Carboxylic acid salt, carboxylic acid generator, resist composition and method for producing resist pattern

Abstract

To provide a carboxylate that makes it possible to produce a resist pattern having excellent line edge roughness, a carboxylic acid generator and a resist composition comprising the same.SOLUTION: The present invention discloses, for example, a carboxylate represented by formula (I-1).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 describes a resist composition that contains a carboxylic acid salt represented by the following formula as a carboxylic acid generator. TIFF0007813531000001.tif2643 Patent Document 2 describes a resist composition that contains a carboxylic acid salt represented by the following formula as a carboxylic acid generator. TIFF0007813531000002.tif5149 Patent Document 3 describes a resist composition that contains a salt represented by the following formula as an acid generator. TIFF0007813531000003.tif2687 Patent Document 4 describes a resist composition that contains a salt represented by the following formula as an acid generator. TIFF0007813531000004.tif2687 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-039502 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-095497 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-085878 [Patent Document 4] Japanese Patent Publication No. 2020-015713 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a carboxylate salt that forms a resist pattern with better line edge roughness (LER) than a resist pattern formed with a resist composition containing the above salt. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007813531000005.tif81104 [In formula (I), R 1 , R 2 and R 3 are each independently -OR 10 , -O-CO-R 10 , -O-CO-OR 10 , -OL 1 -CO-OR 10 Represents. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group optionally having a substituent, and -CH2- contained in the hydrocarbon group optionally being replaced by -O-, -S-, -CO- or -SO2-. L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 10 represents a group having a lactone structure. X 1 , X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of 0 to 5, and when m1 is 2 or greater, the groups in the parentheses may be the same or different. m2 represents an integer of 0 to 4, and when m2 is 2 or greater, the groups in the parentheses may be the same or different. m3 represents an integer of 0 to 4, and when m3 is 2 or greater, the groups in the parentheses may be the same or different. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 may be the same or different from each other. m5 represents an integer of 0 to 4, and when m5 is 2 or more, a plurality of R 5 may be the same or different from each other. m6 represents an integer of 0 to 4, and when m6 is 2 or more, a plurality of R 6 may be the same or different from each other. m7 represents an integer of 0 to 5, and when m7 is 2 or more, a plurality of R 7 may be the same or different from each other. m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of R 8 may be the same or different from each other. m9 represents an integer of 0 to 4, and when m9 is 2 or more, a plurality of R 9 may be the same or different from each other. However, 0≦m1+m7≦5, 0≦m2+m8≦4, and 0≦m3+m9≦4, and at least one of m1, m2, and m3 represents an integer of 1 or more. X 4 represents a single bond, -CH2-, -O-, -S-, -CO-, -SO- or -SO2-. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-.] [2]X 1 , X 2 and X 3 [1] The carboxylate according to [1], wherein [3]R 1 , R 2 and R 3 Ga-O-CO-OR 10 -or-OL 1 -CO-OR 10The carboxylate according to [1] or [2], [4]R 10 The group having a lactone structure of the formula (R 10 -1), formula (R 10 -2) or formula (R 10 The carboxylic acid salt according to any one of [1] to [3], wherein the carboxylic acid salt is a group having a lactone ring group represented by the formula (I-3). TIFF0007813531000006.tif36120[Formula(R 10 -1)~Formula(R 10 -3) Medium, * represents a bond. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R 11 , R 12 and R 13 each independently represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-. m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of R 11 may be the same or different from each other. m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R 12 may be the same or different from each other. m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of R 13 may be the same or different from each other. n10 represents an integer of 1 to 3. [5]X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. [6]X 0is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. [7] A carboxylic acid generator containing the carboxylic acid salt according to any one of [1] to [6]. [8] A resist composition comprising the carboxylic acid generator according to [7], an acid generator other than the carboxylic acid generator, and a resin having an acid labile group. [9] The resist composition according to [8], wherein the resin having an acid labile group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2): TIFF0007813531000007.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding position with —CO—. R a4 and R a5 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. R a6 and R a7 each 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 combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[10] The resist composition according to [8] or [9], further comprising a resin containing a structural unit having a fluorine atom.

[11] (1) A step of applying the resist composition according to any one of [8] to

[10] onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0006] By using a resist composition that uses a carboxylate of the present invention, a resist pattern with good line edge roughness (LER) can be produced. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, "(meth)acrylic monomer" means "at least one of an acrylic monomer and a methacrylic monomer." The terms "(meth)acrylate" and "(meth)acrylic acid" have the same meaning. Regarding groups described herein, those that can have either a linear or branched structure are acceptable. When -CH2- in a hydrocarbon group or the like is replaced with -O-, -S-, -CO-, or -SO2-, the same examples apply to each group. A "combined group" refers to a group in which two or more of the exemplified groups are bonded, and the valence of these groups may vary depending on the bonding form. "Derived from" or "derived from" refers to a polymerizable C=C bond in the molecule becoming a -CC- group by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the term "solid content of the resist composition" refers to the sum of all components in the resist composition excluding the solvent (E), which will be described later.

[0008] [Carboxylate represented by formula (I)] The present invention relates to a carboxylate salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In the salt (I), the negatively charged side is sometimes called the "anion (I)" and the positively charged side is sometimes called the "cation (I)". TIFF0007813531000008.tif81104 [wherein all symbols have the same meanings as defined above.]

[0009] In formula (I), R 1 , R 2 and R 3 L included in 1 Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and Examples of branched alkanediyl groups include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. L 1 is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0010] R 1 , R 2 and R 3 R included in 10represents a group having a lactone structure. The lactone structure refers to a structure obtained by removing one or more hydrogen atoms bonded to the atomic group constituting the lactone ring. The lactone ring is a cyclic ester containing -CO-O- as the atomic group constituting the ring. The lactone structure may contain one or more heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms in addition to -CO-O- as the atomic group constituting the ring, and the hydrogen atoms bonded to the atomic group constituting the lactone ring may be replaced with substituents. The lactone ring may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring with another ring. Among these lactone rings, a γ-butyrolactone ring, an adamantanelactone ring, or a condensed ring of a γ-butyrolactone ring with another ring is preferred because it facilitates the production of the salt (I) described below.

[0011] The lactone ring corresponding to the structure before the hydrogen atom is removed from the lactone structure includes lactone rings having 3 to 18 carbon atoms, and more specifically, includes compounds represented by formula (R-1), formula (R-2), formula (R-3), formula (R-4), formula (R-5), formula (R-6), formula (R-7), and formula (R-8). Furthermore, like the compound represented by formula (R-3) or formula (R-8), the atomic group constituting the ring may contain a heteroatom other than -CO-O-. Furthermore, the hydrogen atom contained in the lactone ring may be replaced by a substituent. TIFF0007813531000009.tif31160 The lactone ring is preferably a lactone ring represented by formula (R-1), formula (R-2), formula (R-3) or formula (R-6).

[0012] R 10 The group having a lactone structure of the formula (R 10 -1), formula (R 10 -2) or formula (R 10 A group having a lactone ring group represented by formula (3) is preferred. TIFF0007813531000010.tif36120[Formula(R 10 -1)~Formula(R 10 -3) Medium, * represents a bond. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R 11 , R 12 and R 13 each independently represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-. m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of R 11 may be the same or different from each other. m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R 12 may be the same or different from each other. m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of R 13 may be the same or different from each other. n10 represents an integer of 1 to 3.

[0013] R 11 , R 12 and R 13 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 11 , R 12 and R 13 The fluorinated alkyl group having 1 to 6 carbon atoms refers to an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom, and examples thereof include perfluoroalkyl groups having 1 to 6 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), as well as 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. R 11 , R 12 and R 13Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, still more preferably 1 to 4, and still more preferably 1 to 3. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, and norbornyl. 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. Specific examples of the alicyclic hydrocarbon group include the groups shown below: The bonding site can be at any position. TIFF0007813531000011.tif44168 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group, etc. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. Groups formed by combination include groups combining an aromatic hydrocarbon group with a chain hydrocarbon group (e.g., aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*), groups combining an alicyclic hydrocarbon group with a chain hydrocarbon group (e.g., alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), and groups combining an aromatic hydrocarbon group with a alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * represents a bonding site. The aromatic hydrocarbon group -alkanediyl group-* includes aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group, a xylyl group, and a cumenyl group. Examples of the alicyclic hydrocarbon group -alkanediyl group-* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl group. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group-* include a phenylcyclohexyl group. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include a cyclohexylphenyl group. In addition, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Furthermore, -CH2- contained in the cyclic hydrocarbon group or chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO-, or -SO2-. In the combined groups, any group may be bonded to the benzene ring.

[0014] Examples of groups in which -CH2- in a hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include a hydroxy group (a group in which -CH2- in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced by -O-), an alkylthio group (a group in which -CH2- at any position in an alkyl group is replaced by -S-), an alkoxycarbonyl group (a group in which -CH2- in an alkyl group is replaced by -S-), and Examples of the alkyl group include a group in which -CH-CH- at any position in the alkyl group is replaced with -O-CO-), an alkylsulfonyl group (a group in which -CH- at any position in the alkyl group is replaced with -SO-), an alkylcarbonyl group (a group in which -CH- at any position in the alkyl group is replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH-CH- at any position in the alkyl group is replaced with -CO-O-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, and a group in which two or more of these groups are combined. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. 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 still more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, etc. 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 still more preferably 1 to 3. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent groups in which a carbonyl group or carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl, propionyl, and butyryl. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy. 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 alkylcarbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and even more preferably 2 or 3 carbon atoms. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. 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 still more preferably 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. Furthermore, examples of groups in which -CH2- in an alicyclic hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2- include the groups shown below. Among the groups shown below, groups in which -O- is replaced with -S- and -CO- is replaced with -SO2- are also included. The bonding site can be at any position. When a -CH2- in a hydrocarbon group is replaced with -O- or -CO-, the total number of carbon atoms in the hydrocarbon group is the number of carbon atoms before the replacement. The number may be one or more.

[0015] m11, m12, and m13 are preferably 0 to 2, and more preferably 0.

[0016] Formula (R 10 -1), formula (R 10 -2) or formula (R 10 Examples of the group having a lactone ring group represented by -3) include the following groups. TIFF0007813531000013.tif46155R 1 , R 2 and R 3 is -O-CO-R 10 , -O-CO-OR 10 , -OL 1 -CO-OR 10 is preferably —O—CO—OR 10 -or-OL 1-CO-OR 10 It is more preferable that: R 1 , R 2 and R 3 The bond positions of X 1 , X 2 and X 3 The bonding position of X may be either o-position, m-position or p-position. 1 , X 2 and X 3 It is preferable that the bond is at the p-position relative to the bonding position of

[0017] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 The fluorinated alkyl group having 1 to 12 carbon atoms refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom, and examples thereof include perfluoroalkyl groups having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), as well as 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and still more preferably 1 to 4. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, and norbornyl. 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. Specific examples of the alicyclic hydrocarbon group include the groups shown below: The bonding site can be at any position. TIFF0007813531000014.tif44168 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group, etc. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. Groups formed by combination include groups combining an aromatic hydrocarbon group with a chain hydrocarbon group (e.g., aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*), groups combining an alicyclic hydrocarbon group with a chain hydrocarbon group (e.g., alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), and groups combining an aromatic hydrocarbon group with a alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * represents a bonding site. The aromatic hydrocarbon group -alkanediyl group-* includes aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group, a xylyl group, and a cumenyl group. Examples of the alicyclic hydrocarbon group -alkanediyl group-* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl group. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group-* include a phenylcyclohexyl group. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include a cyclohexylphenyl group. In addition, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Furthermore, -CH2- contained in the cyclic hydrocarbon group or chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO-, or -SO2-. In the combined groups, any group may be bonded to the benzene ring. Examples of groups in which -CH2- in a hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include a hydroxy group (a group in which -CH2- in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced by -O-), an alkylthio group (a group in which -CH2- at any position in an alkyl group is replaced by -S-), an alkoxycarbonyl group (a group in which -CH2- in an alkyl group is replaced by -S-), and Examples of the alkyl group include a group in which -CH-CH- at any position in the alkyl group is replaced with -O-CO-), an alkylsulfonyl group (a group in which -CH- at any position in the alkyl group is replaced with -SO-), an alkylcarbonyl group (a group in which -CH- at any position in the alkyl group is replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH-CH- at any position in the alkyl group is replaced with -CO-O-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, and a group in which two or more of these groups are combined. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. 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 still more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, etc. 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 still more preferably 1 to 3. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent groups in which a carbonyl group or carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. 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 still more preferably 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. Furthermore, examples of groups in which -CH2- in an alicyclic hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2- include the groups shown below. Among the groups shown below, groups in which -O- is replaced with -S- and -CO- is replaced with -SO2- are also included. The bonding site can be at any position. TIFF0007813531000015.tif47167When -CH2- in a hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-, the number of carbon atoms before the replacement is the total number of carbon atoms in the hydrocarbon group. In addition, the number may be 1 or 2 or more. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the substituent that the hydrocarbon group may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (-CH2- contained in the alkyl group may be replaced with -O- or -CO-). Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. When -CH2- in an alkyl group is replaced with -O- or -CO- as a substituent, the number of carbon atoms before the replacement is counted as the total number of carbon atoms in the alkyl group. Examples of the substituted group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group include the same groups as those described above. The hydrocarbon group may have one or more substituents.

[0018] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 3is preferably an oxygen atom. X 1 , X 2 and X 3 The bond position of S + The bonding position may be either o-position, m-position or p-position relative to the bonding position of S + It is preferably bonded at the p-position or m-position relative to the bonding position of (I), and more preferably at the p-position. m1 is preferably 0, 1 or 2, and more preferably 1. m2 is preferably 0 or 1. m3 is preferably 0 or 1. When m1 is 0 or 1, it is preferred that both m2 and m3 are 1. m4 is preferably 0, 1, 2 or 4. When m4 is 1 or 2, at least one R 4 The bonding position of X 1 When m4 is 2, one of R 4 The bonding position of X 1 and the other R 4 The bonding position of X 1 It is preferable that the bond is at the m-position relative to the bonding position of m5 is preferably 0, 1 or 2. When m5 is 1 or 2, at least one R 5 The bonding position of X 2 When m5 is 2, one of R 5 The bonding position of X 2 and the other R 5 The bonding position of X 2 It is preferable that the bond is at the m-position relative to the bonding position of m6 is preferably 0, 1 or 2. When m6 is 1 or 2, at least one R 6 The bonding position of X 3 When m6 is 2, one of R 6 The bonding position of X 3and the other R 6 The bonding position of X 3 It is preferable that the bond is at the m-position relative to the bonding position of m7 is preferably 0, 1 or 2, and more preferably 0 or 1. Preferably, m8 is 0 or 1. m9 is preferably 0 or 1. When m1+m2+m3 is 2 or more, the groups in the parentheses may be the same or different from each other. 1 ~X 3 When there are multiple of each, R 1 ~R 3 When there are multiple of each, R 4 ~R 6 When there are a plurality of each of these, they may be the same or different. R 4 , R 5 and R 6 are each independently preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms (wherein —CH2— contained in the alkyl group may be replaced with —O— or —CO—), more preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (wherein —CH2— contained in the alkyl group may be replaced with —O— or —CO—), and even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, or an alkyl group having 1 to 4 carbon atoms. R 7 , R 8 and R 9are each independently preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—), more preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—), still more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—), and even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxy group, or a methoxy group. R 7 , R 8 and R 9 When m2 is 0, R 8 The bonding position of S + The bonding position may be either o-position, m-position or p-position relative to the bonding position of S + It is more preferable that m3 is bonded to the p-position relative to the bonding position of R 9 The bonding position of S + The bonding position may be either o-position, m-position or p-position relative to the bonding position of S + It is more preferable that the bond is at the p-position relative to the bonding position of X 4 is preferably a single bond, -CH2-, -O-, or -CO-, more preferably a single bond or -CH2-, and even more preferably a single bond.

[0019] Examples of the cation of the salt (I) include cations represented by the following formulae (Ic-1) to (Ic-53). TIFF0007813531000016.tif230148

[0020] TIFF0007813531000017.tif169153

[0021] TIFF0007813531000018.tif171162

[0022] JPEG0007813531000019.jpg54148

[0023] JPEG0007813531000020.jpg226168

[0024] TIFF0007813531000021.tif234116

[0025] TIFF0007813531000022.tif138165

[0026] In formula (I), X 0 Examples of the hydrocarbon group represented by the formula (I) include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these, etc. -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkenyl group include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. Examples of groups in which -CH2- in a chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include a hydroxy group (a group in which -CH2- in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2- at any position in an alkyl group is replaced by -O-), and a hydroxyl group (a group in which -CH2- at any position in an alkyl group is replaced by -O-). Examples of such groups include alkyl groups in which -CH2-CH2- at any position is replaced with -O-CO-, alkylcarbonyl groups (groups in which -CH2- at any position in an alkyl group is replaced with -CO-), alkylsulfonyl groups (groups in which -CH2- at any position in an alkyl group is replaced with -SO2-), alkylcarbonyloxy groups (groups in which -CH2-CH2- at any position in an alkyl group is replaced with -CO-O-), and alkylthio groups (groups in which -CH2- at any position in an alkyl group is replaced with -S-). Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, and alkylthio group include the same groups as those described above. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, and propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4. The substitution in the alkenyl group or alkynyl group may be any of the substitutions in the alkyl group exemplified above, as long as it contains a carbon-carbon double bond or a carbon-carbon triple bond at any position. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl, and polycyclic cycloalkyl groups such as norbornyl and adamantyl. Specific examples of alicyclic hydrocarbon groups and groups in which -CH2- contained in an alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2- include the following groups. The bonding site can be at any position.

[0027] TIFF0007813531000023.tif84160

[0028] TIFF0007813531000024.tif38158As the alicyclic hydrocarbon group or a group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, groups represented by formulae (y1) to (y71) are preferred, and formulae (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), and formulae (y39) to (y71) are A group represented by any one of the following formulae is more preferred, and groups represented by formula (y3), (y4), formula (y9), formula (y11), formula (y14), formula (y15), formula (y16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), formulas (y49) to (y58), and formulas (y62) to (y71) are even more preferred. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, and still more preferably 3 to 16.

[0029] Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and still more preferably 6 to 10. In the case of a combined group, the above groups may contain groups with different valences (such as an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, a cycloalkanediyl group, a cycloalkanetriyl group, or a cycloalkanetetrayl group).

[0030] The combined groups are: a group comprising a combination of an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein —CH— contained in the chain hydrocarbon group or the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO—); a group comprising a combination of a chain hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and It represents a group formed by combining an alicyclic hydrocarbon group with an aromatic hydrocarbon group (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In addition, in the combination, two or more types of each of the alicyclic hydrocarbon group, the chain hydrocarbon group and the aromatic hydrocarbon group may be combined. Specifically, the combined groups include: Alicyclic hydrocarbon groups such as an adamantylmethylene group and a cyclohexylmethylene group - chain hydrocarbon group-*, (alicyclic hydrocarbon group)2-chain hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Chain hydrocarbon groups-alicyclic hydrocarbon groups-* such as methyladamantyl group and dimethyladamantyl group, (chain hydrocarbon group)2-alicyclic hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a chain hydrocarbon group such as a tolyl group or a xylyl group - an aromatic hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-* such as a methylcyclohexylmethylene group, (chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), an aromatic hydrocarbon group such as a benzyl group - a chain hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); a chain hydrocarbon group such as a tolylmethyl group-aromatic hydrocarbon group-chain hydrocarbon group-* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-*, such as methyladamantanemethyleneadamantyl group and di(methyladamantanemethylene)adamantyl group, (chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group)2-alicyclic hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-alicyclic hydrocarbon group-*, (chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group)2-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group-chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group)2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group-* (-CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Here, * indicates the bonding position with the carbon atom of the carbonyl group.

[0031] X 0 When -CH2- in the hydrocarbon group represented by the formula (I) is replaced by -O-, -S-, -CO- or -SO2-, the number of carbon atoms before the replacement is the total number of carbon atoms in the hydrocarbon group. 0 When a substituent is bonded to a hydrocarbon group represented by the formula: Figure imgf000012_0001, the number of carbon atoms before substitution is the total number of carbon atoms in the hydrocarbon group. X 0 The hydrocarbon group represented by the formula (I) may have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** indicates X 0 represents the bonding position with TIFF0007813531000025.tif17162 Examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms include aryl groups such as phenyl and naphthyl groups. Examples of the combined group include a group in which a hydroxy group is combined with an alkyl group having 1 to 12 carbon atoms, a group in which an alkyl group having 1 to 12 carbon atoms is combined with an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a group in which an alicyclic hydrocarbon group having 3 to 12 carbon atoms is combined with an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the group combining a hydroxy group with an alkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 12 carbon atoms, such as a hydroxymethyl group and a hydroxyethyl group. Examples of the group combining an alkyl group having 1 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as a benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as a tolyl group and a xylyl group. Examples of the group formed by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms include a cyclohexylphenyl group.

[0032] X 0 The hydrocarbon group represented by the formula (I) is preferably an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (-CH- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent; More preferred are alicyclic hydrocarbon groups which may have a hydroxy group or a fluorine atom (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), groups which combine an alicyclic hydrocarbon group with a chain hydrocarbon group (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-, and -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), aromatic hydrocarbon groups which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms, groups represented by formula (aa) or groups represented by formula (bb), More preferably, *-alicyclic hydrocarbon group (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * is -COO - represents the bonding position with the carbon atom of the formula (I), *-alicyclic hydrocarbon group-chain hydrocarbon group (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents -COO - represents the bonding position with the carbon atom of the formula (I), *-chain hydrocarbon group-alicyclic hydrocarbon group (-CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents -COO - represents the bonding position with the carbon atom of the formula (aa), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, * represents a polycyclic alicyclic hydrocarbon group (wherein —CH— contained in the polycyclic alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO—, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom). * represents —COO - represents the bonding position with the carbon atom of the formula (I), *-polycyclic alicyclic hydrocarbon group-chain hydrocarbon group (-CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents -COO - represents the bonding position with the carbon atom of the formula (I), *-chain hydrocarbon group-polycyclic alicyclic hydrocarbon group (-CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents -COO - represents the bonding position with the carbon atom of the formula (aa), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), Particularly preferred are an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group with an alkyl group (wherein the —CH2— contained in the alkyl group may be replaced with —O— or —CO—), a group represented by formula (Y30F), or a phenyl group having a hydroxy group. In the above groups, the alicyclic hydrocarbon group has preferably 3 to 36 carbon atoms, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16, and even more preferably 3 to 12. The chain hydrocarbon group has preferably 1 to 18 carbon atoms, more preferably 1 to 12, even more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4. The aromatic hydrocarbon group has preferably 6 to 36 carbon atoms, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. TIFF0007813531000026.tif26132[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * -COO - represents the bonding position with the carbon atom of [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO2-. R Arepresents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * -COO - represents the bonding position with the carbon atom of

[0033] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0034] X 1a and X 2a Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group combining two or more of these. These hydrocarbon groups may have a substituent. Furthermore, -CH2- contained in these hydrocarbon groups may be replaced with -O-, -S-, -CO-, or -SO2-. Here, the number of carbon atoms in the hydrocarbon group refers to the number of carbon atoms in the unsubstituted hydrocarbon group that does not have a substituent.

[0035] X 1a Examples of the aliphatic hydrocarbon group include chain hydrocarbon groups such as alkanetriyl groups, alicyclic hydrocarbon groups, and combinations thereof. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, a butanetriyl group, a pentanetriyl group, a hexanetriyl group, a heptanetriyl group, an octanetriyl group, a nonanetriyl group, a decanetriyl group, an undecanetriyl group, and a dodecanetriyl group.

[0036] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, and a cyclooctanetriyl group. Examples of the polycyclic alicyclic hydrocarbon group include a norbornanetriyl group and an adamantanetriyl group. Examples of the aromatic hydrocarbon group include a benzenetriyl group, a naphthalenetriyl group, and an anthracenetriyl group. In the case of a combined group, the above groups may contain groups with different valences (such as an alkyl group, an alkanediyl group, an alkanetetrayl group, a cycloalkyl group, a cycloalkanediyl group, or a cycloalkanetetrayl group).

[0037] X 1a The hydrocarbon group represented by the formula (I) has 1 to 24 carbon atoms and may further have one or more substituents. Examples of the substituents include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combinations thereof include the same groups as those described above.

[0038] X 1a The hydrocarbon group represented by the formula (w1-3) is preferably an alkanetriyl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alkanetriyl group having 1 to 6 carbon atoms or a group represented by any of formulas (w1-1) to (w1-11), and even more preferably an alkanetriyl group having 1 to 6 carbon atoms, a polycyclic hydrocarbon group such as a group represented by formula (w1-1) or a group represented by formula (w1-3), or a monocyclic hydrocarbon group such as a group represented by formula (w1-2) or a group represented by formula (w1-6). TIFF0007813531000027.tif46131 [Formula (w1-1) to formula (w1-11), The ring may have a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof. * indicates the bond position.]

[0039] X 2a The hydrocarbon group represented by the formula (I) preferably has 2 to 48 carbon atoms, more preferably 4 to 48 carbon atoms, even more preferably 6 to 44 carbon atoms, even more preferably 8 to 40 carbon atoms, and even more preferably 10 to 38 carbon atoms.

[0040] X 2a Examples of the substituent that the hydrocarbon group in the formula (I) may have include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combinations thereof include the same groups as those described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by the following formula may have one or more substituents.

[0041] X 2a Examples of the hydrocarbon group in include linear or branched chain hydrocarbon groups (for example, alkanediyl groups, etc.), monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and may be a combination of two or more of these groups. Specific examples include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group; branched alkanediyl groups such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; monocyclic alicyclic hydrocarbon groups such as monocyclic cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; polycyclic alicyclic hydrocarbon groups such as polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl; Examples of the aromatic hydrocarbon groups include a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a phenanthrylene group, and a binaphthylene group. In the case of a combined group, the above groups may contain groups with different valences (such as an alkyl group, an alkanetriyl group, an alkanetetrayl group, a cycloalkyl group, a cycloalkanetriyl group, or a cycloalkanetetrayl group). Examples of the combined group include a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined, a group in which a chain hydrocarbon group and an aromatic hydrocarbon group are combined, and a group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined. Specific examples include a group in which one or more alicyclic hydrocarbon groups are bonded to a chain hydrocarbon group (e.g., -chain hydrocarbon group-alicyclic hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group)2, etc.), a group in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (e.g., -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group)2, etc.), and a group in which one or more alicyclic hydrocarbon groups and chain hydrocarbon groups are bonded to a chain hydrocarbon group (e.g., -chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group-chain hydrocarbon group)2, etc.).

[0042] X 2a The hydrocarbon group in a chain hydrocarbon group having 2 to 18 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent); an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), or It is preferably a group (which may have a substituent) comprising a combination of a chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), a chain hydrocarbon group having 4 to 18 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent), or It is more preferable that the group is a combination of a chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-) (the group may have a substituent), a chain hydrocarbon group having 6 to 14 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent), or More preferably, it is a group (which may have a substituent) that combines a chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) with an alicyclic hydrocarbon group having 5 to 14 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-).

[0043] Specifically, X 2a The hydrocarbon group in an alkanediyl group having 2 to 18 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-); an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), or It is preferably a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkyl group may be replaced with -O- or -CO-), an alkanediyl group having 4 to 18 carbon atoms which may have a substituent (-CH- contained in the alkanediyl group may be replaced with -O- or -CO-); a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), It is more preferable that the alkyl group is a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkyl group may be replaced with -O- or -CO-), an alkanediyl group having 6 to 14 carbon atoms which may have a substituent (-CH- contained in the alkanediyl group may be replaced by -O- or -CO-); a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-) and an adamantanediyl group which may have a substituent (-CH2- contained in the adamantanediyl group may be replaced with -O- or -CO-), or It is more preferably a group consisting of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), an adamantanediyl group which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CH2- contained in the alkyl group may be replaced with -O- or -CO-).

[0044] Specifically, X 2a is the formula (X 2 -1), a group represented by the formula (X 2 -2), a group represented by the formula (X 2 -3) or a group represented by the formula (X 2 -4) is preferred. TIFF0007813531000028.tif34158[In the formula, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group combining two or more of these groups, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-, and the alkyl group and the alicyclic hydrocarbon group may have a substituent. * is X a and X b represents the bond position with The combined group may be a combination of one alkyl group and one alicyclic hydrocarbon group described above, or two or more of either one or two or more of both. In this case, the number of carbon atoms in the combined group is 39 or less, and preferably 37 or less.

[0045] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6xExamples thereof include an alkyl group having 1 to 6 carbon atoms (-CH2- contained in the alkyl group may be replaced with -O- or -CO-, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a substituent), or a combination of an alkyl group having 1 to 6 carbon atoms (-CH2- contained in the alkyl group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group and more preferably a group (which may have a substituent) combining a methoxy group, an adamantyl group (wherein —CH— may be replaced by —O— or —CO— and the adamantyl group may have a substituent), or an alkyl group having 1 to 6 carbon atoms (wherein —CH— may be replaced by —O— or —CO—).

[0046] In formula (bb), L A and L B Examples of the alkanediyl group having 1 to 6 carbon atoms include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and branched alkanediyl groups such as propane-1,2-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. The number of carbon atoms in the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group. When -CH2- in an alkanediyl group is replaced with -O- or -CO-, the number of carbon atoms before the replacement is the total number of carbon atoms in the alkanediyl group. Alkanediyl groups include hydroxy groups (a group in which -CH2- in a methyl group is replaced with -O-), carboxy groups (a group in which -CH2-CH2- in an ethyl group is replaced with -O-CO-), alkoxy groups (a group in which -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl groups (a group in which -CH2-CH2- at any position in an alkyl group is replaced with -O-CO-), alkylcarbonyl groups (a group in which -CH2- at any position in an alkyl group is replaced with -CO-), and alkylcarbonyloxy groups (a group in which -CH2- at any position in an alkyl group is replaced with -CO-). It may have an alkanediyloxy group (a group in which -CH- at any position contained in an alkanediyl group is replaced with -O-), an alkanediyloxycarbonyl group (a group in which -CH- at any position contained in an alkanediyl group is replaced with -O-CO-), an alkanediylcarbonyl group (a group in which -CH- at any position contained in an alkanediyl group is replaced with -CO-), or an alkanediylcarbonyloxy group (a group in which -CH-CH- at any position contained in an alkanediyl group is replaced with -CO-). Examples of the alkanediyloxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyloxy group, a butanediyloxy group, and a pentanediyloxy group. Examples of the alkanediyloxycarbonyl group include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanediyloxycarbonyl group, and a butanediyloxycarbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group, an ethylenecarbonyl group, a propanediylcarbonyl group, a butanediylcarbonyl group, and a pentanediylcarbonyl group. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, and a butanediylcarbonyloxy group. L A is preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, and more preferably an alkanediyl group having 1 to 3 carbon atoms which has a fluorine atom. L B is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0047] R A Examples of the hydrocarbon group in include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups formed by combining these. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. Examples of groups in which -CH2- in a chain hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylthio group, and an alkylsulfonyl group. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyl group and alkylthio group include an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, an alkylsulfonyl group having 1 to 17 carbon atoms and an alkylthio group having 1 to 17 carbon atoms, and examples thereof include the same groups as those described above. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl, adamantyl, and norbornyl. Specific examples of the alicyclic hydrocarbon group and the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2- include groups represented by the above formulae (y1) to (y71). The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16, and even more preferably 3 to 12. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, even more preferably 6 to 14, and still more preferably 6 to 10.

[0048] In the case of a combined group, the above groups may contain groups with different valences (such as an alkanediyl group, an alkanetriyl group, a cycloalkanediyl group, or a cycloalkanetriyl group). Groups formed by combination include groups combining an aromatic hydrocarbon group with a chain hydrocarbon group (e.g., aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*), groups combining an alicyclic hydrocarbon group with a chain hydrocarbon group (e.g., alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), and groups combining an aromatic hydrocarbon group with a alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * represents a bonding site. The aromatic hydrocarbon group -alkanediyl group-* includes aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group, a xylyl group, and a cumenyl group. Examples of the alicyclic hydrocarbon group -alkanediyl group-* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl group. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group-* include a phenyladamantyl group. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include an adamantylphenyl group. In the combination, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. B may be bound to In addition to the groups mentioned above, examples of groups in which -CH2- in a hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2- include cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, aromatic hydrocarbon group-carbonyloxy groups, and groups in which two or more of these groups are combined. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. When a -CH2- in a hydrocarbon group is replaced with -O-, -S-, -SO2-, or -CO-, the total number of carbon atoms in the hydrocarbon group is the number of carbon atoms before the replacement, which may be 1 or 2 or more.

[0049] R A Examples of the substituent that the hydrocarbon group may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (-CH2- contained in the alkyl group may be replaced with -O-, -S-, -CO- or -SO2-). Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. Examples of groups in which -CH2- in an alkyl group is replaced with -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, and alkylcarbonyloxy group include alkoxy groups having 1 to 11 carbon atoms, alkoxycarbonyl groups having 2 to 11 carbon atoms, alkylcarbonyl groups having 2 to 12 carbon atoms, and alkylcarbonyloxy groups having 2 to 11 carbon atoms, and include, for example, the same groups as those described above. R A The hydrocarbon group in may have one or more substituents.

[0050] R A The hydrocarbon group in is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent (provided that -CH2- contained in the alkyl group may be replaced with -O-, -S-, -CO- or -SO2-), or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), and more preferably a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms (provided that -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-).

[0051] Examples of the cyclic hydrocarbon group include cyclic hydrocarbon groups such as monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations of these groups. Examples of the alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group include the same groups as those described above. In the combination, two or more types of alicyclic hydrocarbon groups and two or more types of aromatic hydrocarbon groups may be combined. B may be bound to

[0052] A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms, and —CH— contained in the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO—, or —SO—) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-), or It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, It is more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms (-CH2- contained in the alicyclic hydrocarbon group may be replaced with -O- or -CO-). Preferred alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the following groups (the bonding site may be any position): and preferred aromatic hydrocarbon groups include phenyl and naphthyl groups. TIFF0007813531000029.tif1897

[0053] Examples of the carboxylate anion in the carboxylate salt represented by formula (I) include the carboxylate anions described below. TIFF0007813531000030.tif140165

[0054] TIFF0007813531000031.tif236168

[0055] TIFF0007813531000032.tif72168

[0056] TIFF0007813531000033.tif155165

[0057] TIFF0007813531000034.tif173160

[0058] Specific examples of the carboxylate (I) include salts of any combination of the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation, and "~" indicates that the carboxylate (I) corresponds to the anion (I). For example, carboxylate (I-1) is a salt consisting of an anion represented by formula (Ia-1) and a cation represented by formula (Ic-1), carboxylate (I-2) is a salt consisting of an anion represented by formula (Ia-2) and a cation represented by formula (Ic-1), and carboxylate (I-96) is a salt consisting of an anion represented by formula (Ia-1) and a cation represented by formula (Ic-2). TIFF0007813531000035.tif5479 [Table 1] JPEG0007813531000037.jpg73148

[0059] Among these, the carboxylate (I) is preferably a salt obtained by combining an anion represented by any one of formulas (Ia-1) to (Ia-5), (Ia-10) to (Ia-21), and (Ia-57) to (Ia-66) with a cation represented by any one of formulas (Ic-1) to (Ic-53), specifically, Carboxylate (I-1) to Carboxylate (I-5), Carboxylate (I-10) to Carboxylate (I-21), Carboxylate (I-57) to Carboxylate (I-66), Carboxylate (I-96) to Carboxylate (I-100), Carboxylate (I-105) to Carboxylate (I-116), Carboxylate (I-152) to Carboxylate (I-161), Carboxylate (I-191) to Carboxylate (I-195), Carboxylate (I-200) to Carboxylate (I-211), Carboxylate (I-247) to Carboxylate (I-256), Carboxylate (I-286) ~ Carboxylate (I-290), Carboxylate (I-295) ~ Carboxylate (I-306), Carboxylate (I-342) ~ Carboxylate (I-351), Carboxylate (I-381) ~ Carboxylate (I-385), Carboxylate (I-390) ~ Carboxylate (I-401), Carboxylate (I-437) ~ Carboxylate (I-446), Carboxylate (I-476) ~ Carboxylate (I-480), Carboxylate (I-485) ~ Carboxylate (I-496), Carboxylate (I-532) ~ Carboxylate (I -541), Carboxylate (I-571) ~ Carboxylate (I-575), Carboxylate (I-580) ~ Carboxylate (I-591), Carboxylate (I-627) ~ Carboxylate (I-636), Carboxylate (I-666) ~ Carboxylate (I-670), Carboxylate (I-675) ~ Carboxylate (I-686), Carboxylate (I-722) ~ Carboxylate (I-731), Carboxylate (I-761) ~ Carboxylate (I-765), Carboxylate (I-770) ~ Carboxylate (I-781), Carboxylate (I-817) ~ Carboxylate (I-826), Carboxylate (I-856) to Carboxylate (I-860), Carboxylate (I-865) to Carboxylate (I-876), Carboxylate (I-912) to Carboxylate (I-921), Carboxylate (I-951) to Carboxylate (I-955), Carboxylate (I-960) to Carboxylate (I-971), Carboxylate (I-1007) to Carboxylate (I-1016), Carboxylate (I-1046) to Carboxylate (I-1050), Carboxylate (I-1055) to Carboxylate (I-1066),Carboxylate (I-1102) ~ Carboxylate (I-1111), Carboxylate (I-1141) ~ Carboxylate (I-1145), Carboxylate (I-1150) ~ Carboxylate (I-1161), Carboxylate (I-1197) ~ Carboxylate (I-1206), Carboxylate (I-1236) ~ Carboxylate (I-1240), Carboxylate (I-1245) ~ Carboxylate (I-1256), Carboxylate (I-1292) ~ Carboxylate (I-1301), Carboxylate (I-1331) ~ Carboxylate (I-1335), Carboxylate ( I-1340) ~ Carboxylate (I-1351), I-1387) ~ I-1396, I-1426) ~ I-1430, I-1435 ~ I-1446, I-1482 ~ I-1491, I-1521 ~ I-1525, I-1530 ~ I-1541, I-1577 ~ I-1586, I-1616 ~ Carboxylate (I-1620), Carboxylate (I-1625) ~ Carboxylate (I-1636), Carboxylate (I-1672) ~ Carboxylate (I-1681), Carboxylate (I-1711) ~ Carboxylate (I-1715), Carboxylate (I-1720) ~ Carboxylate (I-1731), Carboxylate (I-1767) ~ Carboxylate (I-1776), Carboxylate (I-1806) ~ Carboxylate (I-1810), Carboxylate (I-1815) ~ Carboxylate (I-1826), Carboxylate (I-1862) ~ Carboxylate ( I-1871), Carboxylate (I-1901) ~ Carboxylate (I-1905), Carboxylate (I-1910) ~ Carboxylate (I-1921), Carboxylate (I-1957) ~ Carboxylate (I-1966), Carboxylate (I-1996) ~ Carboxylate (I-2000), Carboxylate (I-2005) ~ Carboxylate (I-2016), Carboxylate (I-2052) ~ Carboxylate (I-2061), Carboxylate (I-2091) ~ Carboxylate (I-2095), Carboxylate (I-2100) ~ Carboxylate (I-2111),Carboxylate (I-2147) ~ Carboxylate (I-2156), Carboxylate (I-2186) ~ Carboxylate (I-2190), Carboxylate (I-2195) ~ Carboxylate (I-2206), Carboxylate (I-2242) ~ Carboxylate (I-2251), Carboxylate (I-2281) ~ Carboxylate (I-2285), Carboxylate (I-2290) ~ Carboxylate (I-2301), Carboxylate (I-2337) ~ Carboxylate (I-2346), Carboxylate (I-2376) ~ Carboxylate (I-2380), Carboxylate ( Carboxylate (I-2385) ~ Carboxylate (I-2396), Carboxylate (I-2432) ~ Carboxylate (I-2441), Carboxylate (I-2471) ~ Carboxylate (I-2475), Carboxylate (I-2480) ~ Carboxylate (I-2491), Carboxylate (I-2527) ~ Carboxylate (I-2536), Carboxylate (I-2566) ~ Carboxylate (I-2570), Carboxylate (I-2575) ~ Carboxylate (I-2586), Carboxylate (I-2622) ~ Carboxylate (I-2631), Carboxylate (I-2661) ~ Carboxylate (I-2665), Carboxylate (I-2670) ~ Carboxylate (I-2681), Carboxylate (I-2717) ~ Carboxylate (I-2726), Carboxylate (I-2756) ~ Carboxylate (I-2760), Carboxylate (I-2765) ~ Carboxylate (I-2776), Carboxylate (I-2812) ~ Carboxylate (I-2821), Carboxylate (I-2851) ~ Carboxylate (I-2855), Carboxylate (I-2860) ~ Carboxylate (I-2871), Carboxylate (I-2907) ~ Carboxylate ( I-2916), Carboxylate (I-2946) ~ Carboxylate (I-2950), Carboxylate (I-2955) ~ Carboxylate (I-2966), Carboxylate (I-3002) ~ Carboxylate (I-3011), Carboxylate (I-3041) ~ Carboxylate (I-3045), Carboxylate (I-3050) ~ Carboxylate (I-3061), Carboxylate (I-3097) ~ Carboxylate (I-3106), Carboxylate (I-3136) ~ Carboxylate (I-3140), Carboxylate (I-3145) ~ Carboxylate (I-3156),Carboxylate (I-3192) ~ Carboxylate (I-3201), Carboxylate (I-3231) ~ Carboxylate (I-3235), Carboxylate (I-3240) ~ Carboxylate (I-3251), Carboxylate (I-3287) ~ Carboxylate (I-3296), Carboxylate (I-3326) ~ Carboxylate (I-3330), Carboxylate (I-3335) ~ Carboxylate (I-3346), Carboxylate ( I-3382) ~ Carboxylate (I-3391), I-3421 ~ I-3425, I-3430 ~ I-3441, I-3477 ~ I-3486, I-3516 ~ I-3520, I-3525 ~ I-3536, I-3572 ~ Carboxylate (I-3581), Carboxylate (I-3611) ~ Carboxylate (I-3615), Carboxylate (I-3620) ~ Carboxylate (I-3631), Carboxylate (I-3667) ~ Carboxylate (I-3676), Carboxylate (I-3706) ~ Carboxylate (I-3710), Carboxylate (I-3715) ~ Carboxylate (I-3726), Carboxylate (I-3762) ~ Carboxylate ( I-3771), Carboxylate (I-3801) ~ Carboxylate (I-3805), Carboxylate (I-3810) ~ Carboxylate (I-3821), Carboxylate (I-3857) ~ Carboxylate (I-3866), Carboxylate (I-3896) ~ Carboxylate (I-3900), Carboxylate (I-3905) ~ Carboxylate (I-3916), Carboxylate (I-3952) ~ Carboxylate (I-3961), Carboxylate (I-3991) to Carboxylate (I-3995), Carboxylate (I-4000) to Carboxylate (I-4011), Carboxylate (I-4047) to Carboxylate (I-4056), Carboxylate (I-4086) to Carboxylate (I-4090), Carboxylate (I-4095) to Carboxylate (I-4106), Carboxylate (I-4142) to Carboxylate (I-4151), Carboxylate (I-4181) to Carboxylate (I-4185), Carboxylate (I-4190) to Carboxylate (I-4201), Carboxylate (I -4237) ~ Carboxylate (I-4246), Carboxylate (I-4276) ~ Carboxylate (I-4280), Carboxylate (I-4285) ~ Carboxylate (I-4296), Carboxylate (I-4332) ~ Carboxylate (I-4341), Carboxylate (I-4371) ~ Carboxylate (I-4375), Carboxylate (I-4380) ~ Carboxylate (I-4391), Carboxylate (I-4427) ~ Carboxylate (I-4436), Carboxylate (I-4466) ~ Carboxylate (I-4470), Carboxylate (I-4475) ~ Carboxylate Carboxylate (I-4486), Carboxylate (I-4522) to Carboxylate (I-4531), Carboxylate (I-4561) to Carboxylate (I-4565), Carboxylate (I-4570) to Carboxylate (I-4581), Carboxylate (I-4617) to Carboxylate (I-4626), Carboxylate (I-4656) to Carboxylate (I-4660), Carboxylate (I-4665) to Carboxylate (I-4676), Carboxylate (I-4712) to Carboxylate (I-4721), Carboxylate (I-4751) to Carboxylate (I-47 55), Carboxylate (I-4760) to Carboxylate (I-4771), Carboxylate (I-4807) to Carboxylate (I-4816), Carboxylate (I-4846) to Carboxylate (I-4850), Carboxylate (I-4855) to Carboxylate (I-4866), Carboxylate (I-4902) to Carboxylate (I-4911), Carboxylate (I-4941) to Carboxylate (I-4945), Carboxylate (I-4950) to Carboxylate (I-4961), Carboxylate (I-4997) to Carboxylate (I-5006) are preferred.

[0060] <Method for producing salt (I)> The salt (I) can be produced by reacting a salt represented by formula (Ia) with a salt represented by formula (Ib) in a solvent. TIFF0007813531000038.tif82157 [wherein all symbols have the same meanings as defined above.] R A , R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A , R B and R C may combine to form an aromatic ring. D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.] Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0061] The salt represented by formula (Ib) can be synthesized with reference to the methods described in JP-A Nos. 2011-39502 and 2014-88367, and examples thereof include salts represented by the following formulas. TIFF0007813531000039.tif131160

[0062] In the salt (Ia), R 1 , R 2 and R 3 But, -OL 1 -CO-OR 10 The salt represented by formula (I-a1) can be produced by reacting a salt represented by formula (Ic) with a compound represented by formula (Id) in a solvent in the presence of a base catalyst. TIFF0007813531000040.tif78165 [wherein all symbols have the same meanings as defined above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, and triethylamine. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0063] Examples of compounds represented by formula (Id) include the compounds represented below, which are readily available on the market and can also be easily produced by known production methods. TIFF0007813531000041.tif20164

[0064] The salt represented by formula (Ic) can be produced by reacting the salt represented by formula (Ie), a compound represented by formula (I-f1), a compound represented by formula (I-f2), and a compound represented by formula (I-f3) in a solvent in the presence of a catalyst. TIFF0007813531000042.tif79161 [wherein all symbols have the same meanings as defined above.] Examples of the catalyst include potassium carbonate and sodium hydride. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually 15° C. to 100° C., and the reaction time is usually 0.5 to 24 hours.

[0065] Examples of the salt represented by formula (Ie) include salts represented by the following formula, which are readily available on the market. TIFF0007813531000043.tif62161

[0066] Examples of the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) include the compounds represented below, which are easily available on the market. TIFF0007813531000044.tif20104

[0067] The salt represented by formula (Ic) can also be produced by reacting the salt represented by formula (Ie), a compound represented by formula (I-f4), a compound represented by formula (I-f5), and a compound represented by formula (I-f6) in a solvent in the presence of potassium carbonate, followed by acid treatment. TIFF0007813531000045.tif135153 [wherein all symbols have the same meanings as defined above.] R ac represents an acid labile group. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually 15° C. to 100° C., and the reaction time is usually 0.5 to 24 hours. The acid includes p-toluenesulfonic acid, hydrochloric acid, and the like.

[0068] Examples of the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) include the compounds represented below, which are easily available on the market. TIFF0007813531000046.tif89155

[0069] In the salt (Ia), R 1 , R 2 and R 3 But -O-CO-R 10 The salt represented by formula (I-a2) can be produced by reacting a salt represented by formula (Ic) with a compound represented by formula (I-d2) in a solvent in the presence of a base catalyst. TIFF0007813531000047.tif77163 [wherein all symbols have the same meanings as defined above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, and triethylamine. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0070] Examples of compounds represented by formula (I-d2) include the compounds represented by the following formulas, which are readily available on the market and can also be easily produced by known production methods. TIFF0007813531000048.tif23159

[0071] In the salt (Ia), R 1 , R 2 and R 3 But, -OR 10 The salt represented by formula (I-a3) can be produced by reacting a salt represented by formula (Ic) with a compound represented by formula (I-d3) in a solvent in the presence of a base catalyst. TIFF0007813531000049.tif79160 [wherein all symbols have the same meanings as defined above.] Examples of the base include sodium hydroxide and potassium hydroxide. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0072] Examples of compounds represented by formula (I-d3) include the compounds represented by the following formulas, which are readily available on the market and can also be easily produced by known production methods. TIFF0007813531000050.tif22144

[0073] In the salt (Ia), R 1 , R 2 and R 3 But, -O-CO-OR 10The salt represented by formula (I-a4) can be produced by reacting a salt represented by formula (Ic) with a compound represented by formula (I-d3) in a solvent in the presence of carbonyldiimidazole. TIFF0007813531000051.tif74163 [wherein all symbols have the same meanings as defined above.] Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0074] [Carboxylic Acid Generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylic acid salt (I). The carboxylic acid salt (I) of the present invention can act as an acid generator in a resist composition. When the carboxylic acid salt (I) is used as an acid generator in a resist composition, the acid generator may contain only one type of carboxylic acid salt (I) or two or more types of carboxylic acid salts (I). Furthermore, as will be described later, the acid generator of the present invention may further contain an acid generator other than the carboxylate (I) that is known in the resist field (hereinafter, sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator other than the carboxylate (I) that is known in the resist field. The acid generator (B) may be used alone or in combination of two or more kinds. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the content of the carboxylic acid salt (I) to the content of the acid generator (B) or the like (mass ratio; carboxylic acid salt (I):acid generator (B)) or the like is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and even more preferably 5:95 to 95:5.

[0075] [Resist Composition] The resist composition contains a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention, an acid generator (B) other than the carboxylic acid salt (I), and a resin having an acid labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid labile group" refers to a group that has a leaving group and that is eliminated upon contact with an acid to form a hydrophilic group (e.g., a hydroxy group or a carboxy group). The resist composition may further contain a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). In the resist composition of the present invention, the content of the carboxylate (I) is preferably from 0.1 to 35% by mass, more preferably from 0.5 to 30% by mass, and even more preferably from 1 to 25% by mass, relative to the solid content of the resist composition.

[0076] <Acid generator (B)> The acid generator (B) may be either nonionic or ionic. Nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Anions of onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0077] The acid generator (B) may be a compound that generates an acid when exposed to radiation, as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, or European Patent No. 126,712. Compounds produced by known methods may also be used. Two or more types of acid generator (B) may be used in combination.

[0078] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007813531000052.tif2962[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and wherein a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation.

[0079] Q b1 and Q b2Examples of the perfluoroalkyl group represented by the formula (I) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Q b1 and Q b2 and are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0080] L b1 Examples of the divalent saturated hydrocarbon group in include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and may also be a group formed by combining two or more of these groups. Specific examples include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; branched alkanediyl groups such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0081] L b1 Examples of the divalent saturated hydrocarbon group represented by the formula (b1-1) in which one -CH2- is replaced with -O- or -CO- include groups represented by any of formulas (b1-1) to (b1-3). In the groups represented by formulas (b1-1) to (b1-3) and specific examples thereof, groups represented by formulas (b1-4) to (b1-11), * and ** represent bonding positions, and * represents bonding position to -Y.

[0082] TIFF0007813531000053.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b4 and L b5The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0083] In the groups represented by formulae (b1-1) to (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group.

[0084] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b7is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-.

[0085] L b1 As the divalent saturated hydrocarbon group represented by the formula (b1-1) or (b1-3), in which one --CH.sub.2-- contained in the group is replaced by --O-- or --CO--, a group represented by the formula (b1-1) or (b1-3) is preferred.

[0086] Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8). TIFF0007813531000054.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b11 and L b12The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0087] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0088] Examples of the group represented by formula (b1-3) include groups represented by formulas (b1-9) to (b1-11). TIFF0007813531000055.tif23140[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0089] In addition, in the groups represented by formulae (b1-9) to (b1-11), when a hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0090] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

[0091] Examples of the group represented by formula (b1-4) include the following. TIFF0007813531000056.tif16154

[0092] Examples of the group represented by formula (b1-5) include the following. TIFF0007813531000057.tif68152

[0093] Examples of the group represented by formula (b1-6) include the following. TIFF0007813531000058.tif32164

[0094] Examples of the group represented by formula (b1-7) include the following. TIFF0007813531000059.tif57146

[0095] Examples of the group represented by formula (b1-8) include the following. TIFF0007813531000060.tif23150

[0096] Examples of the group represented by formula (b1-2) include the following. TIFF0007813531000061.tif31161

[0097] Examples of the group represented by formula (b1-9) include the following. TIFF0007813531000062.tif44137

[0098] Examples of the group represented by formula (b1-10) include the following. TIFF0007813531000063.tif92165

[0099] Examples of the group represented by formula (b1-11) include the following. TIFF0007813531000064.tif84164

[0100] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulae (Y1) to (Y11) and (Y36) to (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced with -O-, -SO2- or -CO-, the number may be 1 or 2 or more. Examples of such groups include groups represented by formulae (Y12) to (Y35) and formulae (Y39) to (Y43). * represents L b1 represents the bonding position with

[0101] The alicyclic hydrocarbon group represented by TIFF0007813531000065.tif83168Y is preferably a group represented by any one of formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), and (Y39) to (Y43), and more preferably a group represented by formula (Y11), (Y15), (Y16), (Y20), or (Y43). Preferred are groups represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43), and more preferred are groups represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring such as those of formulae (Y28) to (Y35), (Y39), (Y40), (Y42), and (Y43), the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, it is preferred that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

[0102] The substituent of the methyl group represented by Y is a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents an integer of 0 to 4. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S(O)2-, or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom. Substituents of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted with a hydroxy group (-CH2- contained in the alkyl group may be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents an integer of 0 to 4. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2-, or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.

[0103] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group. The alicyclic hydrocarbon group may have a chain hydrocarbon group, such as a methylcyclohexyl group or a dimethylcyclohexyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl, xylyl, cumenyl, mesityl, p-methylphenyl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-cyclohexylphenyl and p-adamantylphenyl). The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of groups in which -CH2- in an alkyl group is replaced by -O-, -SO2-, -CO-, etc. include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a combination thereof. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. The alkylsulfonyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. The alkoxycarbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. The alkylcarbonyloxy group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. Examples of the combined group include a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, and a group combining an alkoxy group and an alkylcarbonyloxy group. Examples of the group combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group, etc. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of a group formed by combining an alkoxy group with another alkoxy group include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, etc. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group, etc. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, an ethoxypropionyloxy group, etc. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group in which -CH2- in the alicyclic hydrocarbon group is replaced by -O-, -SO2-, -CO- or the like include groups represented by formulae (Y12) to (Y35) and formulae (Y39) to (Y43).

[0104] Examples of Y include the following: TIFF0007813531000066.tif150158

[0105] Y is preferably an alicyclic hydrocarbon group of 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group of 3 to 20 carbon atoms which may have a substituent, even more preferably an alicyclic hydrocarbon group of 3 to 18 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group substituted with a hydroxy group, and even more preferably an adamantyl group which may have a substituent, wherein -CH2- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced with -CO-, -SO2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by formula (Y42) or formula (Y100) to formula (Y114), and particularly preferably a hydroxyadamantyl group, an oxoadamantyl group, a group containing these, or a group represented by formula (Y42) or formula (Y100) to formula (Y114).

[0106] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-59) (hereinafter, sometimes referred to as "anion (B1-A-1)" depending on the formula number).), and more preferably an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), and formula (B1-A-47) to formula (B1-A-59).

[0107] TIFF0007813531000067.tif74143

[0108] TIFF0007813531000068.tif115156

[0109] TIFF0007813531000069.tif97155

[0110] TIFF0007813531000070.tif160156

[0111] TIFF0007813531000071.tif165161

[0112] where R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. i8 is, for example, a chain 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 combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 Q is a single bond or an alkanediyl group having 1 to 4 carbon atoms. b1 and Q b2 has the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

[0113] Preferred anions in the salt represented by formula (B1) include the anions represented by formulas (B1a-1) to (B1a-38). TIFF0007813531000072.tif206152

[0114] TIFF0007813531000073.tif165155

[0115] Of these, anions represented by any one of formulae (B1a-1) to (B1a-3), (B1a-7) to (B1a-19), and (B1a-22) to (B1a-38) are preferred.

[0116] Z1 +Examples of the organic cation 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 arylsulfonium cations are more preferred. Specific examples include cations represented by any of formulas (b2-1) to (b2-4) (hereinafter, sometimes referred to as "cation (b2-1)" depending on the formula number). TIFF0007813531000074.tif47166In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represent 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, a hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy 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, a hydrogen atom contained 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, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached, and -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5; When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, multiple Rb8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached, and -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. R b11 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 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, and a hydrogen atom contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a hydrogen atom 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. R b11 and R b12 may be bonded to each other to form a ring including the -CH-CO- to which they are bonded, and -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy 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. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, and when r2 is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 are the same or different, and when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, and norbornyl groups, as well as the following groups: TIFF0007813531000075.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, and more preferably has 4 to 12 carbon atoms. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornyl group, an isobornyl group, etc. In the alicyclic hydrocarbon group 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. The fluorinated alkyl group refers to an alkyl group having 1 to 12 carbon atoms and a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluorobutyl group, etc. 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. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenyl, naphthyl, and phenanthryl. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-cyclohexylphenyl and p-adamantylphenyl). When 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 hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl groups. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 and bond to each other together with the sulfur atom to which they are bonded to form a ring which may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Furthermore, the ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring, for example, the following rings. * represents a bonding position. TIFF0007813531000076.tif23144R b9 and R b10 The ring formed by these together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples thereof include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. R b11 and R b12 The ring formed by combining these may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of this ring include a 3- to 12-membered ring, and preferably a 3- to 7-membered ring. Examples include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

[0117] Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferred. Examples of the cation (b2-1) include the following cations. TIFF0007813531000077.tif79158

[0118] TIFF0007813531000078.tif109165

[0119] Examples of the cation (b2-2) include the following cations. TIFF0007813531000079.tif18150

[0120] Examples of the cation (b2-3) include the following cations. TIFF0007813531000080.tif25122

[0121] Examples of the cation (b2-4) include the following cations. TIFF0007813531000081.tif127166

[0122] The acid generator (B) is a combination of the above-mentioned anions and the above-mentioned organic cations, which can be combined arbitrarily. Preferred examples of the acid generator (B) include a combination of an anion represented by any of formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-38) with a cation (b2-1), a cation (b2-3), or a cation (b2-4).

[0123] The acid generator (B) is preferably one represented by formulas (B1-1) to (B1-56), of which those containing an arylsulfonium cation 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), and (B1-31) to (B1-56) are particularly preferred. TIFF0007813531000082.tif98162

[0124] TIFF0007813531000083.tif119163

[0125] TIFF0007813531000084.tif125162

[0126] TIFF0007813531000085.tif125161

[0127] TIFF0007813531000086.tif98130

[0128] TIFF0007813531000087.tif92158

[0129] In the resist composition of the present invention, the content of the acid generator (B) relative to 100 parts by mass of the resin (A) is preferably from 1 to 45 parts by mass, more preferably from 1 to 40 parts by mass, and even more preferably from 3 to 35 parts by mass. The resist composition of the present invention may contain one type of acid generator (B) alone, or may contain multiple types.

[0130] <Resin (A)> Resin (A) has a structural unit having an acid labile group (hereinafter sometimes referred to as "structural unit (a1)"). Resin (A) preferably further contains a structural unit other than structural unit (a1). Examples of structural units other than structural unit (a1) include a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (s)"), structural units other than structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom (hereinafter sometimes referred to as "structural unit (a4)") described below, a structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)") described below, and other structural units derived from monomers known in the art.

[0131] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid labile group contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter also referred to as group (2)). TIFF0007813531000088.tif2397 [In formula (1), R a1 , R a2 and R a3 each 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 any of these; or R a1 and R a2 are bonded to each other to form, together with the carbon atoms to which they are bonded, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates the bond position.] TIFF0007813531000089.tif2379 [In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form, together with the carbon atom to which they are bonded and X, a heterocyclic group having 3 to 20 carbon atoms, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced with -O- or -S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0132] R a1 , R a2 and R a3 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3Examples of the alkenyl group in the formula (I) include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either 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, and norbornyl groups, as well as the following groups (where * represents a bond): a1 , R a2 and R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms. TIFF0007813531000090.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (e.g., a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (e.g., a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3) includes the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding position with -O-. TIFF0007813531000091.tif31135

[0133] R a1’ , R a2’ and R a3’ Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 Examples of the groups include the same as those listed in the above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group with an alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group (such as a benzyl group), an aromatic hydrocarbon group having an alkyl group (such as a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, or a 2-methyl-6-ethylphenyl group), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (such as a p-cyclohexylphenyl group or a p-adamantylphenyl group), and an alicyclic hydrocarbon group having an aromatic hydrocarbon group (such as a phenylcyclohexyl group). R a2’ and R a3’ When they are bonded to each other to form a heterocyclic group together with the carbon atoms to which they are bonded and X, -C(R a1’ )(R a2’ )-XR a3’ Examples of the group include the following: * represents the bonding position. TIFF0007813531000092.tif21142R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0134] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and na=1. The group is preferably a tert-butoxycarbonyl group. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, and R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group, and R a3 is an adamantyl group, ma=0, and na=1. Specific examples of the group (1) include the following: * represents a bond. TIFF0007813531000093.tif154163

[0135] Specific examples of group (2) include the following groups: * represents the bonding position. TIFF0007813531000094.tif55153

[0136] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid labile group.

[0137] Of the (meth)acrylic monomers having an acid labile group, preferred are those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. When a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, the resolution of the resist pattern can be improved.

[0138] Examples of structural units derived from a (meth)acrylic monomer having group (1) include a structural unit represented by formula (a1-0) (hereinafter, sometimes referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter, sometimes referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter, sometimes referred to as structural unit (a1-2)). Preferably, at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2) is used. These may be used alone or in combination of two or more. TIFF0007813531000095.tif42142 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or * -O-(CH2) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a01 , R a4 and R a5 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. R a02 , R a03 and R a04 each 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. R a6 and R a7 each 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 combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0139] R a01 , Ra4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 It is —CO—O— (wherein k01 is preferably an integer of any one of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04 The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and combination thereof in the formula (1) include R a1 ~R a3 Examples of the groups include the same groups as those listed in the above. R a6 and R a7 The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and combinations thereof in the formula (1) include R a1 , R a2 and R a3 Examples of the groups include the same groups as those listed in the above. R a02 , R a03 , and R a04 The alkyl group in the formula (I) 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. R a6 and R a7 The alkyl group in the formula (I) 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. R a6 and R a7 The alkenyl group in the formula (I) 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. R a02 , R a03 and R a04The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms. R a02 , R a03 , R a04 , R a6 and R a7 The aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. In the group in which an alkyl group and an alicyclic hydrocarbon group are combined, the total number of carbon atoms in the combination of the alkyl group and the alicyclic hydrocarbon group is preferably 18 or less. In the group in which an alkyl group and an aromatic hydrocarbon group are combined, the total number of carbon atoms in the combination of the alkyl group and the aromatic hydrocarbon group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group, or a naphthyl group, and even more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, or a phenyl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0140] Examples of the structural unit (a1-0) include structural units represented by any one of formulas (a1-0-1) to (a1-0-18) and Ra01 and structural units in which the methyl group corresponding to the formula (a1-0-1) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group, and structural units represented by any of formulas (a1-0-1) to (a1-0-10), (a1-0-13) and (a1-0-14) are preferred. TIFF0007813531000096.tif99159

[0141] Examples of the structural unit (a1-1) include structural units derived from monomers described in JP-A-2010-204646. Among these, structural units represented by any one of formulas (a1-1-1) to (a1-1-7) and R in the structural unit (a1-1) are preferred. a4 A structural unit in which a methyl group corresponding to the formula (a1-1-1) is replaced with a hydrogen atom is preferred, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferred. TIFF0007813531000097.tif39167

[0142] The structural unit (a1-2) includes a structural unit represented by any one of formulas (a1-2-1) to (a1-2-14) and R a5 and structural units in which the methyl group corresponding to the formula (a1-2-1) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-14) are preferred. TIFF0007813531000098.tif67163

[0143] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 60 mol %, preferably 5 to 50 mol %, and more preferably 10 to 40 mol %, based on all structural units in the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, even more preferably 20 to 80 mol%, and still more preferably 20 to 75 mol%, based on all structural units in the resin (A).

[0144] An example of the structural unit (a1) having the group (2) is a structural unit represented by formula (a1-4) (hereinafter, sometimes referred to as "structural unit (a1-4)"). TIFF0007813531000099.tif3954[In formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -R a32 represents the bonding site with the carbon atom to which it is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents an integer of 0 to 4. When la is an integer of 2 or more, a plurality of R a33 may be the same or different from each other. R a34 and R a35each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form, together with the -CO- to which they are bonded, a divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group and the -CH2- contained in the divalent hydrocarbon group may be replaced with -O- or -S-.]

[0145] R a32 and R a33 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, and a bromine atom. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in the formula (I) include 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, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a32 is preferably 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. R a33 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. R a33 Examples of the alkoxy group in include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. Ra33 Examples of the alkoxyalkyl group in the formula (I) include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a 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. R a33 Examples of the alkoxyalkoxy group in include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in the formula (I) include an acetyl group, a propionyl group, a butyryl group, etc. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in the formula (I) include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy 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 hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0146] *-X a31 -(A a32 -X a32 ) nc-Examples include *-O-, *-CO-O-, *-O-CO-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, and *-CO-O- and *-CO-OA are particularly mentioned. a32 -CO-O- or *-OA a32 -CO-O- is preferred.

[0147] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0148] A a30 is a single bond, *-CO-O- or *-CO-OA a32 -CO-O- is preferred, a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0149] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these groups are combined. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either 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, and norbornyl groups, as well as the following groups (* indicates a bonding site): TIFF0007813531000100.tif10151 Examples of aromatic hydrocarbon groups include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (such as a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, or a 2-methyl-6-ethylphenyl group), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (such as a p-cyclohexylphenyl group or a p-adamantylphenyl group), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. a36 Examples of the group include 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 combining these.

[0150] R a34 is preferably a hydrogen atom. R a35 is preferably 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. R a36 The hydrocarbon group in R 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 combining these, 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. a36The alkyl group and alicyclic hydrocarbon group in R are preferably unsubstituted. a36 The aromatic hydrocarbon group in is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0151] -OC(R a34 )(R a35 )-OR a36 is eliminated on contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-OR a36 is preferably bonded to the o- or p-position of the benzene ring, more preferably to the p-position.

[0152] Examples of the structural unit (a1-4) include structural units derived from monomers described in JP-A-2010-204646. Preferably, the structural units represented by formulas (a1-4-1) to (a1-4-18) and R in the structural unit (a1-4) are a32 and more preferably, the structural units represented by formulas (a1-4-1) to (a1-4-5), (a1-4-10), (a1-4-13), and (a1-4-14), respectively. TIFF0007813531000101.tif100157 When the resin (A) has the structural unit (a1-4), the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on the total of all structural units in the resin (A).

[0153] Examples of the structural unit derived from a (meth)acrylic monomer having the group (2) include a structural unit represented by formula (a1-5) (hereinafter, sometimes referred to as "structural unit (a1-5)"). TIFF0007813531000102.tif4354 formula (a1-5), R a8represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 represents an integer of 1 to 4, * represents L 51 represents the bonding position with L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0154] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group, and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0155] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among these, the structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and the structural unit represented by formula (a1-5-1) or (a1-5-2) is more preferred. TIFF0007813531000103.tif34138 When the resin (A) has the structural unit (a1-5), the content thereof is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, even more preferably 5 to 40 mol %, and even more preferably 5 to 30 mol %, based on the total structural units of the resin (A).

[0156] Further, examples of the structural unit (a1) include the following structural units. When the resin (A) contains the above structural unit, the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on all structural units in the resin (A).

[0157] <Structural unit(s)> The structural unit (s) is derived from a monomer (hereinafter sometimes referred to as "monomer (s)") that does not have an acid labile group. As the monomer from which the structural unit (s) is derived, a monomer that does not have an acid labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using a resin having a structural unit that has a hydroxy group but no acid labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit that has a lactone ring but no acid labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and adhesion to the substrate can be improved.

[0158] <Structural unit (a2)> The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, if a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet) is used as an exposure light source, the structural unit (a2) preferably has a phenolic hydroxy group, and more preferably the structural unit (a2-A) described below. Furthermore, if an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) preferably has an alcoholic hydroxy group, and more preferably the structural unit (a2-1) described below. The structural unit (a2) may contain one type alone or two or more types.

[0159] In the structural unit (a2), the structural unit having a phenolic hydroxy group includes a structural unit represented by formula (a2-A) (hereinafter, sometimes referred to as "structural unit (a2-A)"). TIFF0007813531000105.tif4348[In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 represents the bond position with the carbon atom to which it is bonded. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different from each other.]

[0160] R a50 and R a51 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in the formula (I) include 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, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably 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. R a51 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51Examples of the alkoxyalkyl group in the formula (I) include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a 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. R a51 Examples of the alkoxyalkoxy group in include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in the formula (I) include an acetyl group, a propionyl group, a butyryl group, etc. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group in the formula (I) include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy 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 hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0161] *-X a51 -(A a52 -X a52 ) nb-Examples include *-O-, *-CO-O-, *-O-CO-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, and *-CO-O- and *-CO-OA are particularly mentioned. a52 -CO-O- or *-OA a52 -CO-O- is preferred. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- is preferred, a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred. mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho- or para-position of the benzene ring, more preferably to the para-position.

[0162] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A Nos. 2010-204634 and 2012-12577. The structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-16) and R in the structural unit (a2-A) in the structural units represented by formulas (a2-2-1) to (a2-2-16). a50The structural unit (a2-A) includes a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to (a2-2-14), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to (a2-2-14), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to (a2-2-14), a50 In the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), the structural unit represented by formula (a2-2-12) to formula (a2-2-14), and the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), and the structural unit represented by formula (a2-2-12) to formula (a2-2-14), R in the structural unit (a2-A) a50 In the structural unit represented by formula (a2-2-8), R in the structural unit (a2-A) is more preferably a structural unit represented by formula (a2-2-8) in which a methyl group corresponding to the structural unit represented by formula (a2-2-8) is replaced with a hydrogen atom. a50 More preferably, the structural unit is a structural unit in which a methyl group corresponding to the following formula is replaced with a hydrogen atom: TIFF0007813531000106.tif53168 When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, even more preferably 15 to 65 mol %, and still more preferably 20 to 65 mol %, based on all structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into the resin (A) by polymerizing the structural unit (a1-4) and then treating with an alkali such as tetramethylammonium hydroxide.

[0163] An example of the structural unit (a2) having an alcoholic hydroxy group is a structural unit represented by formula (a2-1) (hereinafter, sometimes referred to as "structural unit (a2-1)"). TIFF0007813531000107.tif3957 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding position with —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0164] In equation (a2-1), L a3 is preferably -O-, -O-(CH2) f1 It is —CO—O— (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0165] Examples of the structural unit (a2-1) include structural units derived from monomers described in JP 2010-204646 A. A structural unit represented by any one of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. TIFF0007813531000108.tif53151 When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, even more preferably 2 to 20 mol %, and still more preferably 2 to 10 mol %, based on the total structural units of the resin (A).

[0166] <Structural unit (a3)> The lactone ring contained in 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 a condensed ring of a monocyclic lactone ring with another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). One of these may be contained alone, or two or more may be contained. TIFF0007813531000109.tif51159 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or -O-(CH2) k3 It represents a group represented by —CO—O— (k3 represents an integer of 1 to 7). L a7 -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OLa9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 may be the same or different.]

[0167] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group. R a24Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, and preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

[0168] L a8 and L a9 Examples of the alkanediyl group in the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.

[0169] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or -O-(CH2) k3 In -CO-O-, k3 is a group in which k3 is any integer of 1 to 4, more preferably -O- and *-O-CH2-CO-O-, and even more preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group, or a methyl group. p1, q1 and r1 each independently represent an integer of preferably 0 to 2, and more preferably 0 or 1.

[0170] In formula (a3-4), R a24 is preferably 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. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8 It is —CO—O—, and more preferably —O—, —O—CH 2 —CO—O— or —O—C 2 H 4 —CO—O—. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007813531000110.tif4151 (in the formula, R a24 , L a7 has the same meaning as above.)

[0171] Examples of the structural unit (a3) ​​include structural units derived from monomers described in JP 2010-204646 A, JP 2000-122294 A, and JP 2012-41274 A. Examples of the structural unit (a3) ​​include structural units represented by any of 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 structural units, R in formulas (a3-1) to (a3-4) a18 , R a19 , R a20 and R a24 A structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom is preferred. TIFF0007813531000111.tif115165When the resin (A) contains the structural unit (a3), the total content thereof is usually 1 to 70 mol %, preferably 1 to 65 mol %, and more preferably 1 to 60 mol %, based on all structural units in the resin (A). Furthermore, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), or the structural unit (a3-4) is preferably 1 to 60 mol %, more preferably 1 to 50 mol %, and even more preferably 1 to 50 mol %, based on the total structural units of the resin (A).

[0172] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007813531000112.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.] R 42 Examples of the saturated hydrocarbon group represented by the formula (I) include chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these groups.

[0173] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* indicates a bonding position): TIFF0007813531000113.tif11160 Examples of groups formed by this combination 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.

[0174] The structural unit (a4) includes at least one structural unit selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4). TIFF0007813531000114.tif3953[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 6a represents a hydrogen atom or a fluorine atom.

[0175] L 4a Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group.

[0176] L 3aExamples of the perfluoroalkanediyl group in the formula (I) include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3 ,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. L 3a Examples of the perfluorocycloalkanediyl group in the formula (I) include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

[0177] L 4a is preferably a single bond, a methylene group, or an ethylene group, and more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0178] The structural unit (a4-0) includes the structural units shown below and R in the structural unit (a4-0) in the structural units shown below. 5a The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007813531000115.tif95165

[0179] TIFF0007813531000116.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1), a41 and R a42 At least one of the groups has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007813531000117.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represents -O-, -CO-, -CO-O- or -O-CO-. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates the bond position, and the * on the right is -O-CO-R a42 ]

[0180] R a42 Examples of the saturated hydrocarbon group in include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.

[0181] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* indicates a bonding position): TIFF0007813531000118.tif11160 Examples of groups formed by this combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0182] R a42 The substituent that may be included in the formula (a-g3) is at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3): Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF0007813531000119.tif752[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes R a42 represents the bond position with However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0183] A a45 Examples of the aliphatic hydrocarbon group in the formula (I) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group; Examples include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl groups, and the following groups (* indicates the bonding position): TIFF0007813531000120.tif11160

[0184] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably a saturated hydrocarbon group having an alkyl group having a halogen atom and / or a group represented by formula (a-g3). R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of perfluorocycloalkyl groups include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), the number of carbon atoms contained in the group represented by formula (a-g3) is a42 The total number of carbon atoms is preferably 15 or less, more preferably 12 or less. When the group represented by formula (a-g3) is contained as a substituent, the number thereof is preferably 1.

[0185] Ra42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 is more preferably a group represented by formula (a-g2). TIFF0007813531000121.tif874[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 represents the bond position with ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 At least one of the groups has at least one halogen atom. * indicates the bond position with the carbonyl group.]

[0186] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0187] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates the bonding position with the carbonyl group): TIFF0007813531000122.tif13161

[0188] A a41Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and branched alkanediyl groups such as propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. A a41 Examples of the substituent in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0189] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and a group formed by combining an alkanediyl group with a divalent alicyclic hydrocarbon group. Specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. Preferably, s is 0.

[0190] In the group represented by formula (a-g1), X a42 In the following examples, * and ** each represent a bond position, and ** represents -O-CO-Ra42 This is the bonding position with TIFF0007813531000123.tif48153

[0191] The structural unit represented by formula (a4-1) includes the structural units shown below and R in the structural unit represented by formula (a4-1) in the structural units shown below. a41 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007813531000124.tif100142

[0192] TIFF0007813531000125.tif123141

[0193] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). TIFF0007813531000126.tif3251[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The maximum total carbon number is 21.]

[0194] L 44 The alkanediyl group of A a41 Examples of the groups include the same groups as those exemplified in R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in L 44 The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.

[0195] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11). f5 The structural unit represented by formula (a4-2) also includes a structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom:

[0196] TIFF0007813531000127.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may contain a fluorine atom. X f12 is *-O-CO- or *-CO-O-(* is A f13 represents the bonding position with . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom, 5 , A f13 and A f14 The total number of carbon atoms in a molecule is limited to 20.

[0197] L 5 The alkanediyl group in a41 Examples of the alkanediyl group include the same groups as those exemplified as the alkanediyl group. A f13 The divalent saturated hydrocarbon group optionally having a fluorine atom in the formula (I) is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group; and perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group. The divalent alicyclic hydrocarbon group optionally having a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

[0198] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 Among these, 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, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, Preferred are fluorinated alkyl groups such as a hexyl group, a perfluorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group, and a perfluorooctyl group, a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, and a perfluoroadamantylmethyl group.

[0199] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group is preferably a group containing a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group containing a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group.

[0200] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a4-1'-11). f7 The structural unit represented by formula (a4-3) also includes a structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom:

[0201] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF0007813531000128.tif3858[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 -CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0202] R f22 The saturated hydrocarbon group of R a42Examples of saturated hydrocarbon groups include the same as those represented by R f22 is preferably an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom or an alicyclic 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, and even more preferably an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom. In formula (a4-4), A f21 As -(CH2) j1 - is preferred, an ethylene group or a methylene group is more preferred, and a methylene group is even more preferred.

[0203] Examples of the structural unit represented by formula (a4-4) include the following structural units and structural units represented by the following formulas: f21 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. When the resin (A) has the structural unit (a4), the content thereof is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and even more preferably 3 to 10 mol %, based on all structural units in the resin (A).

[0204] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a group containing a linear, branched, or cyclic hydrocarbon group, and among these, the structural unit (a5) is preferably a group containing an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by formula (a5-1). TIFF0007813531000130.tif3972[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.]

[0205] R 52 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl. Examples of the aliphatic hydrocarbon group 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. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0206] L 55 The divalent saturated hydrocarbon group in the formula (I) includes a divalent saturated chain hydrocarbon group and a divalent saturated alicyclic hydrocarbon group, and is preferably a divalent saturated chain hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and an alkanediyl group such as a propanediyl group, a butanediyl group, and a pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantanediyl and norbornanediyl.

[0207] L 55Examples of the divalent saturated hydrocarbon group represented by formula (L1-1) in which one -CH2- is replaced with -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulae, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. TIFF0007813531000131.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 represents the bond position with ). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 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. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each 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. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0208] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 is preferably 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 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably 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 is preferably 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. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0209] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007813531000132.tif54134

[0210] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007813531000133.tif24131

[0211] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007813531000134.tif15145

[0212] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007813531000135.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0213] The structural unit (a5-1) includes the structural units shown below and R in the structural unit (a5-1) in the structural units shown below. 51 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. When the resin (A) has the structural unit (a5), the content thereof is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and even more preferably 3 to 15 mol %, based on all structural units in the resin (A).

[0214] <Structural unit (a6)> The structural unit (a6) is a structural unit having an -SO2- group, and preferably has an -SO2- group in a side chain. The 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 or polycyclic structure) having an -SO2- group. A structural unit having a cyclic structure having an -SO2- group is preferred, and a structural unit having a cyclic structure containing an -SO2-O- group (sultone ring) is more preferred.

[0215] The sultone ring may be a ring having the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and the formula (T 1 The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring refers to a bridged ring containing -SO2-O- as an atomic group constituting the ring, and is represented by the formula (T 1 -1) and the formula (T 1 The sultone ring is represented by the formula (T 1 As in the ring represented by formula (2), the atomic group constituting the ring may further contain a heteroatom in addition to —SO—O—. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. TIFF0007813531000137.tif3187

[0216] The sultone ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms.

[0217] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group, and preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group, and preferably a trifluoromethyl group. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Aralkyl groups include benzyl, phenethyl, phenylpropyl, naphthylmethyl, and naphthylethyl groups. Examples of the alkoxycarbonyl group include groups in which an alkoxy group, such as a methoxycarbonyl group or an ethoxycarbonyl group, is bonded to a carbonyl group, and preferred are alkoxycarbonyl groups having 6 or less carbon atoms, more preferably a methoxycarbonyl group. Alkylcarbonyl groups include acetyl, propionyl and butyryl groups.

[0218] From the viewpoint of ease of production of the monomer from which the structural unit (a6) is derived, a sultone ring having no substituent is preferred. The sultone ring is preferably a ring represented by the following formula (T1'). TIFF0007813531000138.tif3172[In formula (T1'), X 11represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 may be the same or different. The binding site is at any position.] X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. R 41 Examples of the substituent include the same as the substituent on the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferred.

[0219] The sultone ring is more preferably a ring represented by formula (T1). TIFF0007813531000139.tif3149[In formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents an integer of 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The binding site is at any position.]

[0220] R 8 is R 41 The same can be mentioned. ma in formula (T1′) and m in formula (T1) are preferably 0 or 1, and more preferably 0.

[0221] Examples of the ring represented by formula (T1') and the ring represented by formula (T1) include the following rings: The binding site is at any position. TIFF0007813531000140.tif53160

[0222] The structural unit having a sultone ring preferably has the following group: In the following group, * represents a bonding site. TIFF0007813531000141.tif50161

[0223] The structural unit having an -SO2- group preferably further has a group derived from a polymerizable group, such as a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, or a methacryloylthio group. Among these, the monomer from which the structural unit (a6) is derived is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.

[0224] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007813531000142.tif4956 [In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. A xx is an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO- or -N(R d )- may be replaced. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 may be the same or different. R c and R d each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0225] R x Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R x Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group, and are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group. R x is preferably 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.

[0226] A xExamples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and may be a combination of two or more of these groups. 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 a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-2,2-diyl group; branched alkanediyl groups such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0227] R 41 , X 11 and ma may be the same as those in formula (T1'). Examples of the sultone ring include those mentioned above, and among these, those having a specific bonding position are preferred.

[0228] Examples of the structural unit (a6) include the following structural units. TIFF0007813531000143.tif100158

[0229] Of these, structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8), and formula (a6-12) are preferred, and structural units represented by formula (a6-1), formula (a6-2), formula (a6-7), and formula (a6-8) are more preferred. When the resin (A) has the structural unit (a6), the content thereof is preferably from 1 to 50 mol %, more preferably from 2 to 40 mol %, and even more preferably from 3 to 30 mol %, based on all structural units in the resin (A).

[0230] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter, sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and the structural unit (II) is preferably a structural unit having a sulfonate group or carboxylate group and an organic cation in a side chain, or a structural unit having a sulfonio group and an organic anion in a side chain.

[0231] The structural unit having a sulfonate group or carboxylate group and an organic cation on the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007813531000144.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, wherein one -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA- represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0232] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: a8 Examples of the alkyl group include the same alkyl groups having 1 to 6 carbon atoms which may have a halogen atom and which are represented by the following formula: A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a linear or branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these may be used in combination. Specific examples thereof include linear alkanediyl 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; butane-1,3-diyl, 2-methylpropane-1,3-diyl, and 2-methylpropane-1,3-diyl; Examples include branched alkanediyl groups such as pentane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; and divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl. Examples of saturated hydrocarbon groups in which -CH2- is replaced with -O-, -S-, or -CO- include divalent groups represented by formulae (X1) to (X53). However, the number of carbon atoms before the -CH2- in the saturated hydrocarbon group is replaced with -O-, -S-, or -CO- is 17 or less. In the following formulae, * and ** represent bonds, and * represents A x1 Represents a bond with . TIFF0007813531000145.tif145161

[0233] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0234] ZA in formula (II-2-A') + is the cation Z1 in the acid generator (B1). + The same can be mentioned.

[0235] The structural unit represented by formula (II-2-A') is preferably a structural unit represented by formula (II-2-A). TIFF0007813531000146.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms; when z2A is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.] R III2 , R III4 , Q a and Q b As the perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula, the above-mentioned Q b1 Examples include the same perfluoroalkyl groups having 1 to 6 carbon atoms as those represented by the following formula:

[0236] The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1). TIFF0007813531000147.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Qb and ZA + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-, and wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom or a hydroxy group. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. X I2 As the divalent saturated hydrocarbon group represented by X III3 Examples of the divalent saturated hydrocarbon group include those similar to those represented by the following formula:

[0237] As the structural unit represented by formula (II-2-A-1), a structural unit represented by formula (II-2-A-2) is more preferred. TIFF0007813531000148.tif5288 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. mA and nA each independently represent 1 or 2.]

[0238] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 Examples of such a structural unit include a structural unit in which the group corresponding to the methyl group in the formula (1) is replaced with a hydrogen atom, a halogen atom (e.g., a fluorine atom), or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (e.g., a trifluoromethyl group), and the structural units described in WO 2012 / 050015.+ represents an organic cation. TIFF0007813531000149.tif87163

[0239] The structural unit having a sulfonio group and an organic anion on the side chain is preferably a structural unit represented by formula (II-1-1). TIFF0007813531000150.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: a8 Examples of the alkyl group include the same alkyl groups having 1 to 6 carbon atoms which may have a halogen atom and which are represented by the following formula: A II1Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. III3 Examples include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms as those represented by the following formula:

[0240] The structural unit containing a cation in formula (II-1-1) includes the structural unit represented by the following formula and R II4 and structural units in which a group corresponding to the methyl group in the above formula (I) is replaced with a hydrogen atom, a fluorine atom, a trifluoromethyl group, or the like. TIFF0007813531000151.tif85130

[0241] A - Examples of the organic anion represented by the formula (A) include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. - The organic anion represented by the formula (B1) is preferably a sulfonate anion, and the sulfonate anion is more preferably an anion contained in the salt represented by the formula (B1) above.

[0242] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007813531000152.tif35135 Examples of sulfonylmethide anions include the following: TIFF0007813531000153.tif29123Carboxylate anions include the following: TIFF0007813531000154.tif49163

[0243] Examples of the structural unit represented by formula (II-1-1) include structural units represented by the following formulas. TIFF0007813531000155.tif98165When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and even more preferably 3 to 10 mol %, based on the total structural units of the resin (A).

[0244] The resin (A) may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well known in the art.

[0245] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2), and even more preferably the structural unit (a1-1) and / or the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-A) or a structural unit represented by formula (a2-1). 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).

[0246] The structural units constituting the resin (A) may be used singly or in combination of two or more, and can be produced by a known polymerization method (e.g., radical polymerization) using monomers that lead to these structural units. The content of each structural unit in the resin (A) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of the 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). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples.

[0247] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of resins other than resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter, sometimes referred to as resin (X)). As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In the resin (X), the content of the structural unit (a4) is preferably 30 mol % or more, more preferably 40 mol % or more, and even more preferably 45 mol % or more, based on the total of all structural units in the resin (X). Examples of structural units that the resin (X) may further have include the structural unit (a2), the structural unit (a3), and structural units derived from other known monomers. Among these, the resin (X) is preferably a resin consisting only of the structural unit (a4) and / or the structural unit (a5), and more preferably a resin consisting only of the structural unit (a4). The structural units constituting the resin (X) may be used singly or in combination of two or more, and can be produced by a known polymerization method (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in the resin (X) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight of resin (X) is the same as that for resin (A). Furthermore, when the resist composition contains resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 40 parts by mass, still more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass, relative to 100 parts by mass of resin (A).

[0248] The content of resin (A) in the resist composition is preferably 80 to 99 mass% based on the solid content of the resist composition, and more preferably 90 to 99 mass%. Furthermore, when a resin other than resin (A) is contained, the total content of resin (A) and the resin other than resin (A) based on the solid content of the resist composition is preferably 80 to 99 mass% based on the solid content of the resist composition, and more preferably 90 to 99 mass%. The solid content of the resist composition and the resin content relative to the solid content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0249] <Solvent (E)> The content of the solvent (E) in the resist composition is usually from 90 to 99.9% by mass, preferably from 92 to 99% by mass, and more preferably from 94 to 99% by mass. The content of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; etc. One type of solvent (E) may be used alone, or two or more types may be used.

[0250] <Quencher (C)> The quencher (C) can be a basic nitrogen-containing organic compound or a salt (excluding the carboxylate represented by formula (I)) that generates an acid with a weaker acidity than the acid generated from the acid generator (B). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15 mass%, more preferably about 0.01 to 10 mass%, even more preferably about 0.1 to 8 mass%, and even more preferably about 0.1 to 7 mass%, based on the solids content of the resist composition. The basic nitrogen-containing organic compound includes amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary amines, secondary amines, and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, Amine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine amine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane Examples of the amines include 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Preferred are aromatic amines such as diisopropylaniline, and more preferred is 2,6-diisopropylaniline. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like.

[0251] The acidity of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) include the salt represented by the following formula, the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid weaker in acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably the weak acid inner salt (D). TIFF0007813531000156.tif94164

[0252] Examples of the weak acid inner salt (D) include the following salts. TIFF0007813531000157.tif72165

[0253] 〈Other components〉 The resist composition of the present invention may optionally contain components other than those described above (hereinafter, these may be referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, can be used.

[0254] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing the carboxylate (I), resin (A), acid generator (B), and, if necessary, resins other than resin (A), solvent (E), quencher (C), and other components (F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing can be selected from 10 to 40°C depending on the type of resin, etc., the solubility of the resin, etc. in the solvent (E), etc. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing method is also not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm.

[0255] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention comprises: (1) applying the resist composition of the present invention onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating is included. The resist composition can be applied to a substrate using a commonly used device such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers and organic substrates with a resist film already formed thereon. Before applying the resist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. The composition after coating is dried to remove the solvent and form a composition layer. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. The pressure during vacuum drying is preferably 1 to 1.0 x 10 5 It is preferable that the pressure is about Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Various exposure light sources can be used, including those that emit ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm); those that convert the wavelength of laser light from a solid-state laser source (such as a YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range; and those that irradiate with electron beams or extreme ultraviolet light (EUV). In this specification, irradiation with these types of radiation may be collectively referred to as "exposure." During exposure, exposure is typically performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called post-exposure bake) to promote the deprotection reaction of the acid labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C. A chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the heated composition. Furthermore, before development, the steps of applying a resist composition, drying, exposing, and heating may be repeated on the composition layer after exposure. The heated composition layer is usually developed using a developer in a developing device. Development methods include dipping, puddling, spraying, and dynamic dispensing. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 300 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant. After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed. When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among these, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant and a small amount of water. During development, development may be stopped by replacing the organic developer with a different type of solvent. The developed resist pattern is preferably washed with a rinse solution. There are no particular limitations on the rinse solution as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0256] <Application> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and is particularly suitable as a resist composition for ArF excimer laser exposure, and is useful for semiconductor microfabrication. [Example]

[0257] The present invention will be explained in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are by mass unless otherwise specified. The weight-average molecular weight is a value determined by gel permeation chromatography under the following analytical conditions: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100, MASS: Agilent LC / MSD). In the following examples, the value of this molecular ion peak is indicated by "MASS."

[0258] Example 1: Synthesis of salt represented by formula (I-1) 20 parts of the compound represented by formula (I-1-a), 2.28 parts of the compound represented by formula (I-1-c), 100 parts of ethyl acetate, and 15 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes. 6.55 parts of the compound represented by formula (I-1-b) were added to the resulting mixed solution and stirred at 23°C for 18 hours. 20 parts of n-heptane and 70 parts of ion-exchanged water were added to the resulting reaction mass and stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated four times. The obtained organic layer was concentrated, and the concentrated mass was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 7.48 parts of a compound represented by formula (I-1-d). 0.95 parts of the compound represented by formula (I-1-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.14 parts of sodium hydride was added. 1.81 parts of the salt represented by formula (I-1-e) were added to the resulting mixture and stirred at 5°C for 3 hours. 6.30 parts of 1N hydrochloric acid were added to the resulting mixture, and the mixture was heated to 23°C and stirred at 23°C for 6 hours. 30 parts of chloroform and 15 parts of ion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, followed by separation and extraction of the organic layer. The resulting organic layer was concentrated, and then 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes. The supernatant was removed and the mixture was concentrated to obtain 1.52 parts of the salt represented by formula (I-1-f). 0.95 parts of a salt represented by formula (I-1-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the mixture was heated to 75°C. 0.54 parts of a compound represented by formula (I-1-g) were added to the resulting mixture, which was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, which was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, which was stirred at 23°C for 30 minutes. This water-washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.12 parts of a salt represented by formula (I-1-h). TIFF0007813531000161.tif66149 0.75 parts of the salt represented by formula (I-1-h), 0.37 parts of the salt represented by formula (I-1-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 0.83 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum):M + 563.2 MASS(ESI(-)Spectrum):M - 195.1

[0259] Example 2: Synthesis of salt represented by formula (I-2) TIFF0007813531000162.tif66146 0.75 parts of the salt represented by formula (I-1-h), 0.37 parts of the salt represented by formula (I-2-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 0.82 parts of the salt represented by formula (I-2). MASS(ESI(+)Spectrum):M + 563.2 MASS(ESI(-)Spectrum):M - 193.1

[0260] Example 3: Synthesis of salt represented by formula (I-4) TIFF0007813531000163.tif66166 0.75 parts of the salt represented by formula (I-1-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.02 parts of the salt represented by formula (I-4). MASS(ESI(+)Spectrum):M + 563.2 MASS(ESI(-)Spectrum):M - 337.1

[0261] Example 4: Synthesis of salt represented by formula (I-748) 0.95 parts of the salt represented by formula (I-1-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the mixture was heated to 75°C. 0.54 parts of the compound represented by formula (I-748-g) were added to the resulting mixture, which was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, which was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, which was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.09 parts of the salt represented by formula (I-748-h). 0.76 parts of the salt represented by formula (I-748-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 0.99 parts of the salt represented by formula (I-748). MASS(ESI(+)Spectrum):M + 565.1 MASS(ESI(-)Spectrum):M - 337.1

[0262] Example 5: Synthesis of salt represented by formula (I-746) TIFF0007813531000166.tif68147 0.76 parts of the salt represented by formula (I-748-h), 0.37 parts of the salt represented by formula (I-2-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 0.84 parts of the salt represented by formula (I-746). MASS(ESI(+)Spectrum):M + 565.1 MASS(ESI(-)Spectrum):M - 193.1

[0263] Example 6: Synthesis of salt represented by formula (I-745) 0.76 parts of the salt represented by formula (I-748-h), 0.37 parts of the salt represented by formula (I-1-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. 0.80 parts of the salt represented by formula (I-745) was obtained by concentrating the resulting organic layer. MASS(ESI(+)Spectrum):M + 565.1 MASS(ESI(-)Spectrum):M - 195.1

[0264] Example 7: Synthesis of salt represented by formula (I-1144) 0.95 parts of the salt represented by formula (I-1-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the mixture was heated to 75°C. 0.61 parts of the compound represented by formula (I-1144-g) were added to the resulting mixture, stirred at 75°C for 5 hours, and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.23 parts of the salt represented by formula (I-1144-h). 0.79 parts of the salt represented by formula (I-1144-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.09 parts of the salt represented by formula (I-1144). MASS(ESI(+)Spectrum):M + 591.2 MASS(ESI(-)Spectrum):M - 337.1

[0265] Example 8: Synthesis of salt represented by formula (I-3234) 2.10 parts of the compound represented by formula (I-1-d) and 20 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.28 parts of sodium hydride was added. 1.91 parts of the salt represented by formula (I-3234-e) were added to the resulting mixture, and the mixture was stirred at 5°C for 3 hours. 12.60 parts of 1N hydrochloric acid were added to the resulting mixture, and the mixture was heated to 23°C and stirred at 23°C for 6 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. The obtained organic layer was concentrated, and then 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue. The mixture was stirred at 23°C for 30 minutes, and the supernatant was removed. The mixture was then concentrated to obtain 2.42 parts of a salt represented by formula (I-3234-f). 1.20 parts of the salt represented by formula (I-3234-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.32 parts of potassium carbonate and 0.10 parts of potassium iodide were added, and the mixture was heated to 75°C. 1.45 parts of the compound represented by formula (I-1144-g) were added to the resulting mixture, which was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, which was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 20 parts of ion-exchanged water were added to the resulting organic layer, which was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.55 parts of the salt represented by formula (I-3234-h). 0.79 parts of the salt represented by formula (I-3234-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.27 parts of the salt represented by formula (I-3234). MASS(ESI(+)Spectrum):M + 921.3 MASS(ESI(-)Spectrum):M - 337.1

[0266] Example 9: Synthesis of salt represented by formula (I-3709) 3.15 parts of the compound represented by formula (I-1-d) and 30 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.42 parts of sodium hydride was added. 2.01 parts of the salt represented by formula (I-3709-e) were added to the resulting mixture, and the mixture was stirred at 5°C for 3 hours. 18.90 parts of 1N hydrochloric acid were added to the resulting mixture, and the mixture was heated to 23°C and stirred at 23°C for 6 hours. 100 parts of chloroform and 50 parts of ion-exchanged water were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. The obtained organic layer was concentrated, and then 5 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue. The mixture was stirred at 23°C for 30 minutes, and the supernatant was removed. The mixture was then concentrated to obtain 3.11 parts of a salt represented by formula (I-3709-f). 1.45 parts of the salt represented by formula (I-3709-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.48 parts of potassium carbonate and 0.15 parts of potassium iodide were added, and the mixture was heated to 75°C. 2.17 parts of the compound represented by formula (I-1144-g) were added to the resulting mixture, which was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, which was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, which was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was isolated. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 2.12 parts of the salt represented by formula (I-3709-h). 1.61 parts of the salt represented by formula (I-3709-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23°C for 12 hours. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated to obtain 1.81 parts of the salt represented by formula (I-3709). MASS(ESI(+)Spectrum):M + 1251.4 MASS(ESI(-)Spectrum):M - 337.1

[0267] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. Hereinafter, these compounds will be referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007813531000176.tif43143

[0268] Synthesis Example 1: Synthesis of Resin A1 Monomers (a1-1-3), (a1-2-6), (a2-1-1), and (a3-4-2) were mixed in a molar ratio of 45:14:2.5:38.5 (monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-1):monomer (a3-4-2)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.8 × 10 3 Resin A1 was obtained in a yield of 69%. This resin A1 has the following structural units. TIFF0007813531000177.tif36126

[0269] Synthesis Example 2: Synthesis of Resin X1 Monomer (a5-1-1) and monomer (a4-0-12) were used as monomers, and they were mixed in a molar ratio of 50:50 [monomer (a5-1-1):monomer (a4-0-12)]. Methyl isobutyl ketone was added in an amount 1.2 times the total amount of monomers by mass to form a solution. Azobis(2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol% relative to the total amount of monomers to this solution, and the mixture was heated at 70°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin. The resin was filtered and measured to obtain a resin having a weight-average molecular weight of 1.0 x 10 4 Resin X1 was obtained in a yield of 91%. This resin X1 has the following structural units. TIFF0007813531000178.tif3082

[0270] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition. [Table 2]

[0271] <Resin> A1, X1: Resin A1, Resin X1 <Acid generator (B)> B1-21: a salt represented by formula (B1-21) B1-22: a salt represented by formula (B1-22) TIFF0007813531000180.tif2897<Carboxylate(I)> I-1: A salt represented by formula (I-1) I-2: A salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-745: A salt represented by the formula (I-745) I-746: A salt represented by the formula (I-746) I-748: A salt represented by the formula (I-748) I-1144: A salt represented by the formula (I-1144) I-3234: A salt represented by the formula (I-3234) I-3709: A salt represented by the formula (I-3709) <Quencher (C)> IX-1 IX-2 IX-3 IX-4 TIFF0007813531000181.tif77136<solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

[0272] <Resist pattern production and evaluation> A 12-inch silicon wafer was coated with an organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] and baked at 205°C for 60 seconds to form an organic antireflective coating with a thickness of 78 nm. The resist composition described above was then spin-coated onto the organic antireflective coating so that the film thickness of the composition layer after drying (pre-baking) would be 100 nm. After coating, the silicon wafer was pre-baked on a direct hot plate for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer on the silicon wafer. The composition layer formed on the silicon wafer was exposed to an ArF excimer laser stepper for immersion exposure [XT:1900Gi; ASML, NA=1.35, Annular σ out =0.85 σ in =0.65 XY-pol. illumination], a mask was used to form a trench pattern (pitch 120 nm / trench width 40 nm) and the exposure dose was changed stepwise. Ultrapure water was used as the immersion medium. After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column in Table 2. Next, the composition layer on this silicon wafer was developed by a dynamic dispensing method at 23°C for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer, thereby producing a negative resist pattern.

[0273] In the obtained resist pattern, the exposure amount at which the width of the trench pattern became 40 nm was defined as the effective sensitivity.

[0274] <Line Edge Roughness Evaluation (LER)> The resulting resist pattern was observed and measured using a scanning electron microscope to measure the amplitude of unevenness on the wall surface. The results are shown in Table 3. The values ​​in the table indicate the amplitude (nm). [Table 3] Compared with the comparative compositions 1 to 4, the compositions 1 to 9 had good line edge roughness (LER). [Industrial Applicability]

[0275] The carboxylate of the present invention and the resist composition containing the carboxylate are capable of obtaining a resist pattern with good line edge roughness (LER), and are therefore suitable for semiconductor microfabrication and extremely useful industrially.

Claims

1. A carboxylic acid salt represented by formula (I): [In formula (I), R １ , R ２ and R ３ are each independently -O-R １０ , —O—CO—R １０ , -O-CO-OR １０ , -O-L １ -CO-O-R １０ Represents. R ４ , R ５ , R ６ , R ７ , R ８ and R ９ each independently represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have a substituent, and -CH 2 - is -O-, -S-, -CO- or -SO ２ It may be replaced with -. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R １０ represents a group having a lactone structure. X １ , X ２ and X ３ each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of 0 to 5, and when m1 is 2 or more, the groups in the parentheses may be the same or different. m2 represents an integer of 0 to 4, and when m2 is 2 or more, the groups in the parentheses may be the same or different. m3 represents an integer of 0 to 4, and when m3 is 2 or more, the groups in the parentheses may be the same or different. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R ４ may be the same or different from each other. m5 represents an integer of 0 to 4, and when m5 is 2 or more, a plurality of R ５ may be the same or different from each other. m6 represents an integer of 0 to 4, and when m6 is 2 or more, a plurality of R ６ may be the same or different from each other. m7 represents an integer of 0 to 5, and when m7 is 2 or more, a plurality of R ７ may be the same or different from each other. m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of R ８ may be the same or different from each other. m9 represents an integer of 0 to 4, and when m9 is 2 or more, a plurality of R ９ may be the same or different from each other. However, 0≦m1+m7≦5, 0≦m2+m8≦4, 0≦m3+m9≦4, and at least one of m1, m2, and m3 represents an integer of 1 or more. X ４ is a single bond, -CH 2 -, -O-, -S-, -CO-, -SO- or -SO ２ Represents -. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -CO- or -SO ２ - may be replaced by .

2. X １ , X ２ and X ３ The carboxylate according to claim 1, wherein is an oxygen atom.

3. R １ , R ２ and R ３ is-O-CO-OR １０ -or-OL １ -CO-O-R １０ 3. The carboxylate according to claim 1 or 2, wherein

4. R １０ The group having a lactone structure of the formula (R １０ -1), formula (R １０ -2) or formula (R １０ 4. The carboxylic acid salt according to claim 1, wherein the carboxylic acid salt is a group having a lactone ring group represented by the formula (I-3). [Formula (R)] １０ -1) ~ Formula (R) １０ -3) Middle * represents a bond. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R １１ , R １２ and R １３ each independently represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and —CH 2 - may be replaced by -O- or -CO-. m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of R １１ may be the same or different from each other. m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R １２ may be the same or different from each other. m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of R １３ may be the same or different from each other. n10 represents an integer of 1 to 3.

5. X ０ an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that the —CH 2 - is -O-, -S-, -CO- or -SO ２ 5. The carboxylate according to claim 1, wherein the carboxylate is an aromatic hydrocarbon group having 6 to 36 carbon atoms, which may be substituted with -.

6. X ０ is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (the —CH 2 - is -O-, -S-, -CO- or -SO ２ 6. The carboxylate according to claim 1, wherein the carboxylate is an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have one or more substituted groups, each of which may be substituted with one or more substituted groups, or a halogen atom, a hydroxyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms.

7. A carboxylic acid generator comprising the carboxylic acid salt according to any one of claims 1 to 6.

8. 8. A resist composition comprising the carboxylic acid generator according to claim 7, an acid generator other than the carboxylic acid generator, and a resin having an acid labile group represented by formula (1) or (2) on a side chain. [In formula (1), R a1 , R a2 and R a3 each independently represent 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 combination thereof, or R a1 and R a2 bond to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond. [In formula (2), R a1' and R a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a3' represents a hydrocarbon group having 1 to 20 carbon atoms; or R a2' and R a3' are bonded to each other to form, together with the carbon atom to which they are bonded and X, a heterocyclic group having 3 to 20 carbon atoms, and —CH 2 — contained in the hydrocarbon group and the heterocyclic group may be replaced by —O— or —S—.] X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.

9. 9. The resist composition according to claim 8, wherein the resin having an acid labile group comprises at least one structural unit selected from the group consisting of structural units represented by formula (a1-1) and structural units represented by formula (a1-2): [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently —O— or *—O—(CH ２ ) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a4 and R a5 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. R a6 and R a7 each 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 combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1′ represents an integer of 0 to 3.

10. 10. The resist composition according to claim 8, further comprising a resin containing a structural unit having a fluorine atom.

11. (1) a step of applying the resist composition according to any one of claims 8 to 10 onto a substrate; (2) a step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) a step of heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising:

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