents a hydrocarbon group having a single bond or a substituent (nb1+1), and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, or -SO2-.

[0054] L b2 represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0055] Y b1 represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -SO-, -SO2- or -CO-.

[0056] nb1 represents an integer between 1 and 6. When nb1 is 2 or greater, the bases within the parentheses may be the same or different. Z1 + This represents an organic cation.

[0057] [ka]

[0058] [In formula (B2), A 1 represents a nitrogen atom or a carbon atom. L b2′ represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0059] Y b1′ represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO- or -SO2-.

[0060] nb5 is A 1 If it is a nitrogen atom, then it is 2, and A 1 If it is a carbon atom, then it is 3. Multiple bases in parentheses may be the same or different from each other, and two bases in parentheses combine to form A 1 They may form a ring together.

[0061] Z2 + This represents an organic cation.

[0062] [ka]

[0063] [In formula (B4), L b14 and L b15 Each of these independently represents a divalent hydrocarbon group having 1 to 72 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0064] Ar B4 and Ar B5 Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar B4 and Ar B5 The substituents may come together to form a ring.

[0065] R B4 and R B5 Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have a halogen atom or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-.

[0066] mB4 represents an integer between 0 and 4, and when mB4 is 2 or greater, multiple R B4 They may be identical or different from one another. mB5 represents an integer between 0 and 4, and when mB5 is 2 or greater, multiple R B5 They may be identical or different from one another.

[0067] Z4 + and Z5 + Each of these independently represents an organic cation. [Invention 8] (1) A step of applying a resist composition according to any one of [Invention 1] to [Invention 7] onto a substrate, (2) A step of drying the coated resist composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

[0068] [Invention 9] A carboxylate salt represented by the above formula (I). [Invention 10] -Ar 1 -X 1 -Ar 2The carboxylate salt according to [Invention 9], wherein the group is represented by formula (IA) or formula (IB) as described above.

[0069] [Invention 11] The carboxylate salt according to [Invention 9] or [Invention 10], wherein the carboxylate salt represented by formula (I) is the carboxylate salt represented by formula (I1) described above.

[0070] [Invention 12] L 1 However, a chain hydrocarbon group having 1 to 12 carbon atoms may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -NR 7 -or may be replaced by -CO-.) A group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group and the cyclic hydrocarbon group are -O-, -NR 7 A carboxylate salt according to any one of [Invention 9] to [Invention 11], which may be replaced by - or -CO-. [Effects of the Invention]

[0071] According to the present invention, resist patterns can be manufactured with good line edge roughness (LER). [Modes for carrying out the invention]

[0072] In this specification, "(meth)acrylic monomer" means "at least one of acrylic monomers and methacrylic monomers." The same applies to "(meth)acrylate" and "(meth)acrylic acid," etc. For groups described herein that can take both linear and branched structures, either is acceptable. Hydrocarbon groups, etc., containing -CH2- are -O-, -S-, -CO-, -SO-, -NR XWhen a group is replaced by -(X is any sign) or -SO2-, the same example shall apply to each group, and the number of carbon atoms before replacement shall be the same as the number of carbon atoms in the hydrocarbon group, etc. "Combined group" means a group formed by bonding two or more of the exemplified groups, and the valencies of these groups may be appropriately changed depending on the bonding configuration. "Derived from" or "induced" means that the polymerizable C=C bond contained in the molecule becomes a -CC- group (single bond) through polymerization. If stereoisomers exist, all stereoisomers are included. Depending on the number of substituents, etc., hydrogen atoms at any position and number contained in the group may be replaced at the bonding site. The number of carbon atoms in a substituent is not included in the number of carbon atoms of the substituent. "Acid-unstable group" means a group in which, upon contact with an acid (e.g., trifluoromethanesulfonic acid, etc.), the leaving group is removed to form a hydrophilic group (e.g., a hydroxyl group or a carboxyl group, etc.). A "base-unstable group" refers to a group that, upon contact with a base (e.g., trimethylamine, tetramethylammonium hydroxide, etc.), detaches a leaving group to form a hydrophilic group (e.g., a carboxyl group or a hydroxyl group, etc.).

[0073] In this specification, "solid content of the resist composition" means the total amount of the resist composition excluding the solvent (E) described later. [Carboxylate salt represented by formula (I)] This invention relates to a carboxylate salt represented by formula (I) (hereinafter sometimes referred to as "carboxylate salt (I)").

[0074] In carboxylate salts (I), the negatively charged side is sometimes called the "anion (I)," and the positively charged side is sometimes called the "cation (I)." (Anion (I)) In equation (I), L 1The hydrocarbon group in this context is a divalent hydrocarbon group, and examples include linear or branched chain hydrocarbon groups, monocyclic or polycyclic (including spiro rings, fused rings, or bridged rings) alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and other cyclic hydrocarbon groups. A group formed by combining two or more of these groups (for example, a hydrocarbon group formed from an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group) is also acceptable. Chain hydrocarbon groups and alicyclic hydrocarbon groups are also called aliphatic hydrocarbon groups, and alicyclic hydrocarbon groups and aromatic hydrocarbon groups are also called cyclic hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 1 to 24, more preferably 1 to 20, even more preferably 1 to 18, and even more preferably 1 to 12.

[0075] Examples of chain-like hydrocarbon groups include alkanediyl groups, such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl, as well as linear alkanediyl groups. Examples of branched alkanediyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The ends of the branched alkanediyl groups may be alkyl groups such as methyl groups.

[0076] The number of carbon atoms in the chain-like hydrocarbon group may be 1 to 24, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, even more preferably 1 to 6, and even more preferably 1 to 4.

[0077] Examples of monocyclic or polycyclic divalent alicyclic hydrocarbon groups include the following groups. The bonding site can be at any position.

[0078] [ka]

[0079] Specifically, examples include monocyclic divalent alicyclic hydrocarbon groups such as monocyclic cycloalkanediyl groups like cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; and polycyclic divalent alicyclic hydrocarbon groups such as cycloalkyl groups like norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, spirocyclohexane-1,2′-cyclopentane, and spiroadamantane-2,3′-cyclopentane, as well as spiro rings having cycloalkyl groups spiro-bonded to norbornyl or adamantyl groups. The number of carbon atoms in the alicyclic hydrocarbon group may be 3 to 24, preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12.

[0080] Examples of aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, biphenylene groups, phenanthrylene groups, and other arylene groups. The number of carbon atoms in the aromatic hydrocarbon group may be 6 to 24, preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0081] Examples of groups combining two or more types include groups combining an alicyclic hydrocarbon group and a chain hydrocarbon group, groups combining an aromatic hydrocarbon group and a chain hydrocarbon group, groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and groups combining an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a chain hydrocarbon group. In the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Also, any of the groups may be X 0 or X 01 They may be bound together.

[0082] Examples of groups combining alicyclic hydrocarbon groups and chain hydrocarbon groups include -divalent alicyclic hydrocarbon group-chain hydrocarbon group-, -chain hydrocarbon group-divalent alicyclic hydrocarbon group-chain hydrocarbon group-, and -chain hydrocarbon group-divalent alicyclic hydrocarbon group-.

[0083] Examples of groups combining an aromatic hydrocarbon group and a chain hydrocarbon group include -divalent aromatic hydrocarbon group-chain hydrocarbon group-, -chain hydrocarbon group-divalent aromatic hydrocarbon group-chain hydrocarbon group-, and -chain hydrocarbon group-divalent aromatic hydrocarbon group-.

[0084] Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, and -alicyclic hydrocarbon group-aromatic hydrocarbon group-alicyclic hydrocarbon group-.

[0085] L 1 The -CH2- contained in hydrocarbon groups with 1 to 28 carbon atoms is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 - may be replaced with this. L 1 The -CH2- group in the hydrocarbon group with 1 to 28 carbon atoms is either -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 If a carbon atom is replaced by a hyphen, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group.

[0086] R 7 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably 1 to 3.

[0087] R 7 Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; more preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; even more preferably, it is a hydrogen atom, a methyl group, or an ethyl group; even more preferably, it is a hydrogen atom or a methyl group; and even more preferably, it is a hydrogen atom.

[0088] The -CH2- contained in the hydrocarbon group is -O-, -S-, -SO-, -SO2-, -NR 7 Groups replaced by - or -CO- include hydroxyl groups (groups in which the -CH2- contained in the methyl group is replaced by -O-), carboxyl groups (groups in which the -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), thiol groups (groups in which the -CH2- contained in the methyl group is replaced by -S-), and amino groups (groups in which the -CH2- contained in the methyl group is replaced by -NR 7 - group replaced by -, oxy group (a group in which -CH2- in the methylene group is replaced by -O-), carbonyl group (a group in which -CH2- in the methylene group is replaced by -CO-), thio group (a group in which -CH2- in the methylene group is replaced by -S-), sulfonyl group (a group in which -CH2- in the methylene group is replaced by -SO2-), peptide group (a group in which -CH2-CH2- in the ethylene group is replaced by -CO-NR 7 -A group replaced by -), alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced by -O-), alkylthio group (a group in which -CH2- at any position in an alkyl group is replaced by -S-), alkylsulfonyl group (a group in which -CH2- at any position in an alkyl group is replaced by -SO2-), alkylamino group (a group in which -CH2- at any position in an alkyl group is replaced by -NR 7-A group replaced by -), alkyl peptide group (where -CH2-CH2- at any position within the alkyl group is -CO-NR 7 عال (A group in which 2-CH2- is replaced by -O-CO-O-), alkoxyalkoxy group (A group in which two -CH2- at any position in an alkyl group are replaced by -O-), alkoxyalkyl group (A group in which one -CH2- at any position in an alkyl group is replaced by -O-), hydroxyalkyl group (A group in which one -CH2- in a methyl group at any position in an alkyl group is replaced by -O-), alkanediyloxy group (A group in which one -CH2- in an alkanediyl group is replaced by -O-) (A group in which the -CH2- at any position is replaced by -O-), Alkanediyloxycarbonyl group (A group in which the -CH2-CH2- at any position in the Alkanediyl group is replaced by -O-CO-), Alkanediylcarbonyl group (A group in which the -CH2- at any position in the Alkanediyl group is replaced by -CO-), Alkanediylcarbonyloxy group (A group in which the -CH2-CH2- at any position in the Alkanediyl group is replaced by -CO-O-), Alkanediyl Xycarbonyloxy group (a group in which -CH2-CH2-CH2- at any position in an alkanediyl group is replaced with -O-CO-O-), alkanediylsulfonyl group (a group in which -CH2- at any position in an alkanediyl group is replaced with -SO2-), alkanediylthio group (a group in which -CH2- at any position in an alkanediyl group is replaced with -S-), alkanediylamino group (a group in which -CH2- at any position in an alkanediyl group is replaced with -NR 7 -A group replaced by -), an alkanediyl peptide group (where -CH2-CH2- at any position in the alkanediyl group is replaced by -CO-NR7 Examples include groups that have been replaced by (-), cycloalkoxy groups, cycloalkylalkoxy groups, aromatic hydrocarbon group-carbonyloxy groups, aromatic hydrocarbon group-carbonyl groups, aromatic hydrocarbon group-oxy groups, and groups that combine two or more of these groups.

[0089] Examples of alkoxy groups include alkoxy groups having 1 to 27 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0090] Examples of alkylthio groups include alkylthio groups having 1 to 27 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, and undecylthio group. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0091] Examples of alkylamino groups include alkylamino groups having 1 to 27 carbon atoms, such as methylamino group, ethylamino group, dimethylamino group, propylamino group, butylamino group, pentylamino group, pentylamino group, and hexylamino group. The number of carbon atoms in the alkylamino group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0092] Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 27 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 28 carbon atoms, such as acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 27 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy groups. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 26 carbon atoms, such as butoxycarbonyloxy groups. Examples of alkoxyalkoxy groups include alkoxyalkoxy groups having 2 to 26 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkoxycarbonyloxy group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3.

[0093] Examples of alkylsulfonyl groups include alkylsulfonyl groups having 1 to 27 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, and undecylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0094] Examples of alkyl peptide groups include alkyl peptide groups having 1 to 27 carbon atoms, such as methyl peptide groups, ethyl peptide groups, and propyl peptide groups. The number of carbon atoms in the alkyl peptide group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0095] Examples of alkoxyalkyl groups include alkoxyalkyl groups having 2 to 27 carbon atoms, such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, propoxymethyl group, propoxyethyl group, isopropoxymethyl group, propoxypropyl group, butoxymethyl group, sec-butoxymethyl group, and tert-butoxymethyl group. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3.

[0096] Examples of hydroxyalkyl groups include hydroxyalkyl groups having 1 to 27 carbon atoms, such as hydroxymethyl group, dihydroxymethyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group, hydroxyisopropyl group, hydroxybutyl group, and hydroxysec-butyl group. The number of carbon atoms in the hydroxyalkyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0097] Examples of alkanediyloxy groups include alkanediyloxy groups having 1 to 27 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The number of carbon atoms in the alkanediyloxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0098] Examples of alkanediyloxycarbonyl groups include alkanediyloxycarbonyl groups having 2 to 27 carbon atoms, such as methyleneoxycarbonyl groups, ethyleneoxycarbonyl groups, propanediyloxycarbonyl groups, and butanediyloxycarbonyl groups. Examples of alkanediylcarbonyl groups include alkanediylcarbonyl groups having 2 to 28 carbon atoms, such as methylenecarbonyl groups, ethylenecarbonyl groups, propanediylcarbonyl groups, butanediylcarbonyl groups, and pentanediylcarbonyl groups. Examples of alkanediylcarbonyloxy groups include alkanediylcarbonyloxy groups having 2 to 27 carbon atoms, such as methylenecarbonyloxy groups, ethylenecarbonyloxy groups, propanediylcarbonyloxy groups, and butanediylcarbonyloxy groups. Examples of alkanediyloxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 26 carbon atoms, such as the butoxycarbonyloxy group. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3.

[0099] Examples of alkanediylsulfonyl groups include alkanediylsulfonyl groups having 1 to 27 carbon atoms, such as methylenesulfonyl groups, ethylenesulfonyl groups, and propylenesulfonyl groups. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0100] Examples of alkanediylthio groups include alkanediylthio groups having 1 to 27 carbon atoms, such as methylenethio groups, ethylenethio groups, and propylenethio groups. The number of carbon atoms in the alkanediylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0101] Examples of alkanediylamino groups include alkanediylamino groups having 1 to 27 carbon atoms, such as methyleneamino groups, ethyleneamino groups, dimethylamino groups, propyleneamino groups, butyleneamino groups, pentyleneamino groups, and hexyleneamino groups. The number of carbon atoms in the alkanediylamino group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0102] Examples of alkanediyl peptide groups include alkanediyl peptide groups having 1 to 27 carbon atoms, such as methylene peptide groups, ethylene peptide groups, and propylene peptide groups. The number of carbon atoms in the alkanediyl peptide group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0103] Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 27 carbon atoms, such as the cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 27 carbon atoms, such as the cyclohexylmethoxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 27 carbon atoms, such as the benzoyloxy group. Examples of aromatic hydrocarbon group-carbonyl groups include aromatic hydrocarbon group-carbonyl groups having 7 to 28 carbon atoms, such as the benzoyl group. Examples of aromatic hydrocarbon group-oxy groups include aromatic hydrocarbon group-oxy groups having 6 to 27 carbon atoms, such as the phenyloxy group.

[0104] Furthermore, the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or combinations thereof may be -O-, -S-, -CO-, -NR 7 The following groups are examples of groups that have been replaced by -, -SO-, or -SO2-. The -O- or -CO- in the groups shown below are replaced by -S-, -SO-, -SO2-, or -NR, respectively. 7 - may be replaced with this. The connection point can be at any position.

[0105] [ka]

[0106] L 1 Examples of substituents that may be present include halogen atoms, cyano groups, nitro groups, etc. 1 The -CH2- contained in the chain hydrocarbon group such as alkyl groups is -O-, -S-, -CO-, -SO-, -NR 7 -By being replaced by -SO2-, effectively, L 1 It can have substituents such as hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, alkoxyalkoxy groups, thiol groups, amino groups, alkylthio groups, alkylsulfonyl groups, alkylamino groups, and alkylpeptide groups. 1 However, in the case of a group that combines an alicyclic hydrocarbon group or an aromatic hydrocarbon group with a chain hydrocarbon group such as an alkyl group, the chain hydrocarbon group such as an alkyl group can substantially be used as a substituent on the alicyclic hydrocarbon group or aromatic hydrocarbon group.

[0107] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The substituent is preferably a C1-C6 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-) or a halogen atom, more preferably a hydroxyl group, a C1-C4 alkoxy group or a halogen atom, and even more preferably a hydroxyl group, a C1-C3 alkoxy group, a fluorine atom or an iodine atom.

[0108] L 1 This refers to a chain hydrocarbon group having 1 to 28 carbon atoms, which may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -CO-, -S-, -SO-, -SO2-, or -NR). 7 -May be replaced by -, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be -O-, -CO-, -S-, -SO-, -SO2- or -NR 7 -May be replaced by -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 -May be replaced by -O-, -NR 7 -or may be replaced by -CO-), a cyclic hydrocarbon group having 3 to 24 carbon atoms that may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -CO-, -SO-, -NR 7 -Or may be replaced by -SO2-.) Or a group formed by combining a chain hydrocarbon group having 1 to 12 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -NR 7 - or -CO- may be replaced, and the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -SO2-, -SO-, -NR 7 - may be replaced by -CO-.) Preferably, it is a chain hydrocarbon group having 1 to 12 carbon atoms, which may have substituents (the -CH2- contained in the chain hydrocarbon group is -O-, -NR7 -or -CO- may be replaced by -O-, -NR 7 - may be replaced by -CO-.) More preferably, it is a chain hydrocarbon group having 1 to 6 carbon atoms (the -CH2- contained in the chain hydrocarbon group is -O-, -NR 7 -or -CO- may be replaced by -O-, -NR 7 - may be replaced by -CO-.) It is more preferable that it be a chain hydrocarbon group having 1 to 6 carbon atoms (the -CH2- contained in the chain hydrocarbon group is -O-, -NR 7 -May be replaced by -CO-.) Or a group formed by combining a chain hydrocarbon group having 1 to 4 carbon atoms and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a halogen atom or a hydroxyl group (the -CH2- contained in the chain hydrocarbon group and the cyclic hydrocarbon group may be -O-, -NR 7 -Or -CO- may be replaced.) It is more preferable that the group is a chain hydrocarbon group having 1 to 6 carbon atoms and a halogen atom (the -CH2- contained in the chain hydrocarbon group is -O-, -NR 7 -May be replaced by -CO-.) Or a group formed by combining a chain hydrocarbon group having 2 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a halogen atom or a hydroxyl group (the -CH2- contained in the chain hydrocarbon group may be -O-, -NR 7 It is even more preferable that it be replaced by - or -CO-.

[0109] In equation (I), X 1Examples of divalent hydrocarbon groups having 1 to 28 carbon atoms in this context include linear or branched chain hydrocarbon groups, monocyclic or polycyclic (including spiro rings, fused rings, or bridged rings) alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and other cyclic hydrocarbon groups. Groups formed by combining two or more of these groups (for example, hydrocarbon groups formed from an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group) are also acceptable.

[0110] Examples of chain-like hydrocarbon groups include alkanediyl groups, such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl, as well as linear alkanediyl groups. Examples of branched alkanediyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The ends of the branched alkanediyl groups may be alkyl groups such as methyl groups.

[0111] The number of carbon atoms in the chain-like hydrocarbon group may be 1 to 24, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, even more preferably 1 to 6, and even more preferably 1 to 4.

[0112] Examples of monocyclic or polycyclic divalent alicyclic hydrocarbon groups include the following groups. The bonding site can be at any position.

[0113] [ka]

[0114] Specifically, monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl are monocyclic divalent alicyclic hydrocarbon groups. Examples of polycyclic divalent alicyclic hydrocarbon groups include cycloalkyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, spirocyclohexane-1,2′-cyclopentane group, and spiroadamantane-2,3′-cyclopentane group, as well as polycyclic cycloalkanediyl groups such as spiro rings having cycloalkyl groups spiro-bonded to norbornyl or adamantyl groups. The number of carbon atoms in the alicyclic hydrocarbon group may be 3 to 24, preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12.

[0115] Examples of aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, biphenylene groups, phenanthrylene groups, diphenylfluorene groups, fluorenyl groups, and other arylene groups. The number of carbon atoms in the aromatic hydrocarbon group may be 6 to 25, preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 12.

[0116] Examples of groups combining two or more types include groups combining an alicyclic hydrocarbon group and a chain hydrocarbon group, groups combining an aromatic hydrocarbon group and a chain hydrocarbon group, groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and groups combining an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a chain hydrocarbon group. In the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Also, any of the groups may be Ar 1 Or Ar 2 They may be bound together.

[0117] Examples of groups that combine an alicyclic hydrocarbon group and a chain hydrocarbon group include -divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-alkanediyl group-, and -alkanediyl group-divalent alicyclic hydrocarbon group-.

[0118] Examples of groups that combine an aromatic hydrocarbon group and a chain-type hydrocarbon group include -divalent aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-alkanediyl group-, and -alkanediyl group-divalent aromatic hydrocarbon group-.

[0119] Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, and -alicyclic hydrocarbon group-aromatic hydrocarbon group-alicyclic hydrocarbon group-.

[0120] X 1 The -CH2- contained in the divalent hydrocarbon group with 1 to 28 carbon atoms is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 - may be replaced with this. R 7 Examples of alkyl groups include methyl, ethyl, isopropyl, and t-butyl groups. In particular, the number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0121] R 7 Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; more preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; even more preferably, it is a hydrogen atom, a methyl group, or an ethyl group; even more preferably, it is a hydrogen atom or a methyl group; and even more preferably, it is a hydrogen atom.

[0122] X 1 The -CH2- group in the divalent hydrocarbon group with 1 to 28 carbon atoms is either -O-, -CO-, -S-, -SO-, -SO2-, or -NR7 If a carbon atom is replaced by a hyphen, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group.

[0123] The -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 The groups that have been replaced by - include hydroxyl group, carboxyl group, thiol group, amino group, oxy group, carbonyl group, thio group, sulfonyl group, peptide group, alkoxy group, alkylthio group, alkylsulfonyl group, alkylamino group, alkylpeptide group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkoxycarbonyloxy group, alkoxyalkoxy group, alkoxyalkyl group, hydroxyalkyl group, alkanediyloxy group, alkanediyloxycarbonyl group, alkanediylcarbonyloxy group, alkanediyloxycarbonyloxy group, alkanediylsulfonyl group, alkanediylthio group, alkanediylamino group, alkanediylpeptide group, cycloalkoxy group, cycloalkylalkoxy group, aromatic hydrocarbon group-carbonyloxy group, aromatic hydrocarbon group-carbonyl group, aromatic hydrocarbon group-oxy group, and alicyclic hydrocarbon group where -CH2- is replaced by -O-, -S-, -SO-, -SO2-, -NR 7 Examples include groups replaced by - or -CO-, and groups formed by combining two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the range of acceptable carbon numbers.

[0124] Furthermore, the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or combinations thereof may be -O-, -S-, -CO-, -NR 7 Groups replaced with -, -SO-, or -SO2- include those similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms. 1 Examples of substituents that may be present on the divalent hydrocarbon group having 1 to 28 carbon atoms include halogen atoms, cyano groups, nitro groups, etc. 1The -CH2- group contained in the alkyl group and other chain hydrocarbon groups contained therein is -O-, -S-, -CO-, -NR 7 By being replaced by -, -SO- or -SO2-, effectively, X 1 X may have substituents such as hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, alkoxyalkoxy groups, alkylamino groups, amino groups, thiol groups, alkylthio groups, alkylsulfonyl groups, and alkylpeptide groups. 1 However, in the case of a group that combines an alicyclic hydrocarbon group or an aromatic hydrocarbon group with a chain hydrocarbon group such as an alkyl group, the chain hydrocarbon group such as an alkyl group can substantially be used as a substituent on the alicyclic hydrocarbon group or aromatic hydrocarbon group.

[0125] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. X 1 These are single bonds, -O-, -S-, -CO-, -SO-, -SO2-, -NR 7 -, a chain-like hydrocarbon group having 1 to 18 carbon atoms which may have substituents (the -CH2- contained in the chain-like hydrocarbon group may be -O-, -S-, -SO2-, -SO-, -NR 7 -or may be replaced by -CO-), a cyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -CO-, -SO-, -NR 7 -Or may be replaced by -SO2-.) Or a group formed by combining a chain hydrocarbon group having 1 to 12 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group and the cyclic hydrocarbon group may be -O-, -S-, -SO2-, -SO-, -NR 7 -Or it may be replaced by -CO-.) Examples include single bonds, -O-, -S-, -CO-, -SO-, -SO2-, -NR 7- A chain hydrocarbon group having 1 to 12 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -S-, -CO-, -NR 7 -, -SO- or -SO2- may be replaced by -, -SO- or -SO2-.), a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -CO-, -NR 7 -, -SO- or -SO2- may be replaced by -, -SO- or -SO2-.) or a group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -S-, -CO-, -NR 7 -, -SO- or -SO2- may be replaced, and the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -SO2-, -NR 7 -, -SO- or -CO- may be replaced.) Preferably, it is a single bond, -O-, -S-, -CO-, -SO-, -SO2-, -NR 7 - A chain hydrocarbon group having 1 to 10 carbon atoms, which may have substituents (the -CH2- contained in the chain hydrocarbon group may be -O-, -S-, -CO-, -NR 7 -, -SO- or -SO2- may be replaced by -, -SO- or -SO2-.), a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -CO-, -NR 7 -, -SO- or -SO2- may be replaced by -, -SO- or -SO2-.) Or a group formed by combining a chain hydrocarbon group having 1 to 6 carbon atoms that may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -SO2-, -NR 7 -, -SO- or -CO- may be substituted. ) is more preferable.

[0126] Ar 1 and Ar 2Examples of aromatic hydrocarbon groups in this context include arylene groups such as phenylene, naphthylene, anthrylene, biphenylene, and phenanthrylene, and aryl groups such as phenyl, naphthyl, biphenyl, anthryl, and phenanthryl. The number of carbon atoms in the aromatic hydrocarbon group may be 6 to 22, preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0127] Ar 1 and Ar 2 The substituents that may be present include halogen atoms, cyano groups, nitro groups, or hydrocarbon groups having 1 to 36 carbon atoms that may have substituents (the -CH2- contained in the hydrocarbon group may be -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 - may be replaced with Ar 1 and Ar 2 The substituents that may be present may together form a ring that may contain heteroatoms. ) are examples. Also, Ar 2 It is also preferable that at least one of the substituents is a hydroxyl group or a carboxyl group.

[0128] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of hydrocarbon groups having 1 to 36 carbon atoms include chain-type hydrocarbon groups such as alkyl groups and alkanediyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.

[0129] Examples of alkyl groups include linear or branched alkyl groups, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.

[0130] Alkanediyl groups include linear or branched alkanediyl groups, such as methylene groups, ethylene groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, and linear alkanediyl groups; and Examples of branched alkanediyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.

[0131] The number of carbon atoms in the chain-like hydrocarbon group may be 1 to 24, preferably 1 to 12, more preferably 1 to 10, even more preferably 1 to 9, even more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0132] Alicyclic hydrocarbon groups may be monocyclic or polycyclic, and include the groups listed below. The bonding site can be at any position.

[0133] [ka]

[0134] Specifically, monocyclic alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl. Polycyclic alicyclic hydrocarbon groups include polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, and norbornyl; cycloalkyl groups such as spirocyclohexane-1,2′-cyclopentane and spiroadamantane-2,3′-cyclopentane; and spiro rings having a norbornyl or adamantyl group each linked to a cycloalkyl group by a spiro. The number of carbon atoms in the alicyclic hydrocarbon group may be 3 to 24, preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12.

[0135] Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, biphenyl groups, anthryl groups, phenanthryl groups, and binaphthyl groups. The number of carbon atoms in the aromatic hydrocarbon group may be 6 to 24, preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0136] Groups formed by combining two or more groups from among chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include groups formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*, alkyl group-aromatic hydrocarbon group-alkanediyl group-*, where the -CH2- contained in the alkanediyl group and the alkyl group is -O-, -CO-, -S-, -NR). 7 -, -SO- or -SO2- may be replaced.), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*, alkyl group-alicyclic hydrocarbon group-alkanediyl group-*, the -CH2- contained in the alicyclic hydrocarbon group, the alkanediyl group and the alkyl group is -O-, -CO-, -S-, -NR 7-, -SO- or -SO2- may be replaced.), a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*, the -CH2- contained in the alicyclic hydrocarbon group is -O-, -CO-, -S-, -NR 7 -, -SO- or -SO2- may be used as examples.) * represents a binding site.

[0137] Examples of aromatic hydrocarbon groups - alkanediyl groups -* include aralkyl groups such as benzyl and phenethyl groups. Examples of alkyl-aromatic hydrocarbon groups-* include tolyl groups, xylyl groups, and cumenyl groups.

[0138] Examples of alicyclic hydrocarbon groups - alkanediyl groups -* include cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl group, and other cycloalkylalkyl groups.

[0139] Examples of alkyl-alicyclic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, and cycloalkyl groups having alkyl groups such as 2-alkyladamantan-2-yl group.

[0140] Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include the phenylcyclohexyl group. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include the cyclohexylphenyl group.

[0141] Furthermore, in the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Also, any of the groups may be Ar 1 Or Ar 2 They may be bound together.

[0142] The -CH2- group in hydrocarbon groups with 1 to 36 carbon atoms is either -O-, -CO-, -S-, -SO-, -SO2-, or -NR. 7 If a carbon atom is replaced by a hyphen, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group.

[0143] R 7 Examples of alkyl groups include methyl, ethyl, isopropyl, and t-butyl groups. In particular, the number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0144] The -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -SO2-, or -NR 7 Examples of groups that can be replaced by - include hydroxyl groups, carboxyl groups, thiol groups, amino groups, oxy groups, carbonyl groups, thio groups, sulfonyl groups, peptide groups, alkoxy groups, alkylthio groups, alkylsulfonyl groups, alkylamino groups, alkylpeptide groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, alkoxyalkoxy groups, alkoxyalkyl groups, hydroxyalkyl groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediyloxycarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, alkanediylamino groups, alkanediylpeptide groups, cycloalkoxy groups, cycloalkylalkoxy groups, aromatic hydrocarbon group-carbonyloxy groups, aromatic hydrocarbon group-carbonyl groups, aromatic hydrocarbon group-oxy groups, and groups that combine two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0145] Furthermore, the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or combinations thereof may be -O-, -S-, -CO-, -NR 7Groups replaced with -, -SO-, or -SO2- include those similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0146] Ar 1 and Ar 2 Examples of substituents that the hydrocarbon group may have include halogen atoms, cyano groups, nitro groups, and the like. Examples of halogen atoms include the same groups as those described above.

[0147] The hydrocarbon group may have one substituent or more substituents. When a hydrocarbon group has a halogen atom, examples of hydrocarbon groups having a halogen atom include chain hydrocarbon groups having a halogen atom such as haloalkyl groups, alicyclic hydrocarbon groups having a halogen atom, and aromatic hydrocarbon groups having a halogen atom.

[0148] A haloalkyl group refers to an alkyl group having a halogen atom, and examples include C1-C36 alkyl fluorides, C1-C36 alkyl chlorides, C1-C36 alkyl bromides, C1-C36 alkyl iodides, and other C1-C36 haloalkyl groups. Examples of haloalkyl groups include C1-C36 perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc. The number of carbon atoms in a haloalkyl group can be 1-18, may be 1-12, preferably 1-9, more preferably 1-6, even more preferably 1-4, and even more preferably 1-3.

[0149] The -CH2- group in the haloalkyl group may be replaced with -O- or -CO-, etc. Examples of such groups include haloalkoxy groups, haloalkoxycarbonyl groups, haloalkylcarbonyl groups, and haloalkylcarbonyloxy groups. Specifically, examples include haloalkoxy groups having 1 to 35 carbon atoms, haloalkoxycarbonyl groups having 2 to 35 carbon atoms, haloalkylcarbonyl groups having 2 to 36 carbon atoms, and haloalkylcarbonyloxy groups having 2 to 35 carbon atoms. For example, a group obtained by replacing one or more hydrogen atoms of the above-mentioned groups with halogen atoms is also included.

[0150] Ar 1 and Ar 2 A ring which may contain heteroatoms formed by substituents that may be present together can be represented by the following formula. In the following groups, Ar 1 and Ar 2 It may further have the substituents described above. * represents a bonding site.

[0151] [ka]

[0152] Here, X 1 Rings containing Ar include 3- to 18-membered rings, 3- to 12-membered rings, 4- to 11-membered rings, or 5- to 10-membered rings. These rings are Ar 1 and / or Ar 2 It may be a fused ring with or a spiro ring or a ring in which a spiro ring is bonded to a fused ring. 1 and Ar 2 Examples of fused rings with X include the group represented by the following formula (IB). Among them, X 1 The ring containing Ar 1 and Ar 2 It is a condensed ring with a 5- to 6-membered ring, which is preferable.

[0153] Examples of heteroatoms in the ring include oxygen atoms, sulfur atoms, and nitrogen atoms. Ar 1 and Ar 2If each of these groups is derived from a benzene ring or a naphthalene ring, then -Ar 1 -X 1 -Ar 2 Examples of - include the group represented by formula (IA) or the group represented by formula (IB).

[0154] [ka]

[0155] [In formulas (IA) and (IB), all symbols have the same meanings as defined above.] X 2 A divalent hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, is X 1 Examples similar to those exemplified earlier can be given.

[0156] X 2 Examples include single bonds, -O-, -S-, -CO-, -SO-, -SO2-, and -NR 7 - Examples include chain hydrocarbon groups having 1 to 10 carbon atoms or cyclic hydrocarbon groups having 3 to 20 carbon atoms, preferably consisting of a single bond, -O-, -S-, -CO-, -SO-, -SO2-, an alkanediyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and more preferably consisting of a single bond, -O-, -S-, -CO-, -SO-, -SO2-, an alkanediyl group having 1 to 4 carbon atoms, or a group derived from a fluorene ring.

[0157] R 3 and R 4 Ar 1 and Ar 2 Examples of substituents that may be present are similar to those exemplified above. R 3 and / or R 4 If R is 1 or greater, 3 and / or R 4 The bonding site in the benzene ring is X 1The binding site may be bound to the o-, m-, or p- position. In particular, it is preferable that at least one is bound to the m- or p- position, and more preferably to the m- position. 3 and / or R 4 The binding site in the naphthalene ring is X 1 If the bond position is at position 1, it can bond to any of positions 2 through 8, X 1 If the bond position is at position 2, it may bond to position 1 or any of positions 3 through 8.

[0158] Furthermore, the bonding sites in the benzene ring of -COO are, respectively, X 1 The binding site may be at the o-, m-, or p- position. Of these, binding at the m- or p- position is preferred. The binding site on the naphthalene ring of -COO is X 1 If the bond position is at position 1, it can bond to any of positions 2 through 8, X 1 If the bond position is at position 2, it may bond to position 1 or any of positions 3 through 8.

[0159] Examples of groups represented by formula (IB) include the following groups. These groups may have the substituents mentioned above. The bonding site can be at any position.

[0160] [ka]

[0161] Ar 1 and Ar 2 Examples include aromatic hydrocarbon groups (Ar) having 6 to 18 carbon atoms, which may have substituents. 1 and Ar 2 The substituents may together form a ring which may contain heteroatoms.) Preferably, it is an aromatic hydrocarbon group having 6 to 12 carbon atoms (Ar) which may have substituents. 1 and Ar 2The substituents may together form a ring which may contain heteroatoms. It is more preferable that the substituents are phenylene or naphthylene (the substituents of the phenylene or naphthylene may together form a ring which may contain heteroatoms).

[0162] Ar 1 and Ar 2 For example, X 1 In the case of a single bond, the substituted C6-C18 aromatic hydrocarbon group (Ar 1 and Ar 2 The substituents may together form a ring which may contain heteroatoms.) Preferably, the substituent is a C6-C12 aromatic hydrocarbon group (Ar 1 and Ar 2 The substituents may together form a ring which may contain heteroatoms. It is more preferable that the substituents are substituted for a phenylene group or a naphthylene group (the substituents of the phenylene group or naphthylene group may together form a ring which may contain heteroatoms).

[0163] Also, Ar 2 It is also preferable that at least one of the substituents is a hydroxyl group or a carboxyl group. m3 is preferably 0, 1, 2, 3, or 4, more preferably 0, 1, 2, or 4, and even more preferably 0, 1, or 2. It is also preferably an integer from 1 to (4 + nn1 × 2).

[0164] m4 is preferably 0, 1, 2, 3, 4, or 5, more preferably 0, 1, 2, 3, or 4, even more preferably 1, 2, 3, or 4, and even more preferably 1, 2, or 3. It is also preferable that it be any integer from 1 to (5 + nn2 × 2).

[0165] R 3This includes halogen atoms, C1-C8 haloalkyl groups, or C1-C12 alkyl groups (the -CH2- contained in the haloalkyl groups and the alkyl groups are -O-, -NR). 7 Examples include halogen atoms, C1-C6 haloalkyl groups, or C1-C10 alkyl groups (the -CH2- contained in the haloalkyl groups and the alkyl groups are -O-, -NR). 7 It is preferable that the atoms are replaced by - or -CO-, and that the atoms are a fluorine atom, an iodine atom, a C1-C6 haloalkyl group or a C1-C8 alkyl group (the -CH2- contained in the haloalkyl group and the alkyl group are -O-, -NR 7 - may be replaced by -CO-.) More preferably, it is a fluorine atom, an iodine atom, a C1-C4 haloalkyl group or a C1-C8 alkyl group (the -CH2- contained in the alkyl group is -O-, -NR 7 It is even more preferable that the group is a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, an amino group, a C1-C4 alkyl group, a C1-C4 fluorinated alkyl group, a C1-C3 alkoxy group, a C3-C6 alkoxyalkoxycarbonyl group, or a C2-C6 alkoxyalkoxy group, and it is even more preferable that the group is a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, an amino group, a C1-C4 alkyl group, a C1-C4 perfluoroalkyl group, a C1-C3 alkoxy group, a C3-C4 alkoxyalkoxycarbonyl group, or a C2-C4 alkoxyalkoxy group, and it is even more preferable that the group is a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, an ethyl group, a carboxyl group, an amino group, a methoxy group, an ethoxy group, an ethoxymethoxycarbonyl group, an ethoxymethoxy group, or a hydroxyl group.

[0166] R 4 This includes halogen atoms, C1-C8 haloalkyl groups, or C1-C12 alkyl groups (the -CH2- contained in the haloalkyl groups and the alkyl groups are -O-, -NR). 7Examples include halogen atoms, C1-C6 haloalkyl groups, or C1-C10 alkyl groups (the -CH2- contained in the haloalkyl groups and the alkyl groups are -O-, -NR). 7 It is preferable that the atoms are replaced by - or -CO-, and that the atoms are a fluorine atom, an iodine atom, a C1-C6 haloalkyl group or a C1-C8 alkyl group (the -CH2- contained in the haloalkyl group and the alkyl group are -O-, -NR 7 - may be replaced by -CO-.) More preferably, it is a fluorine atom, an iodine atom, a C1-C4 haloalkyl group or a C1-C8 alkyl group (the -CH2- contained in the alkyl group is -O-, -NR 7 It is even more preferable that the group is a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, an amino group, a C1-C4 alkyl group, a C1-C4 fluorinated alkyl group, a C1-C3 alkoxy group, a C3-C6 alkoxyalkoxycarbonyl group, or a C2-C6 alkoxyalkoxy group, and it is even more preferable that the group is a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, an amino group, a C1-C4 alkyl group, a C1-C4 perfluoroalkyl group, a C1-C3 alkoxy group, a C3-C4 alkoxyalkoxycarbonyl group, or a C2-C4 alkoxyalkoxy group, and it is even more preferable that the group is a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, an ethyl group, an amino group, a methoxy group, an ethoxy group, an ethoxymethoxycarbonyl group, an ethoxymethoxy group, a hydroxyl group, or a carboxyl group.

[0167] Examples of anions (I) include those represented by the following equations (Ia-1) to (Ia-114).

[0168] [ka]

[0169] [ka]

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176]

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[0177]

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[0178]

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[0179]

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[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [Cation (I)] Z in equation (I) + Examples of organic cations include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, examples include cations represented by any of formulas (b2-1) to (b2-5) (hereinafter, depending on the formula number, they may be referred to as "cation (b2-1)," etc.).

[0184] [ka]

[0185] [In formulas (b2-1) to (b2-5), R b4 ~R b6Each of these independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atoms in the chain hydrocarbon group may be substituted with a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atoms in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0186] R b4 and R b5 These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-.

[0187] R b7 and R b8 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0188] m7 and n8 each independently represent an integer between 0 and 5. When m7 is 2 or more, multiple R b7 They may be the same or different, and when n8 is 2 or more, multiple R b8 They may be the same or different.

[0189] R b9 and R b10 Each of these independently represents either a chain-like hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-.

[0190] R b11 This represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.

[0191] R b11 and R b12 These may be bonded to each other and form a ring including the -CH-CO- groups to which they are bonded, and the -CH2- groups included in the ring may be replaced by -O-, -S-, or -CO-.

[0192] R b13 ~R b18 and R b21 ~R b26 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0193] R b13 and R b14 and R b21 and R b22 These atoms may bond with each other and together with the benzene ring to which they are bonded, form a ring containing a sulfur atom, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-.

[0194] R b27 ~R b29 Each of these independently represents a group containing a hydrogen atom or an acid-unstable group. L b31 and L b41 ~L b43 Each of these independently represents either a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5.

[0195] q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, and when r2 is 2 or more, multiple R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 They are the same or different, and when t2 is 2 or more, multiple R b18 They are either the same or different.

[0196] u3 represents an integer between 1 and 3, satisfying the condition 1 ≤ u3 + q23 ≤ 5. u4 and u5 each independently represent an integer between 0 and 3, satisfying 0 ≤ u4 + o21 ≤ 5 and 0 ≤ u5 + p22 ≤ 5.

[0197] When u3, u4, and u5 are each 2 or more, the bases in the parentheses are either the same or different. o21, p22, q23, r24, t25, and s26 each independently represent an integer between 0 and 4.

[0198] When o21, p22, q23, r24, t25, and s26 are each 2 or more, multiple R b21 ~R b26 These are either identical or distinct from one another. When u2 is 0, then at least one of o2, p2, q2, and r2 is 1 or greater, and R b13 ~R b16Preferably, at least one of them is a halogen atom, and when u2 is 1, then one of o2, p2, s2, t2, q2 and r2 is 1 or more, and R b13 ~R b18 Preferably, at least one of them is a halogen atom.

[0199] Furthermore, when u2 is 0, it is preferable that r2 is 1 or greater, and more preferably 1. Also, when u2 is 0 and r2 is 1 or greater, R b16 It is preferable that the atom is a halogen atom.

[0200] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain-type hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl.

[0201] In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups.

[0202] [ka]

[0203] In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorbornyl group, and isobornyl group. In alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

[0204] A fluorinated alkyl group refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom, such as a fluoromethyl group, difluoromethyl group, trifluoromethyl group, or perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4.

[0205] Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenyl, naphthyl, and phenanthryl groups. Aromatic hydrocarbon groups may have a chain-like hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain-like hydrocarbon group (tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl, p-adamantylphenyl, etc.).

[0206] Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include the p-methoxyphenyl group.

[0207] Examples of chain-like hydrocarbon groups in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl groups.

[0208] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups.

[0209] Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0210] Examples of alkylcarbonyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group.

[0211] R b4 and R b5 The ring formed by the bonding of these atoms to each other and the sulfur atoms to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of such rings include those with 3 to 18 carbon atoms, preferably those with 4 to 18 carbon atoms. Furthermore, examples of sulfur atom-containing rings include those with 3 to 12 membered rings, preferably those with 3 to 7 membered rings, and the following rings are examples. * indicates a bonding site.

[0212] [ka]

[0213] R b9 and R b10The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxatian-4-ium ring.

[0214] R b11 and R b12 The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include oxocycloheptane rings, oxocyclohexane rings, oxonorbornane rings, and oxoadamantane rings.

[0215] R b27 ~R b29 Groups containing acid-unstable groups include -R c30 , -CO-OR c30 or -L c10 -CO-OR c30 The group indicated by (L c10 R represents an alkanediyl group with 1 to 6 carbon atoms. c30 This represents an acid-unstable group. Examples include:

[0216] R b27 ~R b29 Examples of acid-unstable groups include the groups represented by formula (1) or formula (2) as illustrated herein. Among cations (b2-1) to (b2-5), cation (b2-1), cation (b2-4), or cation (b2-5) are preferred.

[0217] The following cations can be considered as cations (b2-1):

[0218] [ka]

[0219] [ka]

[0220] The following cations can be considered as cations (b2-2):

[0221] [ka]

[0222] The following cations can be considered as cations (b2-3):

[0223] [ka]

[0224] The following cations can be considered as cations (b2-4):

[0225] [ka]

[0226] The following cations can be considered as cations (b2-5):

[0227] [ka]

[0228] Examples of carboxylate salts (I) include salts obtained by arbitrarily combining the cations and anions mentioned above. Specific examples of carboxylate salts (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the anion or cation described above, and "~" indicates that the carboxylate salt (I) and the anion (I) correspond to each other. For example, carboxylate salt (I-1) is a salt consisting of the anion represented by formula (Ia-1) and the cation represented by formula (b2-c-1), carboxylate salt (I-2) is a salt consisting of the anion represented by formula (Ia-2) and the cation represented by formula (b2-c-1), and carboxylate salt (I-101) is a salt consisting of the anion represented by formula (Ia-1) and the cation represented by formula (b2-c-2).

[0229] [ka]

[0230] [Table 1]

[0231] JPEG2026093366000046.jpg193170

[0232] JPEG2026093366000047.jpg84170

[0233] In particular, the carboxylate salt (I) is preferably a salt formed by combining an anion represented by any of formulas (Ia-1) to (Ia-114) with a cation represented by any of formulas (b2-c-1), (b2-c-10), (b2-c-13), (b2-c-14), (b2-c-18) to (b2-c-20), (b2-c-27), (b2-c-30), (b2-c-31), or (b2-c-50) to (b2-c-80).

[0234] <Method for producing carboxylate salt (I)> Carboxylate salt (I) can be produced, for example, by reacting a salt represented by formula (Ia) with a compound represented by formula (Ib) in a solvent in the presence of a catalyst.

[0235] [ka]

[0236] (In the formula, symbols other than those listed below have the same meaning as described above. nm2 and nm3 each independently represent 0 or 1. L 1′ L 1 from-(CO) nm2 -X 1′ -(CO) nm3 -(CO-X 1′ ) nm4 Represents the base without the hyphen. X 1´ -O-, -NR 7 It represents -. However, when nm2 = nm3 = 0, nm4 represents 1, and when either nm2 or nm3 is 1, nm4 represents 0. Examples of solvents used in this reaction include chloroform, acetonitrile, methanol, and deionized water.

[0237] Examples of solvents used in this reaction include chloroform and acetonitrile. Examples of catalysts include carbonyldiimidazole, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, and sodium hydroxide.

[0238] The reaction temperature is typically between 5°C and 80°C, and the reaction time is typically between 0.5 hours and 24 hours. Examples of salts represented by formula (Ia) include those represented by the following formula, which are readily available on the market and can be easily manufactured by known methods.

[0239] [ka]

[0240] Compounds represented by formula (Ib) include, for example, the compounds shown below, which are readily available on the market and can also be easily manufactured by known methods.

[0241] [ka]

[0242] [ka]

[0243] [ka]

[0244] [ka]

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylate salt (I). The carboxylate salt (I) of the present invention can act as an acid generator or quencher in a resist composition. When the carboxylate salt (I) is used as an acid generator or quencher in a resist composition, the acid generator or quencher may contain only one type or two or more types of carboxylate salt (I).

[0249] Furthermore, the carboxylic acid generator of the present invention may further contain an acid generator known in the resist field other than carboxylate salt (I) (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator known in the resist field other than carboxylate salt (I), as described later. Acid generator (B) may be used alone or in combination of two or more types.

[0250] When the carboxylic acid generator of the present invention contains an acid generator (B), etc., the ratio (mass ratio; carboxylic acid salt (I): acid generator (B)) of the carboxylic acid salt (I) to the acid generator (B), etc. is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, even more preferably 5:95 to 95:5, even more preferably 10:90 to 90:10, and even more preferably 15:85 to 85:15.

[0251] [Resist composition] The resist composition of the present invention contains a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention. Preferably, the resist composition of the present invention further contains an acid generator other than the carboxylic acid generator (hereinafter sometimes referred to as "acid generator (B)"). The resist composition of the present invention may further contain a resin. Examples of resins include resins containing structural units having acid-unstable groups (hereinafter sometimes referred to as "resin (A)") and / or resins other than resin (A). Here, "acid-unstable group" means a group having a leaving group, in which the leaving group is removed upon contact with an acid to form a hydrophilic group (for example, a hydroxyl group or a carboxyl group).

[0252] The resist composition of the present invention preferably further contains a quencher other than the carboxylate salt (I) (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)").

[0253] In the resist composition of the present invention, the content of carboxylate salt (I) is 0.1% by mass or more and 99.9% by mass or less, preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and even more preferably 1% by mass or more and 25% by mass or less, based on the solid content of the resist composition.

[0254] <Acid Generator (B)> The acid generator (B) may be either a nonionic or ionic compound. Examples of nonionic compounds include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxiimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Typical ionic compounds include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of onium salt anions include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions.

[0255] Furthermore, the acid generator (B) may be part of the structural units that constitute the resin contained in the resist composition of the present invention, as shown in the structural unit (a7) described later. As the acid generator (B), compounds that generate acid by radiation as described in Japanese Patent Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, U.S. Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Compounds manufactured by known methods may also be used.

[0256] The acid generator (B) may be an acid generator having an acid-unstable group. For example, the compound or resin that acts as the acid generator may contain a substructure that constitutes an acid-unstable group, and it is preferable that the acid-unstable group contains group (1) or group (2) described later. If the resist composition of the present invention contains a compound having an acid-unstable group, it does not need to contain a resin containing a structural unit having an acid-unstable group.

[0257] Preferred forms of the acid generator (B) include a salt represented by formula (B1) (hereinafter sometimes referred to as "salt (B1)" or "acid generator (B1)"), a salt represented by formula (B2) (hereinafter sometimes referred to as "salt (B2)" or "acid generator (B2)"), and a salt represented by formula (B4) (hereinafter sometimes referred to as "salt (B4)" or "acid generator (B4)").

[0258] [ka]

[0259] [In formula (B1), L b1 represents a hydrocarbon group having a single bond or a substituent (nb1+1), and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, or -SO2-.

[0260] L b2 represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0261] Y b1 represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -SO-, -SO2- or -CO-.

[0262] nb1 represents an integer between 1 and 6. When nb1 is 2 or greater, the bases within the parentheses may be the same or different. Z1 + This represents an organic cation. L b1 As for (nb1+1) valent hydrocarbon groups, one nb hydrogen atom is removed from a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent group formed by combining two or more of these groups, resulting in 1 or more L b2 A group that bonds with the hydrocarbon group is an example. The number of carbon atoms in the hydrocarbon group is 1 to 48, preferably 1 to 42, more preferably 1 to 36, even more preferably 1 to 30, even more preferably 1 to 24, even more preferably 1 to 18, and even more preferably 1 to 10.

[0263] Examples of chain-like hydrocarbon groups include alkyl groups or alkenyl groups from which one nb hydrogen atom has been removed. Alkyl groups may be linear or branched, and specifically include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and heptadecyl groups. Examples of alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups.

[0264] The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 36, more preferably 1 to 24, even more preferably 1 to 20, even more preferably 1 to 18, even more preferably 1 to 12, and even more preferably 1 to 10.

[0265] Examples of alicyclic hydrocarbon groups include groups obtained by removing one nb hydrogen atom from a monocyclic or polycyclic cycloalkyl group. Examples of monocyclic cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0266] Examples of polycyclic cycloalkyl groups include cycloalkyl groups having a cross-linking structure, cycloalkyl groups formed by the condensation of two or more rings, or cycloalkyl groups formed by the spirolinking of two rings. Examples of cycloalkyl groups having a cross-linking structure include norbornyl groups and adamantyl groups. Examples of cycloalkyl groups formed by the condensation of two or more rings include bicyclo[4.4.0]decanyl groups and steroid groups (steroid skeletons). Examples of cycloalkyl groups formed by the spirolinking of two rings include spirocyclic cycloalkyl groups in which one or more cycloalkyl groups selected from the group consisting of cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups are spirolinked to a cycloalkyl group having 5 to 8 carbon atoms. Furthermore, a double bond may be formed between two carbon atoms in the alicyclic hydrocarbon group.

[0267] More specifically, examples include alicyclic hydrocarbon groups represented by the following formula.

[0268] [ka]

[0269] When the alicyclic hydrocarbon group is a monocyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 24, more preferably 3 to 20, even more preferably 3 to 18, even more preferably 3 to 12, even more preferably 3 to 10, and even more preferably 3 to 8. When the alicyclic hydrocarbon group is a polycyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 6 to 24, more preferably 6 to 20, even more preferably 6 to 18, even more preferably 6 to 12, and even more preferably 7 to 12.

[0270] Aromatic hydrocarbon groups include those obtained by removing one hydrogen atom from the nb side of an aryl group. Examples of aryl groups include phenyl, naphthyl, anthryl, biphenyl, and fluorenyl groups. More specifically, aromatic hydrocarbon groups represented by the following formulas are examples.

[0271] [ka]

[0272] The number of carbon atoms in the aromatic hydrocarbon group is preferably 4 to 24, more preferably 4 to 20, even more preferably 4 to 18, even more preferably 5 to 14, even more preferably 5 to 10, and even more preferably 6 to 10.

[0273] L b1 If the -CH2- contained in the hydrocarbon group is replaced by -O-, -CO-, -S-, -SO-, or -SO2-, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group.

[0274] L b1Among the hydrocarbon groups, groups in which the -CH2- contained in the chain hydrocarbon group is replaced with -O-, -CO-, -S-, -SO-, or -SO2- include hydroxyl groups, carboxyl groups, thiol groups, carbonyl groups, oxy groups, thio groups, sulfonyl groups, alkoxy groups, alkylthio groups, alkylsulfonyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, alkoxyalkoxy groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyloxy groups, alkanediyloxycarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, and groups combining two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0275] L b1 Among the hydrocarbon groups, groups in which the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or combinations thereof is replaced with -O-, -CO-, -S-, -SO-, or -SO2- include groups containing structures such as cyclic ethers, cyclic ketones, cyclic esters (lactones), cyclic thioethers, cyclic acetals, and cyclic sulfonic acid esters (sultones), as well as groups derived from furan rings, thiophene rings, etc. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0276] Groups combining two or more types of groups, such as a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, include groups combining the above-mentioned chain hydrocarbon group and the above-mentioned alicyclic hydrocarbon group, groups combining the above-mentioned chain hydrocarbon group and the above-mentioned aromatic hydrocarbon group, groups combining the above-mentioned alicyclic hydrocarbon group and the above-mentioned aromatic hydrocarbon group, and groups combining the above-mentioned chain hydrocarbon group, the above-mentioned alicyclic hydrocarbon group, and the above-mentioned aromatic hydrocarbon group. Groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group may also be fused rings.

[0277] L b2Examples of divalent hydrocarbon groups include divalent chain hydrocarbon groups, divalent alicyclic hydrocarbon groups, divalent aromatic hydrocarbon groups, and groups formed by combining two or more of these groups. By removing one hydrogen atom from a monovalent hydrocarbon group, Y b1 Examples of groups that bond with it include:

[0278] L b2 The divalent chain hydrocarbon group, divalent alicyclic hydrocarbon group, divalent aromatic hydrocarbon group, and divalent groups formed by combining two or more of these groups are each L, within the limits permitted by the upper limit of the number of carbon atoms. b1 Examples include monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and monovalent groups obtained by removing one hydrogen atom from a combination of two or more of these monovalent groups.

[0279] L b1 and L b2 The hydrocarbon group may have substituents such as halogen atoms, cyano groups, and nitro groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0280] L b1 and L b2 However, if the group is a combination of an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group, the chain hydrocarbon group may be substantially considered as a substituent of the alicyclic hydrocarbon group or aromatic hydrocarbon group. b1 and L b2 The -CH2- in the chain hydrocarbon group contained in the hydrocarbon group is replaced by -O-, -CO-, -S-, -SO-, or -SO2-, L b1 and L b2 The hydrocarbon group may substantially have substituents such as a hydroxyl group, carboxyl group, carbonyl group, oxycarbonyl group, carbonyloxy group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, thiol group, alkylthio group, and alkylsulfonyl group.

[0281] Y b1Examples of cyclic hydrocarbon groups include alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups that combine alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Y b1 The alicyclic hydrocarbon group and aromatic hydrocarbon group are, respectively, L b1 Examples include the same alicyclic hydrocarbon groups and aromatic hydrocarbon groups as exemplified above, and if they do not have substituents, they may be monovalent alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0282] Y b1 Examples of substituents that the methyl group and cyclic hydrocarbon group may have include halogen atoms, cyano groups, nitro groups, or C1-C18 hydrocarbon groups that may have halogen atoms, cyano groups, or nitro groups (the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-). b1 The number of carbon atoms in the methyl group and the cyclic hydrocarbon group that may have is Y b1 The number of carbon atoms in the methyl group and cyclic hydrocarbon group is not included.

[0283] Y b1 The methyl group and cyclic hydrocarbon group may have as substituents, and hydrocarbon groups having 1 to 18 carbon atoms include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these groups. Examples of chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining two or more of these groups include, within the limits permitted by the upper limit of carbon atoms, L b1 Examples include the chain-like hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining two or more of these groups, as exemplified above.

[0284] Also, Y b1 Examples of groups in which the methyl group and cyclic hydrocarbon group may have as substituents, and in which the -CH2- in a hydrocarbon group having 1 to 18 carbon atoms is replaced with -O-, -S-, -CO-, -SO-, or -SO2-, are given within the limits permitted by the upper limit of carbon atoms. b1Groups in which the -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, -SO-, or -SO2- are similar to the groups exemplified above. Also, Y b1 The methyl group and cyclic hydrocarbon group may have as substituents a hydrocarbon group having 1 to 18 carbon atoms, which may constitute a protecting group or a leaving group (acid-unstable group or base-unstable group) commonly used in the field.

[0285] The anion of the salt represented by formula (B1) is preferably the anion represented by the following formula (B1-A1) (hereinafter sometimes referred to as "anion (B1-A1)") or the anion represented by formula (B1-A2) (hereinafter sometimes referred to as "anion (B1-A2)").

[0286] [ka]

[0287] [In formula (B1-A1), L b2 and Y b1 This has the same meaning as formula (B1). Q b1 Q b2 Q b3 and Q b4 Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.

[0288] z1 represents an integer between 0 and 6. When z1 is 2 or greater, the bases within the parentheses may be the same or different. X 1 -O-CO-, -CO-O-, -O-CO-O-, or -O-.

[0289] L b3 represents a (nb2+1) valent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0290] nb2 represents an integer between 1 and 3. When nb2 is 2 or greater, the bases within the parentheses may be the same or different. Q b1 Q b2 Q b3 and Q b4 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

[0291] Q b1 Q b2 Q b3 and Q b4 Examples of perfluoroalkyl groups include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, and perfluorohexyl groups.

[0292] Q b1 and Q b2 Q b1 and Q b2 Preferably, at least one of them contains a fluorine atom or a perfluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, even more preferably a fluorine atom or a trifluoromethyl group, and even more preferably both are fluorine atoms.

[0293] Q b3 and Q b4 Each of these is preferably independently a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms, Q b3 Q is preferably a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms. b4 It is preferable that this is a hydrogen atom or a fluorine atom.

[0294] z1 is preferably an integer between 0 and 3, and more preferably 0, 1, or 2. X 1 It is preferable that it be -O-CO- or -CO-O-.

[0295] L b3 As for the hydrocarbon group in this, within the limits permitted by the upper limit of the number of carbon atoms, L of formula (B1) b1 The same hydrocarbon groups as in the example above can be cited. L b3 It is preferably a single bond, a chain hydrocarbon group having 1 to 12 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), a alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO- or -SO2-), an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have substituents (the -CH2- contained in the aromatic hydrocarbon group may be replaced with -O- or -S-), or a group that is a combination of two or more of these groups, and more preferably a single bond, a chain hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula (Lb3-1). Furthermore, when -CH2- contained in a chain hydrocarbon group is replaced with -O- or -CO-, it is preferable that the number of -CH2- contained in the chain hydrocarbon group that is replaced with -O- or -CO- is 1 to 4, and it is preferable that one -CH2-CH2- contained in the chain hydrocarbon group is replaced with -O-CO- or -CO-O-, or that one -CH2-CH2-CH2- contained in the chain hydrocarbon group is replaced with -O-CO-O-.

[0296] [ka]

[0297] [In formula (Lb3-1), nb2 has the same meaning as the expression (B1-A1). L b31 represents a single bond or a chain-like hydrocarbon group having 1 to 12 carbon atoms, and the -CH2- contained in the chain-like hydrocarbon group may be replaced with -O- or -CO-, and the chain-like hydrocarbon group may have substituents.

[0298] W b3 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO- or -SO2-, and the -CH2- contained in the aromatic hydrocarbon group may be replaced with -O- or -S-, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have substituents.

[0299] * and ** represent bonding sites, where * is X 1 This represents the connection point with [the other element]. In formula (Lb3-1), L b31 The chain-like hydrocarbon group is L as long as the upper limit of the number of carbon atoms allows. b1 Examples of similar groups to the chain-like hydrocarbon groups exemplified above include those mentioned earlier.

[0300] In formula (Lb3-1), W b3 The alicyclic hydrocarbon group and aromatic hydrocarbon group are L as long as the upper limit of the number of carbon atoms allows. b1 Examples of similar groups to the alicyclic hydrocarbon groups and aromatic hydrocarbon groups exemplified above include the alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0301] In formula (Lb3-1), L b31 The chain-like hydrocarbon group may have substituents and W b3 The substituents that the alicyclic hydrocarbon group and aromatic hydrocarbon group may have are L b1 Examples of substituents that the hydrocarbon group may have include groups similar to those exemplified above.

[0302] L b31 Preferably, the component is a single bond or an alkanediyl group having 1 to 6 carbon atoms (the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-).

[0303] W b3Examples of alicyclic hydrocarbon groups and aromatic hydrocarbon groups include the following: In the alicyclic hydrocarbon groups and aromatic hydrocarbon groups shown below, * and ** represent bonding sites, and * is X 1 or L b31 This represents the bonding site with , where ** represents a hydrogen atom, substituent, or L b2 This represents the bonding site with L, and at least one ** is L b2 This represents the bonding site with . Furthermore, in the alicyclic hydrocarbon group shown below, the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-. When the -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO-, -SO-, or -SO2-, it is preferable that an ether ring, ester ring (lactone ring), carbonate ester ring, sulfonic acid ester ring (sultone ring), or acetal ring is formed.

[0304] [ka]

[0305] In equation (B1-A1), L b2 The carbon atoms are preferably single bonds or chain hydrocarbon groups having 1 to 12 carbon atoms (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), and are single bonds, -O-, -O-CO-, -CO-O-, -O-CO-O- or *-L b21 -X 2 -L b22 -**(L b21 and L b22 Either one represents a chain hydrocarbon group having at least 1 to 6 carbon atoms, and the other represents a single bond or a chain hydrocarbon group having 1 to 6 carbon atoms, X 2 represents -O-, -CO-O-, -O-CO-, or -O-CO-O-, * and ** represent binding sites, and ** is Y b1 This represents the bonding site with L. b21 , X 2 and L b22 It is more preferable that the total number of carbon atoms is 12 or less.

[0306] In equation (B1-A1), Y b1 It is preferably a cyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), or an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents, and even more preferably an alicyclic hydrocarbon group having 3 to 16 carbon atoms that may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), or an aromatic hydrocarbon group having 6 to 10 carbon atoms that may have substituents. Specifically, it is more preferably a group represented by the following formulas (Y1) to (Y36). In formulas (Y1) to (Y36), R Yb is a hydrogen atom or Y b1 Among the substituents that the cyclic hydrocarbon group may have, represent an alkyl group having 1 to 4 carbon atoms, R Yc is a hydrogen atom or Y b1 This represents substituents that the cyclic hydrocarbon group may have, and * represents L b2 This represents the bonding site. The alicyclic hydrocarbon group and aromatic hydrocarbon group represented by the following formula may have other substituents, although they are not specifically shown in the following formula.

[0307] [ka]

[0308] The anion represented by formula (B1-A1) is preferably the anion represented by formulas (B1-A1-1) to (B1-A1-85) [hereinafter, depending on the formula number, it may be referred to as "anion (B1-A1-1)", etc.], and more preferably the anion represented by any of formulas (B1-A1-1) to (B1-A1-4), formula (B1-A1-9), formula (B1-A1-10), formula (B1-A1-24) to (B1-A1-33), formula (B1-A1-36) to (B1-A1-40), or formula (B1-A1-47) to (B1-A1-85).

[0309] [ka]

[0310] [ka]

[0311] [ka]

[0312] Here R i2 ~R i7 These are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. i8 For example, this is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by a combination thereof, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 This is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

[0313] Q b1 and Q b2 This expresses the same meaning as above. An example of anion represented by formula (B1-A1) is the anion described in Japanese Patent Publication No. 2010-204646.

[0314] Preferred anions represented by formula (B1-A1) include those represented by formulas (B1a-1) to (B1a-82), respectively. Among these, anions represented by any of the following are preferred: formulas (B1a-1) to (B1a-4), formulas (B1a-7) to (B1a-11), formulas (B1a-14) to (B1a-30), and formulas (B1a-35) to (B1a-70).

[0315] [ka]

[0316] [ka]

[0317] [ka]

[0318] The anion represented by equation (B1-A2) is expressed by the following equation:

[0319] [ka]

[0320] [In formula (B1-A2), L b2 and Y b1 This has the same meaning as formula (B1). R b1 represents a halogen atom or an alkyl group having 1 to 6 carbon atoms, and the -CH2- contained in the alkyl group may be replaced with -O- or -CO-.

[0321] nb4 represents an integer between 1 and 5. When nb4 is 2 or greater, the bases within the parentheses may be the same or different. nb3 represents an integer between 0 and 4. When nb3 is 2 or greater, multiple R b1 They may be the same or different from one another.

[0322] However, the condition 1 ≤ nb4 + nb3 ≤ 5 must be satisfied. In equation (B1-A2), L b2 Examples of hydrocarbon groups and Y b1 Examples of cyclic hydrocarbon groups include L in formula (B1), to the extent permitted by the upper limit of the number of carbon atoms. b2 Examples of hydrocarbon groups and Y b1 Examples of cyclic hydrocarbon groups are the same as those shown. b2 The hydrocarbon group, Y b1 The substituents that the methyl group and cyclic hydrocarbon group may have are also the L of formula (B1) b2 The hydrocarbon group, Y b1 Examples of substituents that the methyl group and cyclic hydrocarbon group may have are the same as those mentioned above.

[0323] These hydrocarbon groups, methyl groups, and cyclic hydrocarbon groups may have one or more substituents. L b2 Preferably, is a chain-like hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the chain-like hydrocarbon group may be replaced with -O- or -CO-), and more preferably, *-CO-OL b41 -(L b41 * is a single bond or a chain hydrocarbon group having 1 to 6 carbon atoms, and the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-. - This represents the bonding site with the benzene ring to which it is bonded. b41 The carbon group is preferably a single bond or a chain-like hydrocarbon group having 1 to 3 carbon atoms, and more preferably *-CO-O-.

[0324] Y b1It is preferably a cyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), or an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents, and Y of formula (B1-A1) b1 or L b1 It is even more preferable that the group is an alicyclic hydrocarbon group or an aromatic hydrocarbon group as exemplified above. Specifically, it is preferably a group represented by formulas (Y1) to (Y36) described above, and more preferably a group represented by formulas (Y1) to (Y19) described above.

[0325] Y b1 The substituents that the cyclic hydrocarbon group may have are preferably halogen atoms or C1-C6 alkyl groups (the -CH2- contained in the alkyl group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-), more preferably fluorine atoms, iodine atoms, or C1-C4 alkyl groups (the -CH2- contained in the alkyl group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-), even more preferably fluorine atoms, iodine atoms, hydroxyl groups, C1-C3 alkoxy groups, or C1-C4 alkyl groups, and even more preferably fluorine atoms, iodine atoms, hydroxyl groups, or C1-C4 alkyl groups. b1 The substituents may be protecting groups or leaving groups (acid-unstable or base-unstable groups) commonly used in the field.

[0326] In formula (B1-A2), nb4 is preferably an integer from 1 to 4, more preferably an integer from 1 to 3, even more preferably 1 or 2, and even more preferably 2. When nb4 is 1 or 2, -L b2 -Y b1 The binding position is SO3 -The following structure is preferable, where the benzene ring is meta-substituted relative to the bonded position.

[0327] [ka]

[0328] [In the above formula, L b2 , Y b1 , R b1 nb3 has the same meaning as formula (B1-A2). In formula (B1-A2), if nb4 is 2 or more, multiple L b2 and Y b1 It is preferable that these are the same group.

[0329] R b1 Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably 1 to 3.

[0330] R b1 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Groups in which the -CH2- group in an alkyl group is replaced with -O- or -CO- include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, oxy groups, and carbonyl groups. These replaced groups are similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0331] R b1It is preferably a halogen atom or an alkyl group having 1 to 4 carbon atoms (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), more preferably a fluorine atom, an iodine atom, or an alkyl group having 1 to 3 carbon atoms (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methoxy group, or a methyl group.

[0332] nb3 is an integer from 0 to 4 (i.e., nb3-1 represents an integer from 0 to 3), preferably an integer from 0 to 3, and more preferably an integer from 0 to 2. In one embodiment, it is preferable that nb3 is 0. In another embodiment, it is preferable that nb3 is 1 or 2. When nb3 is 1, R b1 It is preferable that R is a halogen atom, b1 It is more preferable that nb3 is a fluorine atom or an iodine atom. When nb3 is 2, R b1 Preferably, one of them is a halogen atom, and the other is a halogen atom or an alkyl group having 1 to 4 carbon atoms, R b1 It is more preferable that one of the atoms is a fluorine atom or an iodine atom, and the other atom is a fluorine atom, an iodine atom, or an alkyl group having 1 to 3 carbon atoms.

[0333] Examples of anions represented by formula (B1-A2) include the following anions. Among these, the anions represented by formulas (B2a-1) to (B2a-20) are preferred, and the anions represented by formulas (B2a-1) to (B2a-11) and (B2a-16) to (B2a-20) are more preferred. The following anions are some of the R b1 The figure is omitted and may include substituents that are not shown.

[0334] [ka]

[0335] Examples of acid generators (B2) include salts represented by the following formula.

[0336] [ka]

[0337] [In formula (B2), A 1 represents a nitrogen atom or a carbon atom. L b2′ represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0338] Y b1′ represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO- or -SO2-.

[0339] nb5 is A 1 If it is a nitrogen atom, then it is 2, and A 1 If it is a carbon atom, then it is 3. The groups in parentheses may be the same or different from each other, and two groups in parentheses combine to form A 1 A ring containing the element may be formed.

[0340] Z2 + This represents an organic cation. In equation (B2), L b2′ and Y b1′ An example of this is L in formula (B1-A1). b2 and Y b1 Similar bases can be cited.

[0341] L b2′ This is a single bond, *-L b23 -, *-L b23 -X 2 - or *-L b23 -X 2 -W 2 -X3 -(L b23 X represents a chain-like hydrocarbon group having 1 to 6 carbon atoms, which may contain a fluorine atom. 2 and X 3 These each independently represent -O-, -CO-O-, -O-CO-, -O-CO-O-, or -O-, W 2 (where represents an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O- or -CO-, and * represents the bonding site with SO2.) is preferable.

[0342] Y b1′ It is preferably a methyl group having a fluorine atom or a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents (the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO-, or -SO2-), and more preferably a trifluoromethyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-), or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents. Specifically, it is preferably a trifluoromethyl group or a group represented by formulas (Y1) to (Y36) in formula (B1-A1).

[0343] In the salt anion represented by formula (B2), two -SO2-L b2′ -Y b1′ When these come together to form a ring, an example is the anion represented by formula (B2').

[0344] [ka]

[0345] [In formula (B2′), A 1 , Y b1′ , L b2′ And nb5 has the same meaning as formula (B2). W b4This represents a disulfonylimide ring or disulfonylmethide ring having 2 to 12 carbon atoms, which may contain a fluorine atom. W b4 The disulfonylimide ring or disulfonylmethide ring preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms, and it is preferable that the hydrogen atoms of the methylene group contained in the ring are replaced with fluorine atoms.

[0346] The following are examples of anions in the salt represented by formula (B2). Among these, the anions represented by formulas (B3a-1), (B3a-2), (B3a-12) to (B3a-14) are preferred.

[0347] [ka]

[0348] Another form of compound (B) is the salt represented by formula (B4) (hereinafter sometimes referred to as "salt (B4)" or "acid generator (B4)").

[0349] [ka]

[0350] [In formula (B4), all signs have the same meaning as above.] In equation (B4), L b14 and L b15 An example of this is L in formula (B1) or formula (B1-A1). b1 and L b2 The same type of group can be cited as an example.

[0351] Ar B4 and Ar B5 Examples of aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, biphenylene groups, and phenanthrylene groups. The bonding site can be at any position. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0352] Ar B4 and Ar B5 The substituents that the aromatic hydrocarbon group may have include halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, C1-C12 alkyl groups, C1-C6 fluorinated alkyl groups, C1-C12 alkoxy groups, and groups formed by combining two or more of these groups. These substituents are described in R B4 and R B5 Examples similar to those exemplified earlier can be given.

[0353] Among them, Ar B4 and Ar B5 The group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have substituents; more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkyl fluoride group having 1 to 6 carbon atoms; even more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have a fluorine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl fluoride group having 1 to 3 carbon atoms; and even more preferably a phenylene group or a naphthylene group.

[0354] Ar B4 and Ar B5 If is a phenylene group which may have substituents, the bond position of the fluorene ring is L b14 and L b15 The bonding position may be ortho, meta, or para, but it is preferably meta or para, and more preferably para.

[0355] R B4 and R B5 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. R B4 and R B5 Examples of hydrocarbon groups having 1 to 18 carbon atoms include chain-type hydrocarbon groups such as alkyl groups and alkanediyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.

[0356] Examples of alkyl groups include linear or branched alkyl groups, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Alkanediyl groups include linear or branched alkanediyl groups, such as methylene groups, ethylene groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, and linear alkanediyl groups; and Examples of branched alkanediyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.

[0357] The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0358] Alicyclic hydrocarbon groups may be monocyclic or polycyclic, and include the groups listed below. The bonding site can be at any position.

[0359] [ka]

[0360] Specifically, monocyclic alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl. Polycyclic alicyclic hydrocarbon groups include polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, and norbornyl; cycloalkyl groups such as spirocyclohexane-1,2′-cyclopentane and spiroadamantane-2,3′-cyclopentane; and spiro rings having cycloalkyl groups spiro-bonded to norbornyl or adamantyl groups. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12.

[0361] Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, biphenyl groups, anthryl groups, phenanthryl groups, and binaphthyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0362] Groups formed by combining two or more groups from among chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include groups formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*, alkyl group-aromatic hydrocarbon group-alkanediyl group-*, the -CH2- contained in the alkanediyl group and the alkyl group may be replaced with -O-, -CO-, -S-, -SO- or -SO2-), and groups formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group-alkanediyl group). Examples include diyl group-*, alkyl group-alicyclic hydrocarbon group-*, alkyl group-alicyclic hydrocarbon group-alkanediyl group-*, the -CH2- contained in the alicyclic hydrocarbon group, the alkanediyl group and the alkyl group may be replaced with -O-, -CO-, -S-, -SO- or -SO2-), and groups combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*, the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S-, -SO- or -SO2-). * indicates a bonding site.

[0363] Examples of aromatic hydrocarbon groups - alkanediyl groups -* include aralkyl groups such as benzyl and phenethyl groups. Examples of alkyl-aromatic hydrocarbon groups-* include tolyl groups, xylyl groups, and cumenyl groups.

[0364] Examples of alicyclic hydrocarbon groups - alkanediyl groups -* include cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl group, and other cycloalkylalkyl groups.

[0365] Examples of alkyl-alicyclic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, and cycloalkyl groups having alkyl groups such as 2-alkyladamantan-2-yl group.

[0366] Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include the phenylcyclohexyl group. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include the cyclohexylphenyl group.

[0367] Furthermore, in the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain-like hydrocarbon groups may be combined. Also, any of these groups may be bonded to a benzene ring or the like.

[0368] R B4 and R B5 If the -CH2- contained in the hydrocarbon group represented by is replaced by -O-, -CO-, -S-, -SO-, or -SO2-, the number of carbon atoms before replacement shall be the total number of carbon atoms in the hydrocarbon group. This number may be one or two or more.

[0369] As mentioned above, examples of groups in which the -CH2- contained in a hydrocarbon group is replaced with -O-, -S-, -SO-, -SO2-, or -CO- include hydroxyl groups, thiol groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkylthio groups, alkylsulfonyl groups, oxy groups, carbonyl groups, thio groups, sulfonyl groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediylthio groups, alkanediylsulfonyl groups, cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, aromatic hydrocarbon group-carbonyloxy groups, aromatic hydrocarbon group-carbonyl groups, aromatic hydrocarbon group-oxy groups, and groups combining two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0370] Furthermore, groups in which the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining alicyclic hydrocarbon groups and aromatic hydrocarbon groups is replaced with -O-, -S-, -SO-, -SO2-, or -CO- include the same groups as those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0371] R B4 and R B5 The substituents that the hydrocarbon group may have include halogen atoms, cyano groups, nitro groups, and the like. Examples of halogen atoms include the same groups as those described above.

[0372] The hydrocarbon group may have one substituent or more substituents. R B4 and R B5 However, if it is a hydrocarbon group having a halogen atom, R B4 and R B5 Examples of hydrocarbon groups having halogen atoms include chain hydrocarbon groups having halogen atoms such as haloalkyl groups, alicyclic hydrocarbon groups having halogen atoms, and aromatic hydrocarbon groups having halogen atoms.

[0373] A haloalkyl group refers to an alkyl group having a halogen atom, and examples include C1-C12 alkyl fluorides, C1-C12 alkyl chlorides, C1-C12 alkyl bromides, and C1-C12 alkyl iodides. Examples of haloalkyl groups include C1-C12 perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the haloalkyl group is preferably 1-9, more preferably 1-6, even more preferably 1-4, and even more preferably 1-3.

[0374] The -CH2- group in the haloalkyl group may be replaced with -O- or -CO-, etc. Examples of such groups include haloalkoxy groups, haloalkoxycarbonyl groups, haloalkylcarbonyl groups, and haloalkylcarbonyloxy groups. Specifically, examples include haloalkoxy groups having 1 to 11 carbon atoms, haloalkoxycarbonyl groups having 2 to 11 carbon atoms, haloalkylcarbonyl groups having 2 to 12 carbon atoms, and haloalkylcarbonyloxy groups having 2 to 11 carbon atoms. For example, a group in which one or more hydrogen atoms of the above-executed groups are replaced with halogen atoms can be used.

[0375] mB4 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1. mB5 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0376] R B4 and R B5Each of these is preferably independently a halogen atom, a C1-C6 haloalkyl group, or a C1-C6 alkyl group (the -CH2- contained in the haloalkyl group and the alkyl group may be replaced with -O- or -CO-), more preferably a fluorine atom, an iodine atom, a C1-C6 haloalkyl group, or a C1-C6 alkyl group (the -CH2- contained in the haloalkyl group and the alkyl group may be replaced with -O- or -CO-), and more preferably a fluorine atom, an iodine atom, a C1-C4 haloalkyl group, or a C1-C4 alkyl group (the alkyl group may contain The -CH2- may be replaced with -O- or -CO-. It is more preferably a fluorine atom, an iodine atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a C1-C3 alkoxy group, it is even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 perfluoroalkyl group or a C1-C3 alkoxy group, and it is even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a methoxy group, an ethoxy group or a hydroxyl group.

[0377] The following are examples of anions in the salt represented by formula (B4). Among these, the anions represented by formulas (B4a-1) to (B4a-4) and (B4a-11) to (B4a-14) are preferred.

[0378] [ka]

[0379] Furthermore, in another form of the acid generator (B), a salt obtained by replacing the anion in the salt represented by formula (B1) with a carboxylate anion is also suitably used as the acid generator (B). Examples of carboxylic acid anions include the following:

[0380] [ka]

[0381] Z1 + Z2 + Z4 + and Z5 + As for the organic cation, Z in formula (I) + and Z11 + Examples include those similar to organic cations. The acid generator (B) is a combination of the anion and the organic cation described above, and these can be combined arbitrarily. Preferably, the acid generator (B) is formula (B1a-1) to formula (B1a-4), formula (B1a-7) to formula (B1a-11), formula (B1a-14) to formula (B1a-30), formula (B1a-35) to formula (B1a-70), formula (B2a-1) to formula (B2a-11), formula (B2a-16) to formula (B2a-20), formula (B3a-1) to formula (B3a Examples include combinations of an anion represented by -3) or formula (B3a-11) to formula (B3a-14), formula (B4a-1) to formula (B4a-4), or formula (B4a-11) to formula (B4a-14) with a cation (b2-1), cation (b2-2), cation (b2-3), cation (b2-4), or cation (b2-5).

[0382] Preferably, the acid generator (B) is represented by formulas (B1-1) to (B1-106), (B2-1) to (B2-20), (B3-1) to (B3-28), and (B4-1) to (B4-16), respectively. Among these, those containing arylsulfonium cations are preferred, and those represented by formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), (B1-31) to (B1-105), (B2-1) to (B2-20), (B3-1) to (B3-28), and (B4-1) to (B4-16) are particularly preferred.

[0383] [ka]

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[0392] In the resist composition of the present invention, the total content of the acid generator is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 45% by mass or less, even more preferably 1% by mass or more and 40% by mass or less, and even more preferably 3% by mass or more and 40% by mass or less, based on the solid content of the resist composition. When the resin (A) described later is included, the total content of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, based on 100 parts by mass of the resin (A) described later.

[0393] In the resist composition of the present invention, the total content of salt (I) and acid generator (B), etc., is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 55% by mass or less, even more preferably 1% by mass or more and 450% by mass or less, and even more preferably 3% by mass or more and 45% by mass or less, relative to the solid content of the resist composition. When resin (A) is included, the total content of salt (I) and acid generator (B), etc., is preferably 1 part by mass or more, more preferably 3 parts by mass or more, preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less, relative to 100 parts by mass of resin (A).

[0394] <Resin (A)> Resin (A) contains structural units having acid-unstable groups (hereinafter sometimes referred to as "structural unit (a1)"). Preferably, resin (A) further contains structural units other than structural unit (a1). Examples of structural units other than structural unit (a1) include structural units that do not have acid-unstable groups (hereinafter sometimes referred to as "structural unit (s)") (for example, structural units having halogen atoms as described later (hereinafter sometimes referred to as "structural unit (a4)"), structural units having non-leaved hydrocarbon groups as described later (hereinafter sometimes referred to as "structural unit (a5)"), etc.), and structural units derived from other monomers known in the art.

[0395] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-unstable group (hereinafter sometimes referred to as "monomer (a1)").

[0396] The acid-unstable group contained in resin (A) is preferably the group represented by formula (1) (hereinafter also referred to as group (1)) and / or the group represented by formula (2) (hereinafter also referred to as group (2)).

[0397] [ka]

[0398] [In formula (1), R a1 , R a2 and R a3 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. a1 and R a2 These atoms bond to each other to form a cyclic hydrocarbon group having 3 to 20 carbon atoms, and the alkyl group, the alkenyl group, the cyclic hydrocarbon group, and the aromatic hydrocarbon group may have halogen atoms.

[0399] ma and na each independently represent either 0 or 1, and at least one of ma and na represents 1. * indicates a connection site.

[0400] [ka]

[0401] [In formula (2), R a1′ and R a2′ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a3′ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2′ and R a3′These atoms bond to each other to form a heterocyclic group having 3 to 20 carbon atoms, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced with -O- or -S-, and the hydrocarbon group and the heterocyclic group may have halogen atoms.

[0402] X represents either an oxygen atom or a sulfur atom. na′ represents either 0 or 1. * indicates a connection site. R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups.

[0403] R a1 , R a2 and R a3 Examples of alkenyl groups in this context include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups.

[0404] R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). a1 , R a2 and R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16.

[0405] [ka]

[0406] R a1 , R a2 and R a3 Examples of aromatic hydrocarbon groups in this context include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group.

[0407] Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of such groups include the following: Alicyclic hydrocarbon groups preferably have 3 to 12 carbon atoms. * indicates a bond site with -O-.

[0408] [ka]

[0409] R a1′ , R a2′ and R a3′ Examples of hydrocarbon groups in this context include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.

[0410] Alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these are R a1 , R a2 and R a3 The same types of elements mentioned above can be cited. R a2′ and R a3′ When they bond to each other and form a heterocyclic group with the carbon atoms to which they are bonded and X, -C(R a1′ )(R a2′ )-XR a3′ The following groups are examples. * indicates a binding site.

[0411] [ka]

[0412] R a1′ and R a2′ Preferably, at least one of them is a hydrogen atom. na' is preferably 0. R a1 , R a2 , R a3 , R a1 , R a2′ and R a3′ The halogen atoms that may be present include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0413] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 A group in which the parentheses is an alkyl group, ma=0, and na=1. A tert-butoxycarbonyl group is preferred as the group.

[0414] In equation (1), R a1 , R a2 However, these combine with the carbon atoms to which they bond to form an adamantyl group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), Ra1 and R a2 Each of them is an alkyl group independently, and R a3 This is an adamantyl group with ma=0 and na=1.

[0415] The following are specific examples of group (1). * indicates a bonding site.

[0416] [ka]

[0417] The following are specific examples of group (2). * indicates a bonding site.

[0418] [ka]

[0419] The monomer (a1) is preferably a monomer having an acid-unstable group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-unstable group. Among (meth)acrylic monomers having acid-unstable groups, those having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are preferred. If a resin (A) having structural units derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0420] Structural units derived from (meth)acrylic monomers having group (1) include structural units represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), structural units represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)), or structural units represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-0), structural unit (a1-1), and structural unit (a1-2), and more preferably, it is at least one or two structural units selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used individually or in combination of two or more.

[0421] [ka]

[0422] [In equations (a1-0), (a1-1), and (a1-2), all symbols have the same meanings as described above.] R a01 , R a4 and R a5 Examples of halogen atoms include fluorine, chlorine, bromine, or iodine atoms.

[0423] R a01 , R a4 and R a5Alkyl groups that may have halogen atoms include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, chloromethyl, bromomethyl, and iodomethyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0424] R a01 , R a4 and R a5 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a methyl group is even more preferred.

[0425] L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 It is -CO-O- (where k01 is preferably an integer from 1 to 4, more preferably 1), and more preferably an oxygen atom.

[0426] R a02 , R a03 , R a04 , R a6 and R a7 The alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof in formula (1) are R a1 , R a2 and R a3 Similar groups to those listed above can be cited.

[0427] R a02 , R a03 , and Ra04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0428] R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and even more preferably an ethyl group, an isopropyl group, or a t-butyl group.

[0429] R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group, or a butenyl group.

[0430] R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, and more preferably 6 to 10.

[0431] In groups combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and alicyclic hydrocarbon group is 18 or less. In groups combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and aromatic hydrocarbon group is 18 or less.

[0432] R a02 and R a03Preferably, this is a C1-C6 alkyl group that may have a halogen atom or a C6-C12 aromatic hydrocarbon group that may have a halogen atom, and more preferably a methyl group, ethyl group, phenyl group or naphthyl group that may have a halogen atom.

[0433] R a04 Preferably, this is a C1-C6 alkyl group which may have a halogen atom, or a C5-C12 alicyclic hydrocarbon group which may have a halogen atom, and more preferably a methyl group, ethyl group, cyclohexyl group, or adamantyl group which may have a halogen atom.

[0434] R a6 and R a7 Preferably, the group is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkenyl group having 2 to 6 carbon atoms which may have a halogen atom, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a halogen atom; more preferably, it is a methyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group, or naphthyl group which may have a halogen atom; and even more preferably, it is an ethyl group, isopropyl group, t-butyl group, ethenyl group, or phenyl group which may have a halogen atom.

[0435] m1' is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 10, more preferably an integer between 0 and 8, even more preferably an integer between 0 and 3, and even more preferably 0 or 1.

[0436] n1' is preferably 0 or 1. Examples of structural units (a1-0) include structural units represented by any of the formulas (a1-0-1) to (a1-0-24) and R in structural units (a1-0). a01Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group (an alkyl group having a halogen atom), or another alkyl group are given, and structural units represented by any of the formulas (a1-0-1) to (a1-0-10), (a1-0-13), (a1-0-14), (a1-0-19) to (a1-0-24) are preferred.

[0437] [ka]

[0438] Examples of structural units (a1-1) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646. In particular, structural units represented by any of formulas (a1-1-1) to (a1-1-7) and R in structural unit (a1-1) a4 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is preferred, and a structural unit represented by any of formulas (a1-1-1) to (a1-1-4) is more preferred.

[0439] [ka]

[0440] The structural unit (a1-2) is a structural unit represented by any of the formulas (a1-2-1) to (a1-2-20), and R in the structural unit (a1-2). a5 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of the formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-14).

[0441] [ka]

[0442] When resin (A) contains structural units (a1-0) and / or structural units (a1-1) and / or structural units (a1-2), the total content of these is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total structural units of resin (A). Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, even more preferably 25 to 70 mol%, and even more preferably 30 to 70 mol%.

[0443] When resin (A) contains structural units (a1-0), the content is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, and even more preferably 35 mol% or more, relative to the total structural units of resin (A). Also, 80 mol% or less is mentioned, preferably 75 mol% or less, more preferably 70 mol% or less, even more preferably 65 mol% or less, and even more preferably 60 mol% or less. Specifically, 5 to 80 mol% is mentioned, preferably 5 to 75 mol%, more preferably 10 to 70 mol%, even more preferably 10 to 65 mol%, and even more preferably 10 to 60 mol%.

[0444] When resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), the total content of these is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total structural units of resin (A). Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, the range is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, even more preferably 20 to 80 mol%, even more preferably 20 to 75 mol%, even more preferably 20 to 70 mol%, even more preferably 20 to 65 mol%, and even more preferably 20 to 60 mol%.

[0445] Examples of structural units having a base (2) in structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)").

[0446] [ka]

[0447] [In equations (a1-4), all signs have the same meanings as described above.] R a1 This is R such as equation (a1-0). a01 Examples similar to those exemplified elsewhere can be given. R a17 The halogen atoms and C1-C6 alkyl groups that may have halogen atoms are R such as formula (a1-0). a01 Examples similar to those exemplified elsewhere can be given.

[0448] Ra1 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. R a17 Examples of alkoxy groups in this compound include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a carbon-1 to carbon-3 alkoxy group, even more preferably a methoxy or ethoxy group, and even more preferably a methoxy group.

[0449] R a17 Examples of alkoxyalkyl groups in this context include methoxymethyl group, ethoxyethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxymethyl group, and tert-butoxymethyl group. The alkoxyalkyl group is preferably a C2-C8 alkoxyalkyl group, more preferably a C2-C4 alkoxyalkyl group, even more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.

[0450] R a17 Examples of alkoxyalkoxy groups in this context include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, more preferably one having 2 to 4 carbon atoms, and even more preferably one having methoxyethoxy or ethoxyethoxy.

[0451] R a17 Examples of alkylcarbonyl groups in this compound include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 4 carbon atoms, more preferably one having 2 to 3 carbon atoms, and even more preferably one having acetyl.

[0452] R a17 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms, more preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and even more preferably an acetyloxy group.

[0453] R a17 The group is preferably a halogen atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl group which may have a halogen atom, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0454] A a11 Examples of alkanediyl groups include linear groups such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl. Examples of branched alkanediyl groups include symmetric alkanediyl groups, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, heptane-1,6-diyl group, octane-1,7-diyl group, nonane-1,8-diyl group, decane-1,9-diyl group, and undecane-1,10-diyl group. The number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 or 2.

[0455] R a18 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl groups. A a11 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a18 If a carbon atom is replaced by a hyphen, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the alkanediyl group.

[0456] A a11 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a18 Examples of groups that can be replaced by - include hydroxyl groups, carboxyl groups, carbonyl groups, oxy groups, amino groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylamino groups, peptide groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, and alkanediylamino groups. These replaced groups are similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0457] For example, A a11 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a18 The bases that have been replaced by - include *-O-, *-CO-O-, *-O-CO-, and *-CO-OA. a12 -CO-O-, *-O-CO-A a12 -O-, *-OA a12 -CO-O-, *-CO-OA a12 -O-CO-, *-O-CO-A a12 -O-CO-, *-CO-NR a18 - are some examples. In particular, *-CO-O- and *-CO-OA a12 -CO-O-, *-OA a12 -CO-O- or *-CO-NR a18 - is preferable. Here, A a12 * represents an alkanediyl group with 1 to 8 carbon atoms, and * represents Ra1 This represents the bonding site with the carbon atom to which it is bonded. a12 The alkanediyl group is, within the limits allowed by the upper limit of the number of carbon atoms, A a11 Similar alkanediyl groups can be cited.

[0458] A a11 These are single bonds, *-CO-O- or *-CO-OA a12 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0459] na1 is preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, and even more preferably 1 or 2. na11 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0460] mc is preferably 0 or 1. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups that combine these.

[0461] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Alicyclic hydrocarbon groups may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site).

[0462] [ka]

[0463] Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, phenanthryl groups, and other aryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. In particular, R a36 Examples 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, or groups formed by combining these.

[0464] R a35 and R a36 Examples of divalent heterocyclic groups with 3 to 20 carbon atoms that are formed when these atoms bond with each other and together with the -CO- groups they bond to include the following groups: * represents the bonding site, and one of them is R a34 This is the junction site.

[0465] [ka]

[0466] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, this is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.

[0467] Ra36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination thereof, and more 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. a36 The alkyl group and alicyclic hydrocarbon group in R are preferably unsubstituted. a36 In this context, the aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0468] -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 It is removed upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxyl group or a carboxyl group.

[0469] -X a1 -OC(R a34 )(R a35 )-OR a36 In the case of a benzene ring, A a11 The bond may be at the orthogonal, metagonal, or paragonal position relative to the bond site. In particular, it is preferable that at least one bond is at the orthogonal or paragonal position, and more preferably at the paragonal position. In the case of a naphthalene ring, A a11 If the bond position is at position 1, it can bond to any of positions 2 through 8, A a11 If the bond position is at position 2, it may bond to position 1 or any of positions 3 through 8. In particular, A a11 If the bonding position is at position 1, it is preferable that at least one bond is at positions 3 to 6, and more preferably at position 3 or 4. a11 If the bonding position is at position 2, it is preferable that the bond is at positions 4 through 7, and more preferably at position 5 or 6.

[0470] Examples of structural units (a1-4) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204646. Preferably, structural units represented by formulas (a1-4-1) to (a1-4-42) and R in structural unit (a1-4). a1 Examples of structural units in which the hydrogen atom corresponding to is replaced by a halogen atom, a haloalkyl group, or an alkyl group are given, and more preferably, structural units represented by formulas (a1-4-1) to (a1-4-5), (a1-4-10), (a1-4-13), (a1-4-14), (a1-4-19), and (a1-4-20), respectively.

[0471] [ka]

[0472] If resin (A) contains structural units (a1-4), the content of these units is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total amount of all structural units of resin (A). Also, it is preferably 95 mol% or less, more preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, even more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

[0473] Structural units derived from (meth)acrylic monomers having group (2) include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)").

[0474] [ka]

[0475] [In equations (a1-5), all signs have the same meaning as described above.] R in equation (a1-5) a8 The halogen atom and the alkyl group which may have a halogen atom are R of formula (a1-0). a01 Examples of halogen atoms and alkyl groups that may have halogen atoms are similar to those exemplified.

[0476] R a8 The preferred element is a hydrogen atom, a methyl group, or a trifluoromethyl group. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-.

[0477] s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0478] Examples of structural units (a1-5) include monomer-derived structural units described in Japanese Patent Publication No. 2010-61117. Among these, structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or (a1-5-2) are more preferred.

[0479] [ka]

[0480] If resin (A) contains structural units (a1-5), the content of these units is preferably 1 mol% or more, more preferably 2 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 20 mol% or more, and even more preferably 25 mol% or more, relative to the total structural units of resin (A). Alternatively, it may be 80 mol% or less, preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 45 mol% or less, even more preferably 40 mol% or less, and even more preferably 30 mol% or less. Specifically, 1 to 50 mol% is preferred, 3 to 45 mol% is more preferred, 5 to 40 mol% is even more preferred, and 5 to 30 mol% is even more preferred.

[0481] Examples of structural units (a1) having a base (1) include the structural unit represented by formula (a1-6) (hereinafter sometimes referred to as "structural unit (a1-6)").

[0482] [ka]

[0483] [In equations (a1-6), all signs have the same meanings as described above.] R in equation (a1-6) a61 The halogen atom and the alkyl group which may have a halogen atom are R of formula (a1-0). a01 Examples of halogen atoms and alkyl groups that may have halogen atoms are similar to those exemplified.

[0484] R a61 The preferred element is a hydrogen atom, a methyl group, or a trifluoromethyl group. R a62 , R a63 , R a64 and R a65Examples of alkyl groups in this context include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. C1-C4 alkyl groups are preferred, C1-C3 alkyl groups are more preferred, and methyl or ethyl groups are even more preferred.

[0485] R a62 , R a63 and R a64 Examples of cyclic hydrocarbon groups in this context include alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, and norbornyl groups. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16, and more preferably 3 to 12.

[0486] Examples of aromatic hydrocarbon groups include phenylene groups and naphthylene groups. Substituents that the cyclic hydrocarbon group may have include halogen atoms, hydroxyl groups, C1-C6 alkyl groups, C1-C6 alkoxy groups, C2-C12 alkoxyalkyl groups, C2-C12 alkoxyalkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyloxy groups, acryloyloxy groups, or methacryloyloxy groups.

[0487] R a62 and R a63 Examples of rings formed by the bonding of these elements include adamantane rings, cyclopentane rings, or cyclohexane rings. Specifically, R a62 and R a63 -C(R) when they bond to each other to form a ring a62 )(R a63 )(R a64 Examples of such groups include the following: * indicates a bonding site with an oxygen atom. The number of carbon atoms in the ring is preferably 3 to 16, and more preferably 3 to 12.

[0488] [ka]

[0489] L a61 and L a62 Examples of C1-C4 alkanediyl groups in this compound include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0490] L a61 and L a62 Preferably, each of these is independently a methylene group or an ethylene group. X a61 Preferably, it is a single bond or -CO-O-*, and more preferably a single bond.

[0491] X a62 Preferably, a single bond or *-OL a61 - and more preferably, a single bond. Examples of aromatic hydrocarbon groups with 6 to 20 carbon atoms in Ar include phenylene group, o-methylphenylene group, m-methylphenylene group, p-methylphenylene group, p-ethylphenylene group, p-tert-butylphenylene group, 1-naphthylene group, 2-naphthylene group, 1-antrylene group, 9-antrylene group, biphenylene group, 1-phenanthrylene group, and 2-phenanthrylene group.

[0492] Substituents that an aromatic hydrocarbon group may have include halogen atoms, hydroxyl groups, C1-C6 alkyl groups, C1-C6 alkoxy groups, C2-C12 alkoxyalkyl groups, C2-C12 alkoxyalkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyloxy groups, acryloyloxy groups, or methacryloyloxy groups.

[0493] Examples of halogen atoms include fluorine, iodine, chlorine, and bromine atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. C1-C4 alkyl groups are preferred, methyl or ethyl groups are more preferred, and methyl groups are even more preferred.

[0494] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group.

[0495] Examples of alkoxyalkyl groups include methoxymethyl group, ethoxyethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxymethyl group, and tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.

[0496] Examples of alkoxyalkoxy groups include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, with methoxyethoxy or ethoxyethoxy being more preferred.

[0497] Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. A alkylcarbonyl group having 2 to 3 carbon atoms is preferred, with the acetyl group being more preferred.

[0498] Examples of alkylcarbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably one having 2 to 3 carbon atoms, and more preferably an acetyloxy group.

[0499] Preferred substituents are halogen atoms, hydroxyl groups, C1-C4 alkyl groups, C1-C4 alkoxy groups, or C2-C8 alkoxyalkoxy groups; more preferably fluorine atoms, iodine atoms, hydroxyl groups, methyl groups, methoxy groups, ethoxy groups, ethoxyethoxy groups, or ethoxymethoxy groups; and even more preferably fluorine atoms, iodine atoms, hydroxyl groups, methyl groups, methoxy groups, or ethoxyethoxy groups.

[0500] Ar is preferably a phenylene group which may have a substituent, and more preferably a phenylene group which may have a hydroxyl group. Examples of structural units (a1-6) include those represented by formulas (a1-6-1) to (a1-6-44), with those represented by formulas (a1-6-1) to (a1-6-9) and (a1-6-37) to (a1-6-44) being preferred, those represented by formulas (a1-6-1), (a1-6-2), (a1-6-4), (a1-6-5), (a1-6-7), (a1-6-8), and (a1-6-37) to (a1-6-44) being more preferred, and those represented by formulas (a1-6-7), (a1-6-8), and (a1-6-37) to (a1-6-44) being even more preferred. In the following structural units, R a61 A structural unit in which the hydrogen atom corresponding to is replaced by a methyl group, etc., R a61 Structural units in which the corresponding methyl group is replaced by a hydrogen atom or the like can also be listed as structural units (a1-6), respectively.

[0501] [ka]

[0502] If resin (A) contains structural units (a1-6), the content of these units is preferably 3 mol% or more, more preferably 5 mol% or more, more preferably 7 mol% or more, even more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to the total structural units of resin (A). Also, it is preferably 80 mol% or less, more preferably 75 mol% or less, more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, even more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol%.

[0503] In addition, the following structural units (a1) can also be listed.

[0504] [ka]

[0505] When resin (A) contains structural units represented by formulas (a1-7-1) to (a1-7-7), the content of these units is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total structural units of resin (A). Also, a content of 95 mol% or less is preferred, preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 60 mol% or less. Specifically, 10 to 95 mol% is preferred, 15 to 90 mol% is more preferred, 20 to 85 mol% is even more preferred, 20 to 70 mol% is even more preferred, and 20 to 60 mol% is particularly preferred.

[0506] In addition, the following structural units (a1) can also be listed.

[0507] [ka]

[0508] When resin (A) contains structural units represented by formulas (a1-8-1) to (a1-8-3), the content of these units is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, relative to the total structural units of resin (A). Also, a content of 95 mol% or less is preferred, preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 60 mol% or less. Specifically, 10 to 60 mol% is preferred, 15 to 55 mol% is more preferred, 20 to 50 mol% is even more preferred, 20 to 45 mol% is even more preferred, and 20 to 40 mol% is particularly preferred.

[0509] <Structural unit (s)> Structural units (s) are derived from monomers that do not have acid-unstable groups (hereinafter sometimes referred to as "monomer(s)"). Monomers known in the resist field that do not have acid-unstable groups can be used to derive structural units (s).

[0510] The structural units (s) preferably have a hydroxyl group, a carboxyl group, or a lactone ring. If a resin containing a structural unit having a hydroxyl group or a carboxyl group and not having an acid-unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and not having an acid-unstable group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved. In addition to the structural units described above, structural units (s) may also include structural units having a halogen atom (hereinafter sometimes referred to as "structural unit (a4)"), structural units having a non-leaved hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)"), structural units having a slutone structure (hereinafter sometimes referred to as "structural unit (a6)"), structural units that decompose upon exposure to generate acid (hereinafter sometimes referred to as "structural unit (a7)"), or other structural units well known in the art.

[0511] <Structural Unit (a2)> Structural unit (a2) is a structural unit represented by formula (a2) and has an alcoholic hydroxyl group, a phenolic hydroxyl group, or a carboxyl group.

[0512] [ka]

[0513] [In formula (a2), R a2 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom.

[0514] A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a28 - may be used instead.

[0515] R a28 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. La21 -CH2- represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms, and the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group is -O-, -CO-, -S-, -SO-, -NR a28 -It may be replaced with -SO2-.

[0516] L a22 - represents a chain hydrocarbon group having 1 to 12 carbon atoms, which may have single bonds or fluorine atoms, and the -CH2- contained in the chain hydrocarbon group is -O-, -CO-, -S-, -SO-, -NR a28 -It may be replaced with -SO2-.

[0517] na2 represents an integer between 1 and 5. When na2 is 2 or greater, multiple L a22 They may be the same or different from each other. R in equation (a2) a2 The halogen atoms and alkyl groups that may have halogen atoms in the formula are R of formulas (a1-0) to (a1-2). a01 , R a4 and R a5 Examples similar to those exemplified earlier can be given.

[0518] R a2 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. A a21Examples of alkanediyl groups include linear groups such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl. Examples of branched alkanediyl groups include symmetric alkanediyl groups, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, heptane-1,6-diyl group, octane-1,7-diyl group, nonane-1,8-diyl group, decane-1,9-diyl group, and undecane-1,10-diyl group. The number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 or 2.

[0519] R a28 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl groups. A a21 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a28 If a carbon atom is replaced by a hyphen, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the alkanediyl group.

[0520] A a21 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a28Examples of groups that can be replaced by - include hydroxyl groups, carboxyl groups, carbonyl groups, oxy groups, amino groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylamino groups, peptide groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, and alkanediylamino groups. These replaced groups are similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0521] Among them, A a21 The -CH2- contained in the alkanediyl group is -O-, -CO-, or -NR a28 The bases that have been replaced by - include *-O-, *-CO-O-, *-O-CO-, and *-CO-OA. a22 -CO-O-, *-O-CO-A a22 -O-, *-OA a22 -CO-O-, *-CO-OA a22 -O-CO-, *-O-CO-A a22 -O-CO-, *-CO-NR a28 - are some examples. In particular, *-CO-O- and *-CO-OA a22 -CO-O-, *-OA a22 -CO-O- or *-CO-NR a28 - is preferable. Here, A a22 * represents an alkanediyl group with 1 to 8 carbon atoms, and * represents R a2 This represents the bonding site with the carbon atom to which it is bonded. a22 The alkanediyl group is, within the limits allowed by the upper limit of the number of carbon atoms, A a21 Similar alkanediyl groups can be cited.

[0522] A a21 These are single bonds, *-CO-O- or *-CO-OA a22 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0523] La21 The hydrocarbon group in this context is a (Na2+1) valent hydrocarbon group, and includes linear or branched chain hydrocarbon groups, monocyclic or polycyclic (including spiro rings, fused rings, or bridged rings) alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and other cyclic hydrocarbon groups. It may also be a group formed by combining two or more of these groups (for example, a hydrocarbon group formed from an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group).

[0524] L a21 Examples of chain-like hydrocarbon groups include 2- to 6-valent chain-like hydrocarbon groups such as alkanediyl groups, alkanetriyl groups, alkanetetrayl groups, alkampentile groups, and alkanehexyl groups.

[0525] Examples of alkanediyl groups include A a21 Similar alkanediyl groups can be cited. Examples of alkanetriyl groups include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octantriyl, nonanetriyl, decantriyl, undecanetriyl, dodecanetriyl, tridecanetriyl, tetradecanetriyl, pentadecanetriyl, hexadecantriyl, and heptadecantriyl.

[0526] Examples of alkanetetrayl groups include methanetetrayl, ethanetetrayl, propanetetrayl, butanetetrayl, pentanetetrayl, hexanetetrayl, heptanetetrayl, octanetetrayl, nonanetetrayl, decanetetrayl, undecanetetrayl, dodecanetetrayl, tridecanetetrayl, tetradecanetetrayl, pentadecanetetrayl, hexadecanetetrayl, and heptadecanetetrayl.

[0527] Examples of alkanpentile groups include ethanepentile, propanepentile, butanepentile, pentanepentile, and hexanepentile groups. Examples of alkane hexyl groups include ethane hexyl group, propane hexyl group, butane hexyl group, pentane hexyl group, and hexane hexyl group.

[0528] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 9, even more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 5, and particularly preferably 1 to 4.

[0529] L a21 Examples of monocyclic and polycyclic alicyclic hydrocarbon groups in this context include the following alicyclic hydrocarbon groups. The bonding site can be at any position.

[0530] [ka]

[0531] Examples include cycloalkanediyl groups, cycloalkanetriyl groups, cycloalkanetetrayl groups, cycloalkampentile groups, and cycloalkanehexyl groups, which are alicyclic hydrocarbon groups with a valency of 2 to 6.

[0532] Specifically, monocyclic alicyclic hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclodecanetriyl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclodecanetetrayl group, and monocyclic alicyclic hydrocarbon groups. Examples of polycyclic alicyclic hydrocarbon groups include norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, decahydronaphthalenediyl group, bicyclo[3.3.0]octanediyl group, norbornanetriyl group, adamantanetriyl group, decahydronaphthalenetriyl group, bicyclo[3.3.0]octanedriyl group, norbornanetetrayl group, adamantanetetrayl group, decahydronaphthalenetetrayl group, and bicyclo[3.3.0]octanetetrayl group.

[0533] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 18, even more preferably 3 to 16, even more preferably 3 to 12, even more preferably 6 to 12, and particularly preferably 6 to 10.

[0534] L a21 Examples of aromatic hydrocarbon groups in this context include divalent to hexavalent aromatic hydrocarbon groups such as arylene groups, arenetriyl groups, arenetetrayl groups, arenepentile groups, and arenehexile groups.

[0535] Specifically, examples include phenylene group, naphthylene group, anthreylene group, biphenylene group, phenanthrylene group, benzenetriyl group, naphthalentriyl group, anthracenatelyyl group, biphenylentriyl group, phenanthrentriyl group, benzenetetrayl group, naphthalenetetrayl group, anthracenetetrayl group, biphenylenetetrayl group, phenanthrenetetrayl group, and the like.

[0536] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, even more preferably 6 to 14, even more preferably 6 to 12, and even more preferably 6 to 10.

[0537] Examples of groups formed by combining two or more types include groups formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group, groups formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group, groups formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and groups formed by combining an alicyclic hydrocarbon group, a chain hydrocarbon group and an aromatic hydrocarbon group. In the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Also, any of the groups may be A a21 and L a22 They may be bound together.

[0538] The -CH2- contained in the hydrocarbon group is -O-, -S-, -SO-, -SO2-, -NR a28 Groups replaced by - or -CO- include hydroxyl groups, carboxyl groups, thiol groups, amino groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylamino groups, alkylpeptide groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, alkoxyalkoxy groups, oxy groups, carbonyl groups, thio groups, sulfonyl groups, peptide groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediyloxycarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, alkanediylamino groups, alkanediylpeptide groups, cycloalkoxy groups, cycloalkylalkoxy groups, aromatic hydrocarbon group-carbonyloxy groups, aromatic hydrocarbon group-carbonyl groups, aromatic hydrocarbon group-oxy groups, and groups combining two or more of these groups. Groups in which one or more hydrogen atoms of these groups are replaced at the bonding site are also included. These substituted groups may be similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0539] Furthermore, the -CH2- groups contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining them are -O-, -S-, -CO-, -SO-, -NR a28Groups replaced with - or -SO2- include those similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0540] L a21 The hydrocarbon group in may have one or more substituents. Examples of substituents include halogen atoms, C1-C12 haloalkyl groups, C1-C16 alkyl groups (where the -CH2- group is replaced by -O- or -CO-), acryloyloxy groups, or methacryloyloxy groups.

[0541] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. L a21 The hydrocarbon group in the compound can substantially have substituents such as haloalkyl groups by having a halogen atom as a substituent. Examples of haloalkyl groups include alkyl fluorides, alkyl chlorides, alkyl bromides, alkyl iodides, etc., and examples include chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc. Haloalkyl groups having 1 to 4 carbon atoms are preferred, and haloalkyl groups having 1 to 3 carbon atoms are more preferred. The number of carbon atoms in the haloalkyl group is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0542] L a21 The hydrocarbon group contains a branched structure, L a21The alkyl group may substantially have substituents such as alkyl groups. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. The number of carbon atoms in the alkyl group may be 1 to 12, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0543] L a21 The -CH2- contained in the hydrocarbon group is -O-, -S-, -CO-, -SO-, -NR a28 - or -SO2- replaced by a group, L a21 These groups may substantially have substituents such as hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, thiol groups, alkylthio groups, alkylsulfonyl groups, alkoxyalkyl groups, alkoxyalkoxy groups, alkoxycarbonyloxy groups, amino groups, alkylamino groups, alkylpeptide groups, acryloyloxy groups, and methacryloyloxy groups. Examples of such groups are similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0544] L a21The substituents that the hydrocarbon group in the hydrocarbon group may have are preferably a halogen atom, a C1-C8 haloalkyl group or a C1-C12 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), more preferably a halogen atom, a C1-C6 haloalkyl group or a C1-C10 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), even more preferably a halogen atom, a C1-C4 haloalkyl group, a C1-C6 alkyl group, a hydroxyl group, a C1-C4 alkoxy group or a C2-C8 alkoxyalkoxy group, even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a hydroxyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a hydroxyl group, a methoxy group or an ethoxyethoxy group.

[0545] Also, L a21 When the alkanediyl group is replaced by -O- or -CO-, for example, *-L a23 -X a21 -(L a23 This represents an alkanediyl group with 1 to 8 carbon atoms, X a21 represents -O-, -O-CO-, -CO-O-, or -O-CO-O-, and * represents A a21 It is also preferable that it represents the bonding site with ( ).

[0546] L a21 This includes single bonds, C1-C12 chain hydrocarbon groups which may have substituents (however, the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), and C3-C20 cyclic hydrocarbon groups which may have substituents (however, the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, -NR a28A group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms that may have substituents and a cyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents (however, the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -SO-, -SO2-, -NR a28 Preferably, the -CH2- may be replaced by -O- or -CO-. A chain hydrocarbon group having 1 to 10 carbon atoms that may have substituents (however, the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), or a cyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents (however, the -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR a28 A group formed by combining a chain hydrocarbon group having 1 to 6 carbon atoms that may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents (however, the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -SO-, -SO2-, -NR a28 It is more preferable that it be replaced with - or -CO-.

[0547] L a22Examples of linear alkane diyl groups with 1 to 12 carbon atoms include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl. Examples include branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-dimethylpropane-1,3-diyl group, pentane-2,4-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, and even more preferably 1 to 4.

[0548] The -CH2- group in the chain hydrocarbon group can be -O-, -S-, -CO-, -SO-, or -NR. a28 Examples of groups that replace - or -SO2- include those similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0549] L a22 The fluorine atoms present may be one or two or more. na2 is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3.

[0550] L a21 However, as structural units (a2) in the case of single bonds or chain hydrocarbon groups, for example, the following structural units can be cited. Of the following structural units, R a2 Structural units in which the corresponding methyl group is replaced by a hydrogen atom or the like are also suitable structural units for structural unit (a2), similar to the structural units described below.

[0551] [ka]

[0552] When manufacturing a resist pattern from the resist composition of the present invention, if a high-energy beam such as a KrF excimer laser (248 nm), electron beam, or EUV (ultra-ultraviolet light) is used as the exposure light source, a structural unit (a2) having a phenolic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-A) described later. Furthermore, if an ArF excimer laser (193 nm) or the like is used, a structural unit (a2) having an alcoholic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-C) described later. The structural unit (a2) may consist of one type alone, or it may consist of two or more types.

[0553] In the structural unit (a2), L a21 In cases where is a cyclic hydrocarbon group, an example of a structural unit having a phenolic hydroxyl group or a carboxyl group is the structural unit represented by formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)").

[0554] [ka]

[0555] [In equation (a2-A), all signs have the same meaning as described above.] R a2 and A a21 These are the same types of bases as those exemplified in equation (a2). R a27 Examples of halogen atoms include fluorine, chlorine, iodine, and bromine atoms.

[0556] R a27Examples of C1-C6 alkyl groups that may have a halogen atom include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, chloromethyl, bromomethyl, and iodomethyl groups. The number of carbon atoms in the alkyl group is preferably 1-4, more preferably 1-3, even more preferably methyl or ethyl, and even more preferably methyl.

[0557] R a27 Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 4, more preferably 1 to 3. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, even more preferably a methoxy or ethoxy group, and even more preferably a methoxy group.

[0558] R a27 Examples of alkoxyalkyl groups include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a C2-C8 alkoxyalkyl group, more preferably a C2-C4 alkoxyalkyl group, even more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group.

[0559] R a27Examples of alkoxyalkoxy groups include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, more preferably one having 2 to 4 carbon atoms, and even more preferably one having methoxyethoxy or ethoxyethoxy.

[0560] R a27 Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 3 carbon atoms, with the acetyl group being more preferred.

[0561] R a27 Examples of alkylcarbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.

[0562] R a27 The group is preferably a halogen atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl group which may have a halogen atom, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0563] nA2 is preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, and even more preferably 1 or 2. na21 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0564] mc is preferably 0 or 1. -Xa2 -OH is A in the case of a benzene ring. a21 The bond may be at the ortho, meta, or para position relative to the bond site. In particular, it is preferable that at least one bond is at the meta or para position, and more preferably at the meta position. In the case of a naphthalene ring, A a21 If the bond position is at position 1, it can bond to any of positions 2 through 8, A a21 If the bond position is at position 2, it may bond to position 1 or any of positions 3 through 8. In particular, A a21 If the bonding position is at position 1, it is preferable that at least one bond is at positions 3 to 6, and more preferably at position 3 or 4. a21 If the bonding position is at position 2, it is preferable that the bond is at positions 4 through 7, and more preferably at position 5 or 6.

[0565] Examples of structural units (a2-A) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204634 and Japanese Patent Publication No. 2012-12577. As for the structural unit (a2-A), the structural unit is represented by formulas (a2-2-1) to (a2-2-32), formula (a2-3-1) to (a2-3-24), and in the structural unit represented by formulas (a2-2-1) to (a2-2-32), formula (a2-3-1) to (a2-3-24), the R in the structural unit (a2-A) a2 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include these units.

[0566] [ka]

[0567] [ka]

[0568] When the resin (A) contains structural units (a2-A), the content of structural units (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more, relative to the total structural units. Furthermore, it is preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 65 mol% or less, even more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 45 mol% or less, and even more preferably 40 mol% or less. Specifically, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%.

[0569] The structural unit (a2-A) is derived from the compound represented by formula (a2-A') (hereinafter sometimes referred to as "compound (a2-A)").

[0570] [ka]

[0571] [In equation (a2-A'), all signs have the same meaning as above.] Compound (a2-A′) may be a commercially available product or may be manufactured by a known method.

[0572] The structural unit (a2-A) can be incorporated into resin (A) by polymerizing compound (a2-A'). Alternatively, it can be incorporated into resin (A) by polymerizing using structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Furthermore, the structural unit (a2-A) can be incorporated into resin (A) by polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

[0573] In the structural unit (a2), L a21When is a cyclic hydrocarbon group, structural units having an alcoholic hydroxyl group or a carboxyl group include the structural unit represented by formula (a2-B) (hereinafter sometimes referred to as "structural unit (a2-B)"), the structural unit represented by formula (a2-C) (hereinafter sometimes referred to as "structural unit (a2-C)"), and the structural unit represented by formula (a2-D) (hereinafter sometimes referred to as "structural unit (a2-D)").

[0574] [ka]

[0575] [In formula (a2-B) and formula (a2-C), R a2 This has the same meaning as equation (a2). R a27 This has the same meaning as equation (a²-A).

[0576] L a25 is -O- or *-O-(CH2) k2 -CO-O- represents a bond, and k2 represents an integer from 1 to 7. * represents the bonding site with -CO-. X a2 This represents a single bond or -CO-.

[0577] R a25 and R a26 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. nB2 represents an integer between 1 and 5. When nB2 is 2 or greater, multiple X a2 They may be the same or different from one another.

[0578] nB22 represents an integer between 0 and 8. When nB22 is 2 or greater, multiple R a27 They may be the same or different from one another. nC22 represents an integer between 0 and 10. When nC22 is 2 or greater, multiple R a27 They may be the same or different from each other. L a25Preferably, -O- or -O-(CH2) f1 The result is -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-.

[0579] R a2 The group is preferably a methyl group. X a2 The bond is preferably a single bond. R a25 Preferably, it is a hydrogen atom.

[0580] R a26 This is preferably a hydrogen atom or a hydroxyl group. R a27 The group is preferably a halogen atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl group which may have a halogen atom, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0581] nB2 is preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, and even more preferably 1 or 2. nB22 is preferably an integer from 0 to 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0582] nC22 is preferably an integer from 0 to 6, more preferably an integer from 0 to 3, even more preferably 0, 1 or 2, and even more preferably 0 or 1.

[0583] Examples of structural units (a2-B) and structural units (a2-C) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646, the following structural units, and R in the following structural units. a2Examples of structural units include those in which the corresponding methyl group or hydrogen atom is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. Among these, structural units represented by any of the formulas (a2-B-1) to (a2-B-5) and (a2-C-1) to (a2-C-9) are preferred.

[0584] [ka]

[0585] When resin (A) contains structural unit (a2-B) or structural unit (a2-C), the content is preferably 1 mol% or more, and more preferably 2 mol% or more, relative to the total structural units of resin (A). Also, it is preferably 45 mol% or less, more preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 20 mol% or less, and even more preferably 10 mol% or less. Specifically, it is preferably 1 to 45 mol%, more preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%.

[0586] [ka]

[0587] [In formula (a2-D), R a2 and A a21 These expressions have the same meaning as equation (a2). R a27 This has the same meaning as equation (a²-A).

[0588] R a21 and R a22 Each of these independently represents a fluorinated alkyl group having 1 to 4 carbon atoms. L a24 This represents a single bond or an alkanediyl group having 1 to 3 carbon atoms, and the alkanediyl group may be substituted with a fluorine atom.

[0589] nD2 represents an integer between 1 and 5. When nD2 is 2 or greater, the bases within the parentheses may be the same or different. nD22 represents an integer between 0 and 4. When nD22 is 2 or greater, multiple R a27 They may be the same or different from one another.

[0590] However, 1 ≤ nD² + nD²² ≤ 5. R a21 and R a22 Examples of alkyl fluoride groups include, independently, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, and 4,4,4-trifluorobutyl group.

[0591] R a21 and R a22 A trifluoromethyl group is preferred as the component. L a24 Examples of alkanediyl groups include methylene group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group.

[0592] L a24 A single bond or a methylene group is preferred. R a27 The group is preferably a halogen atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl group which may have a halogen atom, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0593] nD2 is preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, even more preferably 1 or 2, and even more preferably 1. Furthermore, it is preferable that nD2 is 1 and the group in parentheses is bonded to the para position.

[0594] nD22 is preferably an integer between 0 and 3, more preferably an integer between 0 and 2, even more preferably 0 or 1, and even more preferably 0. The structural unit (a2-D) is more preferably a structural unit represented by the following formula (a2-D1) (hereinafter sometimes referred to as "structural unit (a2-D1)").

[0595] [ka]

[0596] [In formula (a2-D1), R a2 , A a21 , R a27 nD2 and nD22 have the same meaning as equation (a2-D). In equation (a2-D1), R a2 This is preferably a hydrogen atom or a methyl group.

[0597] A a21 The bond is preferably a single bond. R a27 The group is preferably a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0598] nD22 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1. nD2 is preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, and even more preferably 1 or 2.

[0599] The following are examples of structural units (a2-D).

[0600] [ka]

[0601] In the structural units represented by equations (a2-D-1) to (a2-D-8), R a2 In structural units in which the hydrogen atom corresponding to is replaced by a methyl group, etc., and in structural units represented by formulas (a2-D-9) to (a2-D-16), R a2 Structural units in which the corresponding methyl group is replaced by a hydrogen atom or the like can also be given as specific examples of structural unit (a2-D). Among these, structural units represented by formulas (a2-D-1) to (a2-D-8) are preferred, structural units represented by formulas (a2-D-1) to (a2-D-4) are more preferred, and structural unit represented by formula (a2-D-1) is even more preferred.

[0602] If resin (A) contains structural units (a2-D), the content is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total structural units of resin (A). Furthermore, it is preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, even more preferably 10 to 70 mol%, and even more preferably 10 to 65 mol%.

[0603] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or it may be a fused ring of a monocyclic lactone ring and another ring. Preferably, it may be a γ-butyrolactone ring, an adamantane lactone ring, or a bridging ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

[0604] The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3) or formula (a3-4). It may contain one of these alone or two or more of them.

[0605] [Chemical formula]

[0606] [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 、L a5 及びL a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -CO-O- (where k3 represents an integer from 1 to 7).

[0607] L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O-.

[0608] L a8 及びL a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding site with the carbonyl group. R a18 、R a19 、R a20 及びR a24 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.

[0609] X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 及びRa23 and R a25 each independently represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0610] p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3.

[0611] w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, the plurality of Rs a21 , R a22 , R a23 and / or R a25 may be the same as or different from each other. R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in R, R, R and R include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group.

[0612] R a18 , R a19 , R a20 and R a24 Examples of the halogen atom and the alkyl group which may have a halogen atom in R, R, R and R are the same as those exemplified by R, R and R of formula (a1-0) to formula (a1-2). a01 , R a4 and R a5 and the like.

[0613] L a8 and L a9Examples of alkanediyl groups in this compound include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0614] L a4 ~L a6 Each is independently, preferably -O- or *-O-(CH2) k3 In -CO-O-, k3 is an integer from 1 to 4, more preferably -O- and *-O-CH2-CO-O-, and even more preferably an oxygen atom.

[0615] L a7 Preferably -O- or *-OL a8 It is -CO-O-, and more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. R a18 , R a19 , R a20 and R a24 Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group.

[0616] R a21 The group is preferably a methyl group. R a22 , R a23 and R a25 Each of these is independently preferably a carboxyl group, a cyano group, or a methyl group.

[0617] p1, q1, and r1 are each independently, preferably integers from 0 to 2, and more preferably 0 or 1. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1.

[0618] In particular, formula (a3-4)' is preferred over formula (a3-4).

[0619] [ka]

[0620] (In the formula, R a24 , L a7 (This expresses the same meaning as above.) Examples of structural units (a3) ​​include those derived from monomers described in Japanese Patent Publication No. 2010-204646, Japanese Patent Publication No. 2000-122294, and Japanese Patent Publication No. 2012-41274. Examples of structural units (a3) ​​include those represented by any of the formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and (a3-4-1) to (a3-4-12), and in the said structural units, R in formulas (a3-1) to (a3-4). a18 , R a19 , R a20 and R a24 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom is preferred.

[0621] [ka]

[0622] When resin (A) contains structural units (a3), the total content is 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total structural units of resin (A). Also, it is 70 mol% or less, preferably 65 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, and even more preferably 20 mol% or less. Specifically, it is 1 to 70 mol%, preferably 3 to 70 mol%, more preferably 3 to 65 mol%, even more preferably 5 to 65 mol%, even more preferably 5 to 60 mol%, and even more preferably 10 to 60 mol%.

[0623] Furthermore, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3), or structural unit (a3-4) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total structural units of resin (A). Also, it is preferably 60 mol% or less, more preferably 55 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, and even more preferably 20 mol% or less. Specifically, 1 to 60 mol% is preferred, 3 to 60 mol% is more preferred, 3 to 55 mol% is even more preferred, 5 to 55 mol% is even more preferred, 5 to 50 mol% is even more preferred, and 10 to 50 mol% is even more preferred.

[0624] <Structural Unit (a4)> The structural unit represented by formula (a4) is shown below.

[0625] [ka]

[0626] [In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents an aliphatic hydrocarbon group having a halogen atom with 1 to 48 carbon atoms, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-. R 42 Aliphatic hydrocarbon groups represented by include linear or branched chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these.

[0627] Examples of chain-type hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups, and branched alkyl groups such as isopropyl and isobutyl groups.

[0628] Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include monocyclic alicyclic hydrocarbon groups that are monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic hydrocarbon groups that are polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site).

[0629] [ka]

[0630] Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0631] Examples of alkanediyl groups include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The end of the branched alkanediyl group may be a methyl group.

[0632] R 42 Examples of halogen atoms contained in the aliphatic hydrocarbon group include fluorine, chlorine, bromine, or iodine atoms. R 42 Groups in which the -CH2- of the aliphatic hydrocarbon group contained in is replaced with -O- or -CO- include hydroxyl groups, carboxyl groups, carbonyl groups, oxy groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, cycloalkoxy groups, cycloalkylalkoxy groups, and groups formed by combining two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0633] As a structural unit (a4), R 42 However, it is preferable that it be an aliphatic hydrocarbon group having a fluorine atom, R 42 However, examples of structural units (a4) that are aliphatic hydrocarbon groups containing a fluorine atom include the structural unit represented by formula (a4-1) (hereinafter sometimes referred to as "structural unit (a4-1)"), the structural unit represented by formula (a4-2) (hereinafter sometimes referred to as "structural unit (a4-2)"), the structural unit represented by formula (a4-3) (hereinafter sometimes referred to as "structural unit (a4-3)"), and the structural unit represented by formula (a4-A) (hereinafter sometimes referred to as "structural unit (a4-A)").

[0634] The structural unit represented by formula (a4-1) is the structural unit shown below.

[0635] [ka]

[0636] [In formula (a4-1), R 41 represents a hydrogen atom or a methyl group. L 41 This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.

[0637] L 42f This represents an alkanediyl group with 1 to 8 carbon atoms containing a fluorine atom, or a cycloalkanediyl group with 3 to 12 carbon atoms containing a fluorine atom. R 42f This represents a hydrogen atom or a fluorine atom. L 41 Examples of alkanediyl groups in this context include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group. The end of the branched alkanediyl group may be a methyl group.

[0638] L 42f Examples of fluorine-containing alkanediyl groups include fluorine-containing methylene groups, fluorine-containing ethylene groups, fluorine-containing propane-1,3-diyl groups, fluorine-containing butane-1,4-diyl groups, fluorine-containing pentane-1,5-diyl groups, fluorine-containing hexane-1,6-diyl groups, fluorine-containing heptane-1,7-diyl groups, fluorine-containing octane-1,8-diyl groups, and other linear alkanediyl groups containing fluorine atoms; Examples of branched alkanediyl groups having a fluorine atom include ethane-1,1-diyl group having a fluorine atom, propane-1,1-diyl group having a fluorine atom, propane-1,2-diyl group having a fluorine atom, propane-2,2-diyl group having a fluorine atom, pentane-2,4-diyl group having a fluorine atom, 2-methylpropane-1,3-diyl group having a fluorine atom, 2-methylpropane-1,2-diyl group having a fluorine atom, pentane-1,4-diyl group having a fluorine atom, and 2-methylbutane-1,4-diyl group having a fluorine atom. The ends of the branched alkanediyl groups may be methyl groups that may also have a fluorine atom.

[0639] L 42f Examples of cycloalkanediyl groups containing a fluorine atom include monocyclic cycloalkanediyl groups containing a fluorine atom, such as cyclobutane-1,3-diyl group containing a fluorine atom, cyclopentane-1,3-diyl group containing a fluorine atom, cyclohexane-1,4-diyl group containing a fluorine atom, cyclohexene-3,6-diyl group containing a fluorine atom, cycloheptane-1,4-diyl group containing a fluorine atom, and cyclooctane-1,5-diyl group containing a fluorine atom. Examples of polycyclic cycloalkanediyl groups containing a fluorine atom include norbornane-1,4-diyl group containing a fluorine atom, norbornane-2,5-diyl group containing a fluorine atom, 5-norbornene-2,3-diyl group containing a fluorine atom, adamantane-1,5-diyl group containing a fluorine atom, and adamantane-2,6-diyl group containing a fluorine atom.

[0640] L 42f The number of fluorine atoms in the alkanediyl group and cycloalkanediyl group having fluorine atoms in the above is 1 or more, and preferably 2 or more. L 42f In the above, the alkanediyl group and cycloalkanediyl group having a fluorine atom are preferably a perfluoroalkanediyl group and a perfluorocycloalkanediyl group, respectively.

[0641] L42f The perfluoroalkanediyl groups in this product include difluoromethylene, perfluoroethylene, perfluoroethylfluoromethylene, perfluoropropane-1,3-diyl, perfluoropropane-1,2-diyl, perfluoropropane-2,2-diyl, perfluorobutane-1,4-diyl, perfluorobutane-2,2-diyl, perfluorobutane-1,2-diyl, perfluoropentane-1,5-diyl, perfluoropentane-2,2-diyl, and perfluoropentane-3 Examples include 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, and perfluorooctane-4,4-diyl group.

[0642] L 42f Examples of perfluorocycloalkanediyl groups in this context include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, and perfluoroadamantanediyl group.

[0643] L 41 Preferably, it is a single bond or an alkanediyl group having 1 to 3 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and even more preferably a single bond or a methylene group.

[0644] L 42f The group is preferably a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and even more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0645] As the structural unit (a4-1), there are the following structural units and the methyl group corresponding to R in the structural unit (a4-1) in the following structural units 41 in which the methyl group is replaced by a hydrogen atom.

[0646]

Chemical formula

[0647] The structural unit represented by the formula (a4-2) is the following structural unit.

[0648]

Chemical formula

[0649] [In the formula (a4-2), R 41 represents a hydrogen atom or a methyl group. L 43f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-.

[0650] R 43f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-.

[0651] However, at least one of L 43f and R 43f has a fluorine atom, and the upper limit of the total carbon number of L 43f and R 43f is 21.] L 43f and R 43f Examples of the aliphatic hydrocarbon group in include linear or branched chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these. L 43f and R 43f Examples of the aliphatic hydrocarbon group in are the same as those of L43f and R 43f As long as the upper limit of the total number of carbon atoms allows, R in equation (a4) 42 Examples of aliphatic hydrocarbon groups include those similar to the aliphatic hydrocarbon groups exemplified.

[0652] L 43f The aliphatic hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms or a group represented by formula (L43f-1).

[0653] [ka]

[0654] [In formula (L43f-1), s represents either 0 or 1. L 45f and L 46f Each of these independently represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, which may contain a fluorine atom.

[0655] L 47f This represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, which may have a single bond or a fluorine atom. X 46f and X 47f These represent -O-, -CO-, -CO-O-, or -O-CO-, respectively, independently.

[0656] However, L 45f , L 46f , L 47f , X 46f and X 47f The total number of carbon atoms is 7 or less. * and ** are binding sites, where ** is -O-CO-R 43f This is the junction site. L in the group represented by formula (L43f-1) 45f , L 46f and L 47fExamples of divalent aliphatic hydrocarbon groups represented by include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic hydrocarbon groups, as well as divalent aliphatic hydrocarbon groups formed by combining alkanediyl groups and divalent alicyclic hydrocarbon groups. Specifically, examples include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, 1-methylpropane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, and 2-methylpropane-1,2-diyl groups.

[0657] s is preferably 0. The following are examples of groups represented by formula (L43f-1). In the following examples, * and ** represent the bonding site, and ** is -O-CO-R 43f This is the junction site.

[0658] [ka]

[0659] R 43f Preferably, it is an aliphatic hydrocarbon group having a fluorine atom. In this case, the structural unit represented by formula (a4-2) is, for example, the structural unit represented by formula (a4-2A) or (formula a4-2B).

[0660] [ka]

[0661] [In equations (a4-2A) and (a4-2B), R 41 and L 43f This represents the same thing as in equation (a4-2). R 43fA This represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom.

[0662] A 43frepresents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-.

[0663] X 43 **-O-CO- or **-CO-O-, where ** is A 43f This represents the connection point. R 43fB This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom.

[0664] However, in equation (a4-2A), L 43f and R 43fA The total number of carbon atoms is 21 or less, and in formula (a4-2B), L 43f , A 43f , X 43 and R 43fB The total number of carbon atoms is 21 or less, A 43f and R 43fB At least one of them has at least one fluorine atom. R 43fA The aliphatic hydrocarbon group is R, as long as the upper limit of the number of carbon atoms allows. 42 Examples include aliphatic hydrocarbon groups similar to those exemplified above.

[0665] R 43fA It is preferably an alkyl group having 1 to 13 fluorine atoms, a cycloalkyl group having 3 to 12 fluorine atoms, or a combination thereof, *-(CF2) n43f -R 42’ (* represents the bonding site with the carbonyl group. n43f represents an integer from 1 to 6. R 42’ represents a hydrogen atom or a fluorine atom. ) or a perfluorocycloalkyl group having 3 to 12 carbon atoms is more preferable.

[0666] A 43f and R 43fB The aliphatic hydrocarbon group is R in formula (a4), as long as the upper limit of the number of carbon atoms allows. 42Examples include aliphatic hydrocarbon groups similar to those exemplified above. A 43f It is preferably a divalent chain hydrocarbon group which may have a fluorine atom, a divalent alicyclic hydrocarbon group, or a group which is a combination thereof, more preferably a divalent chain hydrocarbon group which has a fluorine atom, and even more preferably an alkanediyl fluoride group which has 1 to 6 carbon atoms.

[0667] R 43fB The aliphatic hydrocarbon group which may have a fluorine atom is preferably a chain hydrocarbon group which may have a fluorine atom, an alicyclic hydrocarbon group which may have a fluorine atom, or a group which is a combination thereof, more preferably an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom, a cycloalkyl group having 3 to 12 carbon atoms which may have a fluorine atom, or a group which is a combination thereof, such as a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, or a 1,1,2,2,3,3,4,4-o Alkyl fluorides such as fluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, and perfluoroadamantylmethyl group are even more preferred.

[0668] In formula (a4-2B), *-A 43f -X 43 -R 43fB An example of a structure that the group represented by can take is shown below (* indicates the bonding site with the carbonyl group).

[0669] [ka]

[0670] The structural units represented by formula (a4-2A) are the structural units shown below and the R in the structural units represented by formula (a4-2A) in the structural units below. 41 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom.

[0671] [ka]

[0672] The structural units represented by formula (a4-2B) are the structural units shown below and the R in the structural units represented by formula (a4-2B) in the structural units below. 41 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom.

[0673] [ka]

[0674] Another example of a structural unit (a4) is the structural unit represented by formula (a4-3).

[0675] [ka]

[0676] [In formula (a4-3), R 41 represents a hydrogen atom or a methyl group. L 44f This represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may contain a fluorine atom, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-.

[0677] R 44fThis represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may contain a fluorine atom, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-. However, L 44f and R 44f At least one of them has a fluorine atom, L 44f and R 44f The upper limit for the total number of carbon atoms is 21. L 44f and R 44f Examples of aliphatic hydrocarbon groups in this context include linear or branched chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these. 44f and R 44f Examples of aliphatic hydrocarbon groups in L 44f and R 44f As long as the upper limit of the total number of carbon atoms allows, R in equation (a4) 42 Examples of aliphatic hydrocarbon groups include those similar to the aliphatic hydrocarbon groups exemplified.

[0678] L 44f It is preferably an alkanediyl group having 1 to 14 carbon atoms (the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), and -(CH2) j1 -,-(CH2) j2 -O-(CH2) j3 - or - (CH2) j4 -CO-O-(CH2) j5 It is more preferable that the group is represented by - (j1 to j5 each independently represent an integer from 1 to 6). It is also even more preferable that it is an alkanediyl group having 1 to 4 carbon atoms (one -CH2- in the alkanediyl group may be replaced by -O-, and one -CH2-CH2- in the alkanediyl group may be replaced by -CO-O- or -O-CO-).

[0679] R 44fPreferably, the group is an aliphatic hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom; more preferably, an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom; more preferably, an alkyl group having 3 to 10 carbon atoms and containing a fluorine atom; even more preferably, an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom; and even more preferably, an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom.

[0680] As a structural unit represented by formula (a4-3), for example, the following structural unit and the structural unit represented by the following formula, R in structural unit (a4-3) 41 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom.

[0681] [ka]

[0682] Another example of a structural unit (a4) is the structural unit represented by formula (a4-A).

[0683] [ka]

[0684] [In formula (a4-A), R 44 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom.

[0685] X 44 * represents a single bond or *-CO-O-. * represents R 44 This represents the bonding site with the carbon atom to which it is bonded. L 44 represents an aliphatic hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -SO2-, -SO-, or -CO-.

[0686] R 45 This represents an alkyl fluoride with 1 to 8 carbon atoms. R 46 L represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms, and the fluorinated alkyl group is L 44 It may combine with to form an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-.

[0687] mi represents an integer between 1 and 4. When mi is 2 or greater, the bases within the parentheses may be the same or different. R 44 The halogen atoms and alkyl groups that may have halogen atoms in the formula are R of formulas (a1-0) to (a1-2). a01 , R a4 and R a5 Examples similar to those exemplified earlier can be given.

[0688] R 44 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom, a methyl group or an ethyl group is even more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0689] L 44 Examples of aliphatic hydrocarbon groups in this context include chain hydrocarbon groups, monocyclic or polycyclic (including spiro rings, fused rings, or bridged rings) alicyclic hydrocarbon groups, and groups formed by combining two or more of these groups (for example, a hydrocarbon group formed from an alicyclic hydrocarbon group and a chain hydrocarbon group).

[0690] Examples of chain-like hydrocarbon groups include divalent to pentavalent chain-like hydrocarbon groups such as alkanediyl groups, alkanetriyl groups, alkanetetrayl groups, and alkampentile groups. Examples of alkanediyl groups include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group, and Examples of branched alkanediyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.

[0691] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 9, even more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 5, and particularly preferably 1 to 4.

[0692] Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include the following alicyclic hydrocarbon groups. The bonding site can be at any position.

[0693] [ka]

[0694] Examples include cycloalkanediyl groups, cycloalkanetriyl groups, cycloalkanetetrayl groups, cycloalkampentile groups, and other alicyclic hydrocarbon groups with a valency of 2 to 5. Specifically, monocyclic alicyclic hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group, and Examples include cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, decahydronaphthalenediyl group, bicyclo[3.3.0]octanediyl group, spirocyclohexane-1,2'-cyclopentane-diyl group, and spiroadamantane-2,3'-cyclopentane-diyl group, as well as polycyclic alicyclic hydrocarbon groups such as spiro rings having a norbornanediyl group or adamantanediyl group and a cycloalkanediyl group each linked by a spiro.

[0695] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12.

[0696] Examples of groups combining two or more types include groups combining alicyclic hydrocarbon groups and chain hydrocarbon groups. In the combination, two or more types of alicyclic hydrocarbon groups and chain hydrocarbon groups may be combined. Also, any of the groups may be X 44 They may be bound together.

[0697] Examples of groups combining alicyclic hydrocarbon groups and chain hydrocarbon groups include groups in which an alicyclic hydrocarbon group is bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-, etc.), groups in which a chain hydrocarbon group is bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-, etc.), groups in which an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-, etc.), and groups in which an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to an alicyclic hydrocarbon group. Examples include groups to which a hydrogenated group is bonded (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-, etc.), groups to which a chain hydrocarbon group is bonded with a chain hydrocarbon group and a chain hydrocarbon group and a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-, etc.), and groups to which a chain hydrocarbon group is bonded with a chain hydrocarbon group and a chain hydrocarbon group and a chain hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-, etc.).

[0698] * is X 44 This represents the connection point. Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. L 44 The -CH2- contained in the aliphatic hydrocarbon group having 1 to 28 carbon atoms may be replaced with -O-, -S-, -SO-, -SO2-, or -CO-.

[0699] L 44 If the -CH2- group in an aliphatic hydrocarbon group having 1 to 28 carbon atoms is replaced by -O-, -S-, -SO-, -SO2-, or -CO-, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the aliphatic hydrocarbon group.

[0700] Groups in which the -CH2- contained in an aliphatic hydrocarbon group is replaced with -O-, -S-, -SO2-, -SO-, or -CO- include hydroxyl groups, carboxyl groups, thiol groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkoxycarbonyloxy groups, oxy groups, carbonyl groups, thio groups, sulfonyl groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, alkanediylcarbonyloxy groups, alkanediylsulfonyl groups, alkanediylthio groups, cycloalkoxy groups, cycloalkylalkoxy groups, and groups combining two or more of these groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0701] Other examples include groups in which one or more hydrogen atoms of the aforementioned group are replaced by bonding sites. Groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -O-, -S-, -SO-, -CO-, or -SO2- include those similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0702] L 44 The aliphatic hydrocarbon group in may have one or more substituents. Examples of substituents include halogen atoms, C1-C4 haloalkyl groups, C1-C12 alkyl groups, C3-C18 alicyclic hydrocarbon groups, or C6-C18 aromatic hydrocarbon groups (the -CH2- contained in the alkyl group or alicyclic hydrocarbon group may be replaced with -O- or -CO-).

[0703] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. C1-C4 haloalkyl groups include C1-C4 alkyl fluorides, C1-C4 alkyl chlorides, C1-C4 alkyl bromides, and C1-C4 alkyl iodides. Examples of haloalkyl groups include C1-C4 perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the haloalkyl group is preferably 1-3, more preferably 1 or 2.

[0704] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.

[0705] Examples of alicyclic hydrocarbon groups having 3 to 18 carbon atoms include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups, and polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, and norbornyl groups. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16, more preferably 3 to 12, and even more preferably 3 to 10.

[0706] Examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and binaphthyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 12, and even more preferably 6 to 10.

[0707] If the -CH2- group in an alkyl group is replaced with -O- or -CO-, the number of carbon atoms before replacement shall be the total number of carbon atoms in the alkyl group. Examples of replaced groups include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, and alkoxycarbonyloxy groups. These replaced groups are similar to those exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0708] The number of carbon atoms in the alkoxy group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3.

[0709] Furthermore, examples of groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -O- or -CO- include those similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0710] L 44The substituents that the aliphatic hydrocarbon group in the above may have are preferably halogen atoms, C1-C3 haloalkyl groups, C1-C6 alkyl groups, C3-C10 alicyclic hydrocarbon groups, or C6-C10 aromatic hydrocarbon groups (the -CH2- contained in the alkyl group or alicyclic hydrocarbon group may be replaced with -O- or -CO-), more preferably fluorine atoms, iodine atoms, C1-C3 perfluoroalkyl groups, or C1-C4 alkyl groups (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), and even more preferably fluorine atoms, iodine atoms, trifluoromethyl groups, methyl groups, hydroxyl groups, or methoxy groups.

[0711] L 44 R 46If the alkyl fluoride does not form an alicyclic hydrocarbon group, it may be a C1-C12 chain hydrocarbon group which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), a C3-C18 alicyclic hydrocarbon group which may have substituents (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O- or -CO-), or a C1-C6 chain hydrocarbon group which may have substituents and an alicyclic hydrocarbon group which may have substituents It is preferably a group formed in combination with a hydrogenated group (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O- or -CO-), and may have substituents. It may be a chain hydrocarbon group having 1 to 8 carbon atoms (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 12 carbon atoms may have substituents, or may have substituents. More preferably, the group is a combination of a chain hydrocarbon group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 5 to 12 carbon atoms which may have substituents, a chain hydrocarbon group having 1 to 6 carbon atoms and It is more preferable that the group is formed by combining a C5- to C12 alicyclic hydrocarbon group which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-), or by combining a C5- to C12 alicyclic hydrocarbon group which may have substituents, a C1- to C6 chain hydrocarbon group, and a C5- to C12 alicyclic hydrocarbon group which may have substituents (the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-).

[0712] R 45Examples of C1-C8 fluoride alkyl groups in this include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, and 1,1-bis(trifluoro)methyl Examples include -2,2,2-trifluoroethyl group, 2-(perfluoropropyl)ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2-(perfluorobutyl)ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group, perfluoroheptyl group, and perfluorooctyl group. The number of carbon atoms in the alkyl fluoride group is preferably 1 to 6, more preferably 1 to 5, even more preferably 1 to 4, and even more preferably 1 to 3.

[0713] R 46 In this context, alkyl fluorides with 1 to 6 carbon atoms are R as long as the upper limit of the carbon number allows. 45 Examples of alkyl fluorides include alkyl fluorides with 1 to 6 carbon atoms.

[0714] R 45 R 46In the case of a fluorinated alkyl group having 1 to 6 carbon atoms, it is preferably a fluorinated alkyl group having 1 to 6 carbon atoms, more preferably a fluorinated alkyl group having 1 to 3 carbon atoms, even more preferably a trifluoromethyl group, a perfluoroethyl group, or a perfluoropropyl group, and even more preferably a trifluoromethyl group.

[0715] R 45 R 46 When is a hydrogen atom, it is preferably a C1-C6 alkyl fluoride, more preferably a C1-C5 alkyl fluoride, and even more preferably a C3-C5 alkyl fluoride.

[0716] R 46 is L 44 When it combines with and forms an alicyclic hydrocarbon group having 3 to 12 carbon atoms, R 46 is L 44 Examples of groups formed by bonding with include the group represented by the following formula. In the following formula, * and ** represent bonding sites, and of the two ** symbols, one represents the bonding site with the hydroxyl group and the other represents R 45 This represents the bonding site with L 44A L 44 It is part of the hydrocarbon group and represents a single bond or an alkanediyl group with 1 to 4 carbon atoms. 46 is L 44 The number of carbon atoms in the alicyclic hydrocarbon group formed by bonding with is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.

[0717] [ka]

[0718] R 46 It is preferable that this is a hydrogen atom or a fluorinated alkyl group having 1 to 3 carbon atoms. mi is preferably an integer between 1 and 3, more preferably 1 or 2, and even more preferably 1.

[0719] Examples of structural units (a4-A) include the following structural units. In the following structural units, R 44 Structural units in which the corresponding methyl group is replaced by a hydrogen atom, halogen atom, haloalkyl group, or alkyl group other than a methyl group, and R 44 Structural units in which the corresponding hydrogen atom is replaced by a halogen atom, a haloalkyl group, or an alkyl group can also be given as specific examples of structural unit (a4-A).

[0720] [ka]

[0721] If resin (A) contains structural units (a4), the content of these units is preferably 1 to 97 mol%, more preferably 1 to 95 mol%, even more preferably 1 to 90 mol%, even more preferably 1 to 20 mol%, even more preferably 2 to 15 mol%, and particularly preferably 3 to 10 mol% relative to the total structural units of resin (A).

[0722] <Structural Unit (a5)> Examples of non-eliminating hydrocarbon groups in structural unit (a5) include groups having linear, branched, or cyclic hydrocarbon groups. Among these, structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.

[0723] An example of a structural unit (a5) is the structural unit represented by formula (a5-1).

[0724] [ka]

[0725] [In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in this alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.

[0726] L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. R 52 The alicyclic hydrocarbon group in this compound may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl groups.

[0727] Examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl.

[0728] Examples of substituted alicyclic hydrocarbon groups include the 3-methyladamantyl group. R 52 Preferably, it is an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably, an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0729] L 55 Examples of divalent saturated hydrocarbon groups in this context include divalent chain-type saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, with divalent chain-type saturated hydrocarbon groups being preferred. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups, which are all types of alkanediyl groups.

[0730] The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic saturated hydrocarbon groups include cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include adamantanediyl and norbornanediyl.

[0731] L 55 Groups in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO- include, for example, the groups represented by formulas (L1-1) to (L1-4). In the following formulas, * and ** represent bonding sites, respectively, and * represents the bonding site with the oxygen atom.

[0732] [ka]

[0733] [In formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 This represents the connection site.

[0734] L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less.

[0735] In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.

[0736] However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms.

[0737] L x6 and L x7Each of these independently represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less.

[0738] In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.

[0739] W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less. L x1 Preferably, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.

[0740] L x2 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

[0741] L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.

[0742] L x6 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

[0743] L x8 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.

[0744] W x1 Preferably, this is a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group. Examples of groups represented by formula (L1-1) include the divalent groups shown below.

[0745] [ka]

[0746] Examples of groups represented by formula (L1-2) include the divalent groups shown below.

[0747] [ka]

[0748] Examples of groups represented by formula (L1-3) include the divalent groups shown below.

[0749] [ka]

[0750] Examples of groups represented by formula (L1-4) include the divalent groups shown below.

[0751] [ka]

[0752] L55 Preferably, it is a single bond or a group represented by formula (L1-1). The structural units (a5-1) are the structural units shown below and the R in the structural unit (a5-1) within the structural units below. 51 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom.

[0753] [ka]

[0754] If resin (A) contains structural units (a5), the content of these units is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol%, relative to the total structural units of resin (A).

[0755] <Structural Unit (a6)> Structural unit (a6) is a structural unit having an -SO2- group, and it is preferable that it has an -SO2- group in its side chain.

[0756] A structural unit having an -SO2- group may have a linear structure having an -SO2- group, a branched structure having an -SO2- group, or a cyclic structure (monocyclic and polycyclic) having an -SO2- group. Preferably, it is a structural unit having a cyclic structure having an -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0757] As a sultone ring, the following equation (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 A ring represented by (T-4) is an example. The bonding site can be at any position. The sultone ring may be monocyclic, but it is preferably polycyclic. A polycyclic sultone ring means a bridging ring containing -SO2-O- as the atomic group constituting the ring, and is represented by formula (T 1 -1) and formula (T 1 A ring represented by equation (T) is an example. A Sultone ring is given by equation (T1 As shown in (2), the ring may contain heteroatoms in addition to -SO2-O- as part of the atomic group constituting the ring. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms, with oxygen atoms being preferred.

[0758] [ka]

[0759] The sultone ring may have substituents, and examples of substituents include C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group, halogen atoms, hydroxyl groups, cyano groups, C1-C12 alkoxy groups, C6-C12 aryl groups, C7-C12 aralkyl groups, glycidyloxy groups, C2-C12 alkoxycarbonyl groups, and C2-C4 alkylcarbonyl groups.

[0760] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl groups, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably methyl groups.

[0761] Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl, with trifluoromethyl being preferred.

[0762] Examples of alkyl groups having a hydroxyl group include hydroxymethyl groups and 2-hydroxyethyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups.

[0763] Examples of aryl groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

[0764] Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, naphthylmethyl, and naphthylethyl groups. Examples of alkoxycarbonyl groups include groups in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group.

[0765] Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. From the viewpoint of ease of production of monomers that lead to structural unit (a6), a sultone ring without substituents is preferred.

[0766] As the sultone ring, the ring represented by the following formula (T1') is preferred.

[0767] [ka]

[0768] [In formula (T1′), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41This represents a C1-C12 alkyl group which may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, a C1-C12 alkoxy group, a C6-C12 aryl group, a C7-C12 aralkyl group, a glycidyloxy group, a C2-C12 alkoxycarbonyl group, or a C2-C4 alkylcarbonyl group.

[0769] ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They may be the same or different. The connection point can be at any location. X 11 This is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

[0770] R 41 Examples include substituents similar to those of a sultone ring, and C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group are preferred. ma is preferably 0 or 1, and more preferably 0.

[0771] The following rings can be represented by formula (T1'). The bonding site can be at any position. In particular, rings with a bonding site at position 1 or 3 are preferred.

[0772] [ka]

[0773] The structural unit having the -SO2- group preferably further has a group derived from a polymerizable group. Examples of polymerizable groups include vinyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, acryloylthio group, and methacryloylthio group.

[0774] In particular, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer. The structural unit (a6) is preferably a structural unit represented by formula (a6-0).

[0775] [ka]

[0776] [In formula (a6-0), R x This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom.

[0777] A xx is an oxygen atom, -N(R c )- or represents a sulfur atom. A x represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -N(R d )- may be replaced with this.

[0778] X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 This represents the same base as described above. ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They may be the same or different.

[0779] R c and R d Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R x , R c and R d R is the R of equation (a1-0). a01 Similar to the examples given earlier, the same types of bases can be cited.

[0780] R xPreferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group. A x Examples of divalent saturated hydrocarbon groups include linear alkanediyl groups, branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups are also acceptable.

[0781] Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group Linear alkanediyl groups such as dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; Branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; Monocyclic, divalent, alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, 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.

[0782] A x The bond position to the sultone ring can be any position, but it is preferably at position 1. The following structural units (a6-0) can be listed:

[0783] [ka]

[0784] In particular, structural units represented by formulas (a6-1), (a6-2), (a6-6), (a6-7), (a6-8), and (a6-12) are preferred, and structural units represented by formulas (a6-1), (a6-2), (a6-7), and (a6-8) are more preferred.

[0785] If resin (A) contains structural units (a6), the content of these units is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and even more preferably 3 to 30 mol%, relative to the total structural units of resin (A).

[0786] <Structural unit (a7)> The resin (A), etc., may further contain structural units (hereinafter sometimes referred to as "structural unit (a7)") that decompose upon exposure to generate acid. Specifically, structural unit (a7) is the structural unit described in Japanese Patent Application Publication No. 2016-79235, and is preferably a structural unit having a sulfonic acid anion or carboxylic acid anion and an organic cation in its side chain, or a structural unit having a sulfonium cation and an organic anion in its side chain.

[0787] The structural unit having a sulfonic acid anion or carboxylic acid anion and an organic cation in its side chain is preferably the structural unit represented by formula (a7-A).

[0788] [ka]

[0789] [In formula (a7-A), R a7 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom.

[0790] X a71 These are single bonds, or -O-, -CO-, -S-, -SO-, -SO2-, -NR a71 - represents a phenylene group which may have substituents, or a group which is a combination thereof.

[0791] R a71 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L a71 and L a72 Each of these independently represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-.

[0792] X a72 ***-CO-O-, ***-O-CO-, ***-O-CO-O-, ***-O-, where *** is L a71 This represents the connection point. na7 represents an integer between 0 and 2. When na7 is 2, the bases within the parentheses may be the same or different.

[0793] RA - This represents a sulfonate anion or a carboxylate anion. ZA + This represents an organic cation. R a7 R is the R of equation (a1-0). a01 Examples of groups similar to those exemplified in the above include R. a7 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom, a methyl group or an ethyl group is even more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0794] R a71 Examples of C1-C6 alkyl groups in this compound include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

[0795] X a71 These are single bonds, -O-, -CO-, -NR a71 - Preferably, the group is a phenylene group which may have substituents or a combination thereof, and may be a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, *-CO-NR a71 -**, *-NR a71 -CO-O-**, *-O-CO-NR a71 -** or *-Ax-Ph-Ay-** is more preferable.

[0796] In the above base, * and ** represent binding sites, and * is R a7 This represents the bonding site with the bonded carbon atom. Ax and Ay each independently represent one or more bond species selected from the group consisting of single bonds, ether bonds, thioether bonds, amide bonds, ester bonds, and carbonate ester bonds. Ph represents a phenylene group which may have substituents.

[0797] X a71 However, in the case of a group represented by *-Ax-Ph-Ay-**, it is preferable that it be a linking group represented by the following formula (X10).

[0798] [ka]

[0799] [In formula (X10), Ax is R a7 This represents the type of bond that bonds to the carbon atom to which it is bonded, and it represents one or more types of bonds selected from the group consisting of single bonds, ether bonds, thioether bonds, ester bonds, carbonate ester bonds, and amide bonds.

[0800] Ay is L a71 This represents the type of bond that binds to a given element, and is one or more types of bond selected from the group consisting of single bonds, ether bonds, thioether bonds, ester bonds, carbonate ester bonds, and amide bonds.

[0801] Rx represents a halogen atom, a hydroxyl group, a C1-C6 alkyl fluoride group, a C1-C18 alkyl group, or a C1-C6 alkoxy group. mx represents an integer between 0 and 4, and if mx is an integer greater than or equal to 2, multiple Rx values ​​may be the same or different from each other. If either Ax or Ay is a single bond, it is preferable that the other is one or more selected from the group consisting of ether bonds, thioether bonds, ester bonds, carbonate ester bonds, and amide bonds.

[0802] If either Ax or Ay is an amide bond, then -CO-NR a71 A bond represented by - is preferable. The bonding position of Ay on the phenylene group is preferably at the m-position or p-position relative to the bonding position of Ax, and more preferably at the p-position.

[0803] Rx is preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, or an ethyl group. mx is preferably 0, 1, or 2.

[0804] X a71 For example, a single bond, as shown in the following equation (X 10 -1)~Formula(X 10 Examples of groups represented by -10) include * which is -R a7 This represents the bonding site with the carbon atom to which it is bonded. ** indicates L a71 This represents the connection point with X. 20 -O- or -NR a71 - represents

[0805] [ka]

[0806] Expression(X 10 -1)~Formula(X 10 The following are specific examples of the group represented by -10):

[0807] [ka]

[0808] Among them, X a71 This is a single bond and formula (X 10 -1′), equation (X 10 -3′)~Formula(X 10 It is preferably a group represented by one of the following formulas (X -10′), and is a single bond or a group represented by formula (X 10 -1′), equation (X 10 -4′), formula (X 10 -5′), formula (X 10 -6′) and equation (X 10 It is more preferable that the group be represented by any of the following formulas (X -10′), and is a single bond, formula (X 10 The base represented by formula (X -1'), formula (X 10 A base or formula (X -5′) represented by the base or formula (X 10 It is even more preferable that the group be represented by -6').

[0809] L a71 As for the hydrocarbon group, one hydrogen atom is removed from a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining two or more of these groups, X a71 and X a72 Groups that bond with L are also mentioned. a72 As for the hydrocarbon group, one hydrogen atom is removed from a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining two or more of these groups, X a72 and RA - Examples of groups that bond with it include:

[0810] L a71 and L a72Examples of chain-like hydrocarbon groups include groups obtained by removing one hydrogen atom from an alkyl or alkenyl group. Alkyl groups may be linear or branched, and specifically include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and heptadecyl groups. Examples of alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups.

[0811] The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 20, more preferably 1 to 18, and even more preferably 1 to 10. L a71 and L a72 Examples of alicyclic hydrocarbon groups include groups obtained by removing one hydrogen atom from a monocyclic or polycyclic cycloalkyl group. Examples of monocyclic cycloalkyl groups include cyclobutyl, cycloheptyl, cyclohexyl, cyclopentyl, and cyclooctyl groups.

[0812] L a71 and L a72Examples of polycyclic cycloalkyl groups include cycloalkyl groups having a cross-linking structure, cycloalkyl groups formed by the condensation of two or more rings, or cycloalkyl groups formed by the spirolinking of two rings. Examples of cycloalkyl groups having a cross-linking structure include norbornyl groups and adamantyl groups. Examples of cycloalkyl groups formed by the condensation of two or more rings include bicyclo[4.4.0]decanyl groups and steroid groups (steroid skeletons). Examples of cycloalkyl groups formed by the spirolinking of two rings include spirocyclic cycloalkyl groups in which one or more cycloalkyl groups selected from the group consisting of cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups are spirolinked to a cycloalkyl group having 5 to 8 carbon atoms. Furthermore, a double bond may be formed between two carbon atoms in the alicyclic hydrocarbon group. More specifically, examples of alicyclic hydrocarbon groups represented by the following formulas include:

[0813] [ka]

[0814] When the alicyclic hydrocarbon group is a monocyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 12, and even more preferably 3 to 8. When the alicyclic hydrocarbon group is a polycyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 6 to 18, and more preferably 7 to 12.

[0815] L a71 and L a72 Examples of aromatic hydrocarbon groups include those obtained by removing one hydrogen atom from an aryl group. Examples of aryl groups include phenyl, naphthyl, anthryl, biphenyl, and fluorenyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 5 to 14, more preferably 6 to 14, and even more preferably 6 to 10.

[0816] L a71 and L a72If the -CH2- contained in the hydrocarbon group is replaced by -O-, -CO-, -S-, -SO-, or -SO2-, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group.

[0817] L a71 and L a72 Among the hydrocarbon groups, groups in which the -CH2- contained in the chain hydrocarbon group is replaced with -O-, -CO-, -S-, -SO-, or -SO2- include hydroxyl groups, carboxyl groups, thiol groups, carbonyl groups, oxy groups, thio groups, sulfonyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkanediyloxy groups, alkanediyloxycarbonyl groups, alkanediylcarbonyl groups, and alkanediylcarbonyloxy groups. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0818] L a71 and L a72 Among the hydrocarbon groups, groups in which the -CH2- contained in alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining them is replaced with -O-, -CO-, -S-, -SO-, or -SO2- include groups containing structures such as cyclic ethers, cyclic ketones, cyclic esters (lactones), cyclic thioethers, cyclic acetals, and cyclic sulfonic acid esters (sultones), as well as groups derived from furan rings, thiophene rings, etc. These replaced groups are similar to the groups exemplified herein, within the limits permitted by the upper limit of the number of carbon atoms.

[0819] L a71 and L a72Examples of groups combining two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include groups combining the above-mentioned chain hydrocarbon group and alicyclic hydrocarbon group, groups combining the above-mentioned chain hydrocarbon group and aromatic hydrocarbon group, groups combining the above-mentioned alicyclic hydrocarbon group and aromatic hydrocarbon group, and groups combining the above-mentioned chain hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group. Groups combining alicyclic hydrocarbon groups and aromatic hydrocarbon groups may also be fused rings.

[0820] L a71 and L a72 The hydrocarbon group may have substituents such as halogen atoms, cyano groups, and nitro groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0821] L a71 and L a72 However, if the group is a combination of an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group, the chain hydrocarbon group may be substantially considered as a substituent of the alicyclic hydrocarbon group or aromatic hydrocarbon group. a71 and L a72 The -CH2- in the chain hydrocarbon group contained in the hydrocarbon group is replaced by -O-, -CO-, -S-, -SO-, or -SO2-, L a71 and L a72 The hydrocarbon group may substantially have substituents such as a hydroxyl group, carboxyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, thiol group, alkylthio group, and alkylsulfonyl group.

[0822] na7 is preferably 0 or 1. ZA in equation (a7-A) + Examples include cations similar to those in the salt represented by formula (B1).

[0823] In equation (a7-A), L a71 and La72 If the hydrocarbon group is a saturated hydrocarbon group, then in formula (a7-B) described below, A b7 It may also contain groups similar to those exemplified as divalent linking groups.

[0824] Examples of structural units represented by formula (a7-A) include those represented by formula (a7-A1).

[0825] [ka]

[0826] [In formula (a7-A1), R a7 , X a71 , L a71 , X a72 na7, RA - and ZA + This expresses the same meaning as above.

[0827] z7 represents an integer between 0 and 6. Q a7 Q b7 , R z71 and R z72 Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and when z7 is 2 or more, multiple R z71 and R z72 They may be the same or different from each other. Q a7 Q b7 , R z71 and R z72 In this, the perfluoroalkyl group having 1 to 6 carbon atoms or the alkyl group having 1 to 6 carbon atoms is R a7 Examples of groups similar to those exemplified above include the following.

[0828] Examples of structural units represented by formula (a7-A) include the following structural unit, R a7Examples include structural units in which the group corresponding to the methyl group is replaced by a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a C1-C6 alkyl group which may have a halogen atom (e.g., a trifluoromethyl group), and structural units described in International Publication No. 2012 / 050015. ZA + This represents an organic cation.

[0829] [ka]

[0830] [ka]

[0831] The structural unit having a sulfonio group and an organic anion in its side chain is preferably the structural unit represented by formula (a7-B).

[0832] [ka]

[0833] [In formula (a7-B), R a7 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom.

[0834] A b7 This represents a single bond or a divalent linking group. R b71 This represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have substituents. R b72 and R b73 Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have substituents, and R b72 and R b73 These atoms may bond to each other, forming a ring with the sulfur atom to which they are bonded.

[0835] A - This represents an organic anion. R a7 Examples of halogen atoms and alkyl groups that may have halogen atoms include halogen atoms and alkyl groups that may have halogen atoms similar to those of formula (a7-A).

[0836] R b71 Examples of divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, represented by this formula, include phenylene groups and naphthylene groups. R b72 and R b73 Examples of hydrocarbon groups represented by this symbol include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.

[0837] Examples of alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these are the same as those described above. A b7 Examples of divalent linking groups represented by include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O-, -S-, -SO-, -SO2-, or -CO-.

[0838] Examples of divalent saturated hydrocarbon groups include divalent chain-type saturated hydrocarbon groups such as linear or branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof are also possible.

[0839] Specifically, linear alkane diyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, etc.; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4 Examples include branched alkanediyl groups such as -diyl groups and 2-methylbutane-1,4-diyl groups; divalent monocyclic alicyclic saturated hydrocarbon groups such as monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl groups, cyclopentane-1,3-diyl groups, cyclohexane-1,4-diyl groups, and cyclooctane-1,5-diyl groups; and divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl groups, norbornane-2,5-diyl groups, adamantane-1,5-diyl groups, and adamantane-2,6-diyl groups.

[0840] Examples of groups in which the -CH2- group in a saturated hydrocarbon group is replaced by -O-, -S-, -SO-, -SO2-, or -CO- include the divalent groups shown below. However, the number of carbon atoms before the -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, -SO-, -SO2-, or -CO- is 17 or less. In the following formulas, * and ** represent bonding sites, and * is R b71 This represents the connection point.

[0841] [ka]

[0842] [where, X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0843] X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. The cation-containing structural units in formula (a7-B) are the structural units and R represented below. a7 Examples include structural units in which the group corresponding to the methyl group is replaced by a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a C1-C6 alkyl group that may have a halogen atom (e.g., a trifluoromethyl group).

[0844] [ka]

[0845] A - Examples of organic anions represented by include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions. - The organic anion represented is preferably a sulfonic acid anion, and more preferably the sulfonic acid anion is the same as the anion exemplified in compound (B). Examples of sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions are the same as the anions exemplified in compound (B).

[0846] Examples of structural units represented by formula (a7-B) include the following structural units:

[0847] [ka]

[0848] When the resin (A) contains structural units (a7), the content of structural units (a7) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total structural units of the resin (A).

[0849] Resin (A) is preferably a resin consisting of structural unit (a1) and structural unit (s). The structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1), structural unit (a1-2) (preferably a structural unit having a cyclohexyl group or a cyclopentyl group), structural unit represented by formula (a1-4), structural unit represented by formula (a1-5), and structural unit represented by formula (a1-6), more preferably at least two, and even more preferably structural unit (a1-1) and / or structural unit (a1-2).

[0850] The structural unit (s) is preferably at least one selected from the group consisting of structural units (a2) and structural units (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-A) or a structural unit represented by formula (a2-C). The structural unit (a3) ​​is preferably at least one selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2), and a structural unit represented by formula (a3-4).

[0851] Each structural unit constituting resin (A) may be used individually or in combination of two or more types, and these structural units can be produced by known polymerization methods (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in resin (A) can be adjusted by the amount of monomer used in polymerization.

[0852] The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,500 or more, even more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, even more preferably 15,000 or less), but it may also contain oligomers with a smaller weight-average molecular weight. In this specification, the weight-average molecular weight is the value obtained by gel permeation chromatography under the conditions described in the examples.

[0853] <Resins other than resin (A)> The resist composition of the present invention may also contain resins other than resin (A). Examples of resins other than resin (A) include resins containing structural units similar to resin (A), except that resin (A) does not contain structural unit (a1) (hereinafter sometimes referred to as "resin (AX)"), resins containing structural unit (a4) and / or structural unit (a5) (hereinafter sometimes referred to as "resin (X)"), etc.

[0854] Examples of resin (AX) include resins containing structural unit (a2), and resins containing structural unit (a2-A) are preferred. In resin (AX), the content of structural unit (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total amount of all structural units in resin (AX). Furthermore, it is preferably 80 mol% or less, and more preferably 70 mol% or less.

[0855] Structural units that resin (X) may further contain include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. In particular, resin (X) is preferably composed only of structural unit (a4) and / or structural unit (a5), and more preferably composed only of structural unit (a4).

[0856] When resin (X) contains structural unit (a4), the content of structural unit (a4) in resin (X) is preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, relative to the total amount of all structural units in resin (X). Also, it is preferably 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, it is preferably 20 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. When resin (X) contains structural unit (a5), the content of structural unit (a5) is preferably 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, relative to the total amount of all structural units in resin (X). Furthermore, a value of 100 mol% or less is cited, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, a value of 20 to 100 mol% is cited, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably...

Claims

1. A resist composition containing a carboxylate salt represented by formula (I). 【Chemistry 1】 [In formula (I), L １ represents a hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. R ７ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X １ represents a single bond, -O-, -S-, -CO-, -SO-, -SO ２ -, -NR ７ -, or a divalent hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH ２ - in the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -SO ２ -, or -NR ７ -. Ar １ and Ar ２ Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar １ and Ar ２ The substituents may come together to form a ring that may contain heteroatoms. Z ＋ This represents an organic cation.

2. -Ar １ -X １ -Ar ２ The resist composition according to claim 1, wherein the group is represented by formula (I-A) or formula (I-B). 【Chemistry 2】 [In formulas (I-A) and (I-B), X １ This expresses the same meaning as above. R ３ and R ４ Each of these independently represents a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced by -, R ３ and R ４ These may come together to form a ring that may contain heteroatoms. R ７ This expresses the same meaning as above. X ２ These are single bonds, -O-, -S-, -CO-, -SO-, -SO ２ -, -NR ７ - Represents a divalent hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. nn1 and nn2 each independently represent either 0 or 1. m3 represents an integer between 0 and (4 + nn1 × 2), and when m3 in equation (I-A) or (m3-1) in equation (I-B) is 2 or greater, multiple R ３ They may be identical or different from one another. m4 represents an integer between 0 and (5 + nn² × 2), and when m4 in equation (I-A) or (m4-1) in equation (I-B) is 2 or greater, multiple R ４ They may be identical or different from one another. * is L １ or COO － This is a bonding site with the carbon atoms that make up the molecule.

3. The resist composition according to claim 1 or 2, wherein the carboxylate represented by formula (I) is the carboxylate represented by formula (I1). 【Transformation 3】 [In formula (I1), L １ represents a hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. R ７ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar １ and Ar ２ Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar １ and Ar ２ The substituents may come together to form a ring that may contain heteroatoms. R ５ and R ６ Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have a halogen atom or substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -NR ７ -, -SO- or -SO ２ It may be replaced with -. m5 represents an integer from 0 to 4, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 4, and when m6 is 2 or greater, multiple R ６ They may be identical or different from one another. Z ＋ Each of these independently represents an organic cation.

4. L １ However, a chain hydrocarbon group having 1 to 12 carbon atoms may have substituents (the chain hydrocarbon group contains -CH ２ - is -O-, -NR ７ A group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the chain hydrocarbon group and the cyclic hydrocarbon group contain -CH ２ - is -O-, -NR ７ The resist composition according to claim 1 or 2, wherein - or -CO- may be replaced.

5. The resist composition according to claim 1 or 2, further comprising a resin containing a structural unit represented by formula (a2-A). 【Chemistry 4】 [In formula (a2-A), R ａ２ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R ａ２７ This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A ａ２１ This represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH ２ - stands for -O-, -CO-, or -NR ａ２８ It may be replaced with -. R ａ２８ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ａ２ This represents a single bond or a carbonyl group. nA2 represents an integer from 1 to 5, and when nA2 is 2 or greater, the bases within the parentheses may be the same or different. na21 represents an integer from 0 to 4, and when na21 is 2 or greater, multiple R ａ２７ They may be the same or different from one another. mc represents an integer between 0 and 2.

6. The resin further comprises structural units having acid-unstable groups, The resist composition according to claim 5, wherein the structural unit having the acid-unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a1-4), a structural unit represented by formula (a1-5), and a structural unit represented by formula (a1-6). 【Transformation 5】 [In formulas (a1-0), (a1-1), and (a1-2), L ａ０１ , L ａ１ and L ａ２ These are, independently, -O- or *-O- (CH ２ ) ｋ１ This represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bonding site with -CO-. R ａ０１ , R ａ４ and R ａ５ Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R ａ０２ , R ａ０３ and R ａ０４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group consisting of a combination thereof, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. R ａ６ and R ａ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination thereof, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. m1' represents an integer between 0 and 14. n1 represents an integer between 0 and 14. n1' represents an integer between 0 and 3. 【Transformation 6】 [In formula (a1-4), R ａ１ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R ａ１７ This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A ａ１１ This represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH ２ - stands for -O-, -CO-, or -NR ａ１８ It may be replaced with -. R ａ１８ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ａ１ This represents a single bond or a carbonyl group. R ａ３４ and R ａ３５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ａ３６ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ａ３４ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ａ３５ and R ａ３６ are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH ２ - contained in the hydrocarbon group and the divalent heterocyclic group may be replaced by -O- or -S-. na1 represents an integer from 1 to 5, and when na1 is 2 or greater, the bases within the parentheses may be the same or different. na11 represents an integer from 0 to 4, and when na11 is 2 or greater, multiple R ａ１７ They may be the same or different from one another. mc represents an integer between 0 and 2. 【Transformation 7】 [In formula (a1-5), R ａ８ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z ａ１ is a single bond or *-(CH ２ ) ｈ３ -CO-L ５４ - represents, h3 represents an integer from 1 to 4, and * represents L ５１ This represents the connection point. L ５１ , L ５２ , L ５３ and L ５４ These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3. 【Transformation 8】 [In formula (a1-6), R ａ６１ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R ａ６２ , R ａ６３ and R ａ６４ Each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, or R ａ６４ R represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, and ａ６２ and R ａ６３ These atoms bond with each other, forming a ring with 3 to 20 carbon atoms together with the carbon atoms they bond to. X ａ６１ These are single bonds, -CO-O-* or -CO-NR ａ６５ - represents *, where * represents the bonding site with Ar, R ａ６５ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ａ６２ This is a single bond, *-O-L ａ６１ - or * - CO-O-L ａ６２ - represents the bonding site with Ar, and L ａ６１ and L ａ６２ Each of these independently represents an alkanediyl group having 1 to 4 carbon atoms. Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents.

7. Furthermore, it contains an acid generator, The resist composition according to claim 1 or 2, wherein the acid generator comprises a salt represented by formula (B1), a salt represented by formula (B2), or a salt represented by formula (B4). 【Chemistry 9】 [In formula (B1), L ｂ１ This represents a hydrocarbon group having a single bond or a substituent (nb1+1), and the hydrocarbon group contains -CH ２ - stands for -O-, -S-, -CO-, -SO-, or -SO ２ It may be replaced with -. L ｂ２ This represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH ２ - stands for -O-, -S-, -CO-, -SO-, or -SO ２ It may be replaced with -. Y ｂ１ This represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -SO-, -SO ２ It may be replaced with - or -CO-. nb1 represents an integer between 1 and 6. When nb1 is 2 or greater, the bases within the parentheses may be the same or different. Z1 ＋ This represents an organic cation. 【Chemistry 10】 [In formula (B2), A １ represents a nitrogen atom or a carbon atom. L ｂ２′ This represents a divalent hydrocarbon group having 1 to 24 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH ２ - stands for -O-, -S-, -CO-, -SO-, or -SO ２ It may be replaced with -. Y ｂ１′ This represents a methyl group which may have substituents or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the cyclic hydrocarbon group contains -CH ２ - stands for -O-, -S-, -CO-, -SO-, or -SO ２ It may be replaced with -. nb5 is A １ If it is a nitrogen atom, then it is 2, and A １ If it is a carbon atom, then it is 3. The groups in parentheses may be the same or different from each other, and two groups in parentheses combine to form A １ They may form a ring together. Z2 ＋ This represents an organic cation. 【Chemistry 11】 [In formula (B4), L ｂ１４ and L ｂ１５ Each of these independently represents a divalent hydrocarbon group having 1 to 72 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH ２ - stands for -O-, -S-, -CO-, -SO-, or -SO ２ It may be replaced with -. Ar Ｂ４ and Ar Ｂ５ Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar Ｂ４ and Ar Ｂ５ The substituents may come together to form a ring. R Ｂ４ and R Ｂ５ Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have a halogen atom or substituents, and the hydrocarbon group contains -CH ２ - stands for -O-, -CO-, -S-, -SO-, or -SO ２ It may be replaced with -. mB4 represents an integer between 0 and 4, and when mB4 is 2 or greater, multiple R Ｂ４ They may be identical or different from one another. mB5 represents an integer between 0 and 4, and when mB5 is 2 or greater, multiple R Ｂ５ They may be identical or different from one another. Z4 ＋ and Z5 ＋ Each of these independently represents an organic cation.

8. (1) A step of applying the resist composition according to claim 1 or 2 onto a substrate, (2) A step of drying the coated resist composition to form a composition layer, (3) Exposure step of the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

9. A carboxylate salt represented by formula (I). 【Chemistry 12】 [In formula (I), L １ represents a hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. R ７ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X １ These are single bonds, -O-, -S-, -CO-, -SO-, -SO ２ -, -NR ７ - Represents a divalent hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. Ar １ and Ar ２ Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar １ and Ar ２ The substituents may come together to form a ring that may contain heteroatoms. Z ＋ This represents an organic cation.

10. -Ar １ -X １ -Ar ２ The carboxylate salt according to claim 9, wherein the group is represented by formula (I-A) or formula (I-B). 【Chemistry 13】 [In formulas (I-A) and (I-B), X １ This expresses the same meaning as above. R ３ and R ４ Each of these independently represents a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced by -, R ３ and R ４ These may come together to form a ring that may contain heteroatoms. R ７ This expresses the same meaning as above. X ２ These are single bonds, -O-, -S-, -CO-, -SO-, -SO ２ -, -NR ７ - Represents a divalent hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. nn1 and nn2 each independently represent either 0 or 1. m3 represents an integer between 0 and (4 + nn1 × 2), and when m3 in equation (I-A) or (m3-1) in equation (I-B) is 2 or greater, multiple R ３ They may be identical or different from one another. m4 represents an integer between 0 and (5 + nn² × 2), and when m4 in equation (I-A) or (m4-1) in equation (I-B) is 2 or greater, multiple R ４ They may be identical or different from one another. * is L １ or COO － This is a bonding site with the carbon atoms that make up the molecule.

11. The carboxylate salt according to claim 9 or 10, wherein the carboxylate salt represented by formula (I) is the carboxylate salt represented by formula (I1). 【Chemistry 14】 [In formula (I1), L １ represents a hydrocarbon group having 1 to 28 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -SO-, -SO ２ - or - NR ７ It may be replaced with -. R ７ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar １ and Ar ２ Each of these independently represents an aromatic hydrocarbon group having 6 to 24 carbon atoms, which may have substituents, and Ar １ and Ar ２ The substituents may come together to form a ring that may contain heteroatoms. R ５ and R ６ Each of these independently represents a hydrocarbon group having 1 to 18 carbon atoms, which may have a halogen atom or substituents, and the hydrocarbon group contains -CH ２ - is -O-, -CO-, -S-, -NR ７ -, -SO- or -SO ２ It may be replaced with -. m5 represents an integer from 0 to 4, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 4, and when m6 is 2 or greater, multiple R ６ They may be identical or different from one another. Z ＋ Each of these independently represents an organic cation.

12. L １ However, a chain hydrocarbon group having 1 to 12 carbon atoms may have substituents (the chain hydrocarbon group contains -CH ２ - is -O-, -NR ７ A group formed by combining a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the chain hydrocarbon group and the cyclic hydrocarbon group contain -CH ２ - is -O-, -NR ７ The carboxylate salt according to claim 9 or 10, wherein it may be replaced with - or -CO-.

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