Carboxylate, carboxylic acid generator, resist composition, and method for producing a resist pattern

Abstract

To provide a carboxylate capable of producing a resist pattern having good line edge roughness (LER), a carboxylic acid generator and a resist composition.SOLUTION: There are provided a carboxylate represented by the formula (I), a carboxylic acid generator and a resist composition. [In the formula, R1 and R2 each represent -O-L1-CO-O-R10; L1 represents an alkanediyl group; R4, R5, R7 and R8 each represent a halogen atom, an alkyl fluoride group or the like; R10 represents a group represented by the formula (IC); RA represents a saturated hydrocarbon group; u1 represents an integer of 0 to 2; s1 represents 1 or 2, t1 represents 0 or 1, provided that s1+t1=1 or 2; L2 represents a hydrocarbon group; X1 and X2 each represent S or O; m1 represents an integer of 1 to 5, m2 and m8 represent an integer of 0 to 5, m4, m5 and m7 represent an integer of 0 to 4, provided that 1≤m1+m7≤5 and 0≤m2+m8≤5; X0 represents a hydrocarbon group.]SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007704571000001.tif1454 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007704571000002.tif3490 Non-Patent Document 1 describes a salt represented by the following formula. TIFF0007704571000003.tif1084 Patent Document 3 describes a salt represented by the following formula. TIFF0007704571000004.tif2489 Patent Document 4 describes a salt represented by the following formula. TIFF0007704571000005.tif1156

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Documents

[0004]

Non-Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] The present invention provides a carboxylate that forms a resist pattern having better line edge roughness (LER) than a resist pattern formed by a resist composition containing the above salt.

MEANS FOR SOLVING THE PROBLEMS

[0006] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007704571000006.tif30138[In formula (I), R 1 and R 2 each independently represents -O-R 10 , -O-CO-R 10 , -O-CO-O-R 10 , -O-L 1 -CO-O-R 10 . L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 4 , R 5 , R 7 and R 8 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, the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S-, or -SO2-. R 10 represents a group represented by formula (IC). X 1 and X 2 each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of 1 to 5, and when m1 is 2 or more, the groups in a plurality of parentheses may be the same or different from each other. m2 represents any integer from 0 to 5. When m2 is 2 or more, the groups within the plurality of parentheses may be the same or different from each other. m4 represents any integer from 0 to 4. When m4 is 2 or more, the plurality of Rs 4 may be the same or different from each other. m5 represents any integer from 0 to 4. When m5 is 2 or more, the plurality of Rs 5 may be the same or different from each other. m7 represents any integer from 0 to 4. When m7 is 2 or more, the plurality of Rs 7 may be the same or different from each other. m8 represents any integer from 0 to 5. When m8 is 2 or more, the plurality of Rs 8 may be the same or different from each other. However, 1 ≦ m1 + m7 ≦ 5 and 0 ≦ m2 + m8 ≦ 5. 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-. TIFF0007704571000007.tif2881[In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of Rs A are the same or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L 2 represents a single bond or 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-. * represents a bonding site. [2]X 1 and X 2 are oxygen atoms, the carboxylate salt according to [1]. [3]L 2The carboxylate salt described in [1] or [2], wherein the group is a methylene group. [4] m2 is 0, m8 is 1, and R 8 is a branched alkyl group having 3 or 4 carbon atoms, and is the carboxylate salt according to any one of [1] to [3]. [5] R 4 or R 5 is an iodine atom, a fluorine atom, or a trifluoromethyl group, and is the carboxylate salt according to any one of [1] to [4]. [6] The bonding position of R in the benzene ring 4 is the o-position or m-position with respect to X 1 , or the bonding position of R in the benzene ring 5 is the o-position or m-position with respect to X 2 , and is the carboxylate salt according to [5]. [7] X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, -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, and is the carboxylate salt according to any one of [1] to [6]. [8] X 0 is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or an aromatic hydrocarbon group which may have a halogen atom, a hydroxy group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and is the carboxylate salt according to any one of [1] to [7]. [9] X 0 is a group represented by the formula (aa), and is the carboxylate salt according to [7]. TIFF0007704571000008.tif2737 [In the formula (aa), X a and X b each independently represent -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-. * represents the bonding position with the carbon atom of -COO - . A carboxylic acid generator containing the carboxylate salt according to any one of

[10] [1] to [9]. A resist composition containing the carboxylic acid generator according to

[10] [1], an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group. The resist composition according to

[11] , wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). TIFF0007704571000009.tif46102[In the formula (a1-1) and the formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents an integer of any one 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 group combining these. m1 represents an integer of any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1' represents an integer of any one of 0 to 3. The resist composition according to

[11] or

[12] , further containing a resin containing a structural unit having a fluorine atom.

[14] (1) Applying the resist composition according to any one of

[11] to

[13] onto a substrate; (2) Drying the applied composition to form a composition layer; (3) Exposing the composition layer; (4) Heating the exposed composition layer, and (5) Developing the heated composition layer, a method for manufacturing a resist pattern including these steps.

Effect of the Invention

[0007] By using the resist composition containing the carboxylate of the present invention, a resist pattern can be manufactured with good line edge roughness (LER).

Embodiment for Carrying Out the Invention

[0008] In this specification, the “(meth)acrylic monomer” means “at least one of an acrylic monomer and a methacrylic monomer”. Expressions such as “(meth)acrylate” and “(meth)acrylic acid” also represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either one. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples are applicable to each group. The “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of those groups may be appropriately changed depending on the bonding form. “Derived from” or “induced from” refers to the fact that the polymerizable C = C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0009] 〔Salt represented by formula (I)〕 The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as “salt (I)”). Among salts (I), the side with a negative charge may be referred to as "anion (I)", and the side with a positive charge may be referred to as "cation (I)". TIFF0007704571000010.tif30138[wherein all the symbols have the same meanings as described above.]

[0010] In formula (I), R 1 and R 2 The alkandiyl group in L 1 includes linear alkandiyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group; and branched alkandiyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group. L 1 is preferably an alkandiyl group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0011] R 1 and R 2 The R 10 contained in is a group represented by formula (IC). TIFF0007704571000011.tif2882[In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of R A are the same or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L 2represents a hydrocarbon group having 1 to 36 carbon atoms which may have a single bond or a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents a bonding site. L 2 Examples of the hydrocarbon group having 1 to 36 carbon atoms for L include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, alkynediyl groups, and monocyclic or polycyclic alicyclic hydrocarbon groups), aromatic hydrocarbon groups, etc., and hydrocarbon groups formed by combining two or more of these groups may also be used. L 2 -CH2- contained in the hydrocarbon group in may be replaced by -O-, -S-, -CO- or -SO2-.

[0012] Examples of the alkanediyl group include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group are included. The number of carbon atoms of the alkanediyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenediyl group include ethenediyl group, propenediyl group, isopropenediyl group, butenediyl group, isobutenediyl group, tert-butenediyl group, pentenediyl group, hexenediyl group, heptenediyl group, octenediyl group, isooctenediyl group, nonenediyl group. Examples of the alkynediyl group include an ethynediyl group, a propynediyl group, an isopropynediyl group, a butynediyl group, an isobutynediyl group, a tert-butynediyl group, a pentynediyl group, a hexynediyl group, an octynediyl group, a nonynediyl group, and the like.

[0013] Examples of the group in which -CH2- contained in the alkanediyl group is replaced by -O-, -S-, -CO- or -SO2- include a hydroxy group (a group in which -CH2- contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in the methyl group is replaced by -S-), an alkanediyl-oxy group (a group in which -CH2- at an arbitrary position contained in the alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at an arbitrary position contained in the alkanediyl group is replaced by -O-CO-), an alkanediyl-carbonyl group (a group in which -CH2- at an arbitrary position contained in the alkanediyl group is replaced by -CO-), an alkanediyl-carbonyloxy group (a group in which -CH2-CH2- at an arbitrary position contained in the alkanediyl group is replaced by -CO-O-), an alkanediyl-thio group (a group in which -CH2- at an arbitrary position contained in the alkanediyl group is replaced by -S-), an alkanediyl-sulfonyl group (a group in which -CH2- at an arbitrary position contained in the alkanediyl group is replaced by -SO2-), and the like. Examples of the alkanediyl-oxy group include an alkanediyl-oxy group having 1 to 17 carbon atoms, such as a methylene-oxy group, an ethylene-oxy group, a propanediyl-oxy group, a butanediyl-oxy group, a pentanediyl-oxy group, a hexanediyl-oxy group, an octanediyl-oxy group, a 2-ethylhexanediyl-oxy group, a nonanediyl-oxy group, a decanediyl-oxy group, an undecanediyl-oxy group, and the like. Examples of the alkanediyl oxycarbonyl group include alkanediyl oxycarbonyl groups having 2 to 17 carbon atoms, such as a methylene oxycarbonyl group, an ethylene oxycarbonyl group, a propanediyl oxycarbonyl group, a butanediyl oxycarbonyl group, a pentanediyl oxycarbonyl group, a hexanediyl oxycarbonyl group, an octanediyl oxycarbonyl group, a 2-ethylhexanediyl oxycarbonyl group, a nonanediyl oxycarbonyl group, a decanediyl oxycarbonyl group, an undecanediyl oxycarbonyl group, and the like. Examples of the alkanediyl carbonyl group include alkanediyl carbonyl groups having 2 to 18 carbon atoms, such as a methylene carbonyl group, an ethylene carbonyl group, a propanediyl carbonyl group, a butanediyl carbonyl group, a pentanediyl carbonyl group, a hexanediyl carbonyl group, an octanediyl carbonyl group, a 2-ethylhexanediyl carbonyl group, a nonanediyl carbonyl group, a decanediyl carbonyl group, an undecanediyl carbonyl group, and the like. Examples of the alkanediyl carbonyloxy group include alkanediyl carbonyloxy groups having 2 to 17 carbon atoms, such as a methylene carbonyloxy group, an ethylene carbonyloxy group, a propanediyl carbonyloxy group, a butanediyl carbonyloxy group, a pentanediyl carbonyloxy group, a hexanediyl carbonyloxy group, an octanediyl carbonyloxy group, a 2-ethylhexanediyl carbonyloxy group, a nonanediyl carbonyloxy group, a decanediyl carbonyloxy group, an undecanediyl carbonyloxy group, and the like. Examples of the alkanediyl thio group include alkanediyl thio groups having 1 to 17 carbon atoms, such as a methylene thio group, an ethylene thio group, a propanediyl thio group, a butanediyl thio group, a pentanediyl thio group, a hexanediyl thio group, a heptanediyl thio group, an octanediyl thio group, a nonanediyl thio group, a decanediyl thio group, an undecanediyl thio group, a dodecanediyl thio group, a 2-methylpropanediyl thio group, and the like. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, and a propylenesulfonyl group. In addition, substitution in the alkenediyl group and the alkynediyl group can be those containing a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the exemplified substitution in the above-described alkanediyl group.

[0014] Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene-3,6-diyl group, and a cyclooctane-1,5-diyl group. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkanediyl groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, a 5-norbornene-2,3-diyl group, an adamantane-1,5-diyl group, and an adamantane-2,6-diyl group. For example, the following groups and the like can be mentioned. The bonding site can be at an arbitrary position. TIFF0007704571000012.tif44168 The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and still more preferably 3 to 12. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include the groups represented below and the groups in which -O- of the groups represented below is replaced by -S-. The bonding site can be at an arbitrary position. TIFF0007704571000013.tif47158

[0015] Examples of the aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. When -CH2- contained in a hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more. Examples of the hydrocarbon group formed by combining two or more types include a group formed by combining an alkanediyl group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group. In the combination, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. For example, -alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-alicyclic hydrocarbon group-, -alkanediyl group-alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkanediyl group- and the like can be mentioned. Any of these groups may be bonded to an oxygen atom.

[0016] L 2 Examples of the substituent of the hydrocarbon group of L include a halogen atom, a cyano group, a hydroxy group, a carboxy group, 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 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 and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. 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, a dodecyloxy group and the like. 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, a butoxycarbonyl group and the like, examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, a butyryl group and the like, and examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. L 2 The hydrocarbon group in 2 may have one substituent or a plurality of substituents.

[0017] L 2 L is preferably a single bond, an alkanediyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group combining an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-), more preferably an alkanediyl group having 1 to 6 carbon atoms, still more preferably an alkanediyl group having 1 to 3 carbon atoms, and still more preferably a methylene group.

[0018] Preferably, s1 is 1, preferably, t1 is 1, and preferably, the sum of s1 and t1 is 2. The group represented by the formula (IC) is preferably a group represented by the following. TIFF0007704571000014.tif2395

[0019] In the group represented by the formula (IC), when u1 is 1 and R A is a group bonded to the carbon atom adjacent to L 2 is represented by the following formula. TIFF0007704571000015.tif3144R AExamples of the saturated hydrocarbon group include a chain saturated hydrocarbon group such as an alkyl group, an alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these. R A Examples of the alkyl group of A include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. The alicyclic saturated hydrocarbon group may be monocyclic, polycyclic, or spirocyclic. Examples of the alicyclic saturated hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc., and polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, etc. The combined group may be a group formed by combining one alkyl group and one alicyclic saturated hydrocarbon group as described above, or a group formed by combining two or more of either or both. R 1 and R 2 are preferably -O-CO-R 10 , -O-CO-O-R 10 , -O-L 1 -CO-O-R 10 and more preferably -O-CO-O-R 10 , -O-L 1 -CO-O-R 10 . R 1 and R 2 may be bonded to the ortho position, meta position, or para position with respect to the bonding positions of X 1 and X 2 respectively. Among them, it is preferably bonded to the para position with respect to the bonding positions of X 1 and X 2 .

[0020] R 4 、R 5 、R 7 and R 8Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 4 , R 5 , R 7 and R 8 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 further preferably 1 to 3. R 4 , R 5 , R 7 and R 8 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. 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, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, further preferably 1 to 6, and even 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. Specifically, examples of the alicyclic hydrocarbon group include the same groups as those exemplified by L 2 The groups exemplified by 2 can be mentioned. 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 number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group - alkanediyl group - *, alkyl group - aromatic hydrocarbon group - *), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, alicyclic hydrocarbon group - alkanediyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group formed by combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents a bonding site. Examples of the aromatic hydrocarbon group - alkanediyl group - * include aralkyl groups such as a benzyl group and a phenethyl group. Examples of the alkyl group - aromatic hydrocarbon group - * include a tolyl group, a xylyl group, a cumenyl group, etc. Examples of the alicyclic hydrocarbon group - alkanediyl group - * include cycloalkylalkyl groups such as a cyclohexylmethyl group, a cyclohexylethyl group, a 1-(adamantan-1-yl)methyl group, and a 1-(adamantan-1-yl)-1-methylethyl. 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 the combination, the alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may each be combined with two or more types. Also, any of these groups may be bonded to the benzene ring. Examples of a group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2- include a hydroxy group (a group in which -CH2- contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), a thiol (a group in which -CH2- contained in the methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in the alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -O-CO-), an alkylthio group (a group in which -CH2- at any position contained in the alkyl is replaced by -S-), an alkylsulfonyl group (a group in which -CH2- at any position contained in the alkyl is replaced by -SO2-), an alkylcarbonyl group (a group in which -CH2- at any position contained in the alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -CO-O-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, and the like. 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, and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 1, more preferably 1 to 6, and even more preferably 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group, and alkylcarbonyloxy group represent a group in which a carbonyl group or carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 12 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as cyclohexyloxy group and the like. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as cyclohexylmethoxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include aromatic hydrocarbon group-carbonyl-oxy groups having 7 to 17 carbon atoms, such as benzoyloxy group and the like. In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O- or -CO- include L 2 groups similar to the groups exemplified by When -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Further, the number may be one or two or more. R 4 R 5 R 7 and R 8 Examples of the substituent that the hydrocarbon group of may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-). Examples of the halogen atom include groups similar to the groups described above. Examples of the alkyl group having 1 to 12 carbon atoms include groups similar to the groups described above. When -CH2- contained in the alkyl group as the substituent is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the alkyl group. Examples of the replaced group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group include groups similar to the groups described above. The hydrocarbon group may have one substituent or a plurality of substituents.

[0021] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 1 and X 2 The bonding positions of may be any of the ortho position, meta position, and para position with respect to the bonding position of I + Among them, it is preferably bonded to the meta position or para position with respect to the bonding position of I + and more preferably bonded to the para position. m1 is preferably 1 or 2, more preferably 1. m2 is preferably 0, 1 or 2. m4 is preferably 0, 1, 2 or 4, more preferably 0, 1 or 2. m5 is preferably 0, 1, 2 or 4, more preferably 0, 1 or 2. m7 is preferably 0, 1 or 2, more preferably 0 or 1. m8 is preferably 0 or 1. R 4 and R 5 are each independently preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C6 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group or a C1-C4 alkyl group. R 7 and R 8 are each independently preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C6 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and even more preferably a fluorine atom, an iodine atom, a C1-C4 perfluoroalkyl group or a C1-C4 alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and still 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. When m2 is 0, m8 is 1 and R 8is preferably a branched alkyl group having 3 or 4 carbon atoms. When m4 is 2, R 1 is preferably in the p-position relative to the bonding position of X 1 , and preferably, one of the two Rs 4 is in the m-position relative to the bonding position (1-position) of X 1 and the other is in the o-position, and preferably, one is at the 3-position and the other is at the 6-position. When m5 is 2, R 2 is preferably in the p-position relative to the bonding position of X 2 , and preferably, one of the two Rs 5 is in the m-position relative to the bonding position (1-position) of X 2 and the other is in the o-position, and preferably, one is at the 3-position and the other is at the 6-position.

[0022] Examples of the cation of the salt (I) include cations represented by the following formulas (I-c-1) to (I-c-40). TIFF0007704571000016.tif217146

[0023] TIFF0007704571000017.tif231160

[0024] TIFF0007704571000018.tif183159

[0025] TIFF0007704571000019.tif181160

[0026] In the formula (I), examples of the hydrocarbon group represented by X 0 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. The -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 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 even more preferably 1 to 4. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, nonynyl group, etc. Examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include hydroxy group (the group in which -CH2- contained in the methyl group is replaced by -O-), carboxy group (the group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), thiol group (the group in which -CH2- contained in the methyl group is replaced by -S-), alkoxy group (the group in which -CH2- at any position contained in the alkyl group is replaced by -O-), alkoxycarbonyl group (the group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -O-CO-), alkylcarbonyl group (the group in which -CH2- at any position contained in the alkyl group is replaced by -CO-), alkylcarbonyloxy group (the group in which -CH2-CH2- at any position contained in the alkyl group is replaced by -CO-O-), alkylthio group (the group in which -CH2- at any position contained in the alkyl group is replaced by -S-), alkylsulfonyl group (the group in which -CH2- at any position contained in the alkyl group is replaced by -SO2-), etc. The thiol group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, and alkylcarbonyloxy group are, for example, a thiol group having 1 to 17 carbon atoms, 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. Examples of the alkylsulfonyl group include an alkylsulfonyl group having 1 to 17 carbon atoms, and the same groups as described above. Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, and a propylthio group. In addition, the substitution in the alkenyl group and alkynyl group may be any one that contains a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the exemplified substitution in the above-described alkyl group. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group, and polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group. Specific examples of the group in which the alicyclic hydrocarbon group and -CH2- contained in the alicyclic hydrocarbon group are replaced by -O-, -S-, -CO-, or -SO2- include the following groups. In the following groups, the bonding site can be at an arbitrary position. TIFF0007704571000020.tif79161

[0027] TIFF0007704571000021.tif58160X 0The alicyclic hydrocarbon group represented by or the -CH2- contained in the alicyclic hydrocarbon group replaced by -O-, -S-, -CO- or -SO2- is preferably a group represented by formulas (Y1) to (Y71), more preferably a group represented by any of formulas (Y1) to (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), and formulas (Y39) to (Y71), and even more preferably a group 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), and formulas (Y49) to (Y58), and formulas (Y62) to (Y71). The number of carbon atoms of 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.

[0028] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, groups having different valences (alkanediyl group, alkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) may be included in the above-mentioned groups.

[0029] The combined group means A group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A group formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group (the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and A group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, two or more alicyclic hydrocarbon groups, chain hydrocarbon groups and aromatic hydrocarbon groups may be combined respectively. Specifically, examples of the combined group include An alicyclic hydrocarbon group-chain hydrocarbon group-*, such as an adamantylmethylene group or a cyclohexylmethylene group, ((alicyclic hydrocarbon group)2-chain hydrocarbon group-*(wherein -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-alicyclic hydrocarbon group-*, such as a methyladamantyl group or a dimethyladamantyl group, ((chain hydrocarbon group)2-alicyclic hydrocarbon group-*(wherein -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-aromatic hydrocarbon group-*, such as a tolyl group or a xylyl group, (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-)), A 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-*(wherein -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-chain hydrocarbon group-*, such as a benzyl group, (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-)), A chain hydrocarbon group-aromatic hydrocarbon group-chain hydrocarbon group-*, such as a tolylmethyl 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 methyladamantylmethylenadamantyl group and di(methyladamantylmethylene)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 - *(wherein -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 - *(wherein -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 - alicyclic hydrocarbon group)2 - chain hydrocarbon group - *(wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), etc. Here, * represents the bonding position with the carbon atom of the carbonyl group.

[0030] X 0 When -CH2- contained in the hydrocarbon group represented by is replaced by -O-, -S-, -CO- or -SO2-, the carbon number before replacement is taken as the total carbon number of the hydrocarbon group. Also, X 0When a substituent is bonded to the hydrocarbon group represented by , the total number of carbon atoms before substitution is defined as the total number of carbon atoms of the hydrocarbon group. X 0 The hydrocarbon group represented by 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 formed by 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, a nonyl group, and the like. 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, a dodecyloxy group, and the like. 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-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and the like. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group, and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents the bonding position with X 0 and the bonding position with . As the aromatic hydrocarbon group having 6 to 10 carbon atoms, aryl groups such as phenyl group and naphthyl group can be mentioned. Examples of the combined group include a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group combining a halogen atom and an alkyl group having 1 to 12 carbon atoms, and the like. Examples of the group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 12 carbon atoms such as hydroxymethyl group and hydroxyethyl group. Examples of the group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as tolyl group and xylyl group. Examples of the group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include cyclohexylphenyl group. Examples of the group combining a halogen atom and an alkyl group having 1 to 12 carbon atoms include perfluoroalkyl groups having 1 to 12 carbon atoms such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, and the like.

[0031] X 0 As the hydrocarbon group represented by, preferably, an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (wherein -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. More preferably, it is an alicyclic hydrocarbon group which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -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, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group), an aromatic hydrocarbon group which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), Even more preferably, it is a *-alicyclic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * represents the bonding position to the carbon atom of -COO - .), a *-alicyclic hydrocarbon group-chain hydrocarbon group (wherein -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, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * represents the bonding position to the carbon atom of -COO - .), a *-chain hydrocarbon group-alicyclic hydrocarbon group (wherein -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, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * represents the bonding position to the carbon atom of -COO -represents the bonding position with the carbon atom of ().), an aromatic hydrocarbon group which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, a *-polycyclic alicyclic hydrocarbon group (the -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the polycyclic alicyclic hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of ().), a *-polycyclic alicyclic hydrocarbon group - chain hydrocarbon group (the -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, the -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, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of ().), a *-chain hydrocarbon group - polycyclic alicyclic hydrocarbon group (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, the -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, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of ().), an aromatic hydrocarbon group which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), Particularly preferably, an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-), a group represented by formula (Y30F) or a phenyl group having a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group. Based on the above, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, still more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. 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 even more preferably 6 to 10. TIFF0007704571000023.tif26127[In formula (aa), X a and X b each independently represents -O- or -S-. X 1 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 2 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-. * represents the bonding position with the carbon atom of -COO - .] [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 to 14 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 substituents, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position to the carbon atom of -COO - .

[0032] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0033] X 1a and X 2a Examples of the hydrocarbon group represented by include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining two or more of these. Note that these hydrocarbon groups may have substituents. Further, -CH2- contained in these hydrocarbon groups may be replaced by -O-, -S-, -CO- or -SO2-. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group having no substituents and no replacements.

[0034] X 1a Examples of the aliphatic hydrocarbon group of include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group formed by combining these. 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, a dodecanetriyl group, and the like.

[0035] 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, a cyclooctanetriyl group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include a norbornanetriyl group, a norbornanetriyl group, an adamantanetriyl group, and the like. Examples of the aromatic hydrocarbon group include a benzene triyl group, a naphthalene triyl group, an anthracene triyl group, and the like. In the case of a combined group, groups having different valences in the above-described groups (such as an alkyl group, an alkane diyl group, an alkane tetrayl group, a cycloalkyl group, a cycloalkane diyl group, a cycloalkane tetrayl group, etc.) may be included.

[0036] X 1a The hydrocarbon group represented by [X] has 1 to 24 carbon atoms and may further 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 obtained by combining these. Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group obtained by combining these are the same as those described above.

[0037] X 1a The hydrocarbon group represented by [X] 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 formula (w1-1) to formula (w1-11), still more preferably a polycyclic hydrocarbon group such as an alkanetriyl group having 1 to 6 carbon atoms, 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). TIFF0007704571000024.tif53143 [In 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 group combining these. * represents a bonding position.

[0038] X 2a The number of carbon atoms of the hydrocarbon group represented by is preferably 2 to 48, more preferably 4 to 48, still more preferably 6 to 44, even more preferably 8 to 40, and even still more preferably 10 to 38.

[0039] X 2a Examples of the substituent that the hydrocarbon group in 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 a group combining these are the same as those described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by may have one substituent or a plurality of substituents.

[0040] X 2a Examples of the hydrocarbon group in include a linear or branched chain hydrocarbon group (e.g., an alkanediyl group, etc.), a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and those combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic alicyclic hydrocarbon groups which are monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic alicyclic hydrocarbon groups which are polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group; Aromatic hydrocarbon groups such as phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group, binaphthylene group and the like can be mentioned. In the case of a combined group, groups with different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) in the above-mentioned groups may be included. Examples of the combined group include a group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, examples include a group in which one or more alicyclic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (for example, -aliphatic hydrocarbon group - alicyclic hydrocarbon group, -aliphatic hydrocarbon group -(alicyclic hydrocarbon group)2, etc.), a group in which one or more aliphatic hydrocarbon groups are bonded to an alicyclic hydrocarbon group (for example, -alicyclic hydrocarbon group - aliphatic hydrocarbon group, -alicyclic hydrocarbon group -(aliphatic hydrocarbon group)2, etc.), a group in which one or more alicyclic hydrocarbon groups and aliphatic hydrocarbon groups are bonded to an aliphatic hydrocarbon group (for example, -aliphatic hydrocarbon group - alicyclic hydrocarbon group - aliphatic hydrocarbon group, -aliphatic hydrocarbon group -(alicyclic hydrocarbon group - aliphatic hydrocarbon group)2, etc.).

[0041] X 2a Examples of the hydrocarbon group in include an aliphatic hydrocarbon group having 2 to 18 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-, and the aliphatic hydrocarbon group may have a substituent), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the -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 a group combining an aliphatic hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent), and it is preferably an aliphatic hydrocarbon group having 4 to 18 carbon atoms (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-, and the aliphatic hydrocarbon group may have a substituent), or A group combining an acyclic hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is more preferable. An acyclic hydrocarbon group having 6 to 14 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-, and the acyclic hydrocarbon group may have a substituent), or A group combining an acyclic hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the acyclic hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is even more preferable.

[0042] Specifically, for X 2a the hydrocarbon group in is, for example, An alkanediyl group having 2 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent), An alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -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), A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent), or A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) (the group may have a substituent) is preferred. An alkanediyl group having 4 to 18 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent). A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent), or More preferably, it is a group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) (the group may have a substituent). An alkanediyl group having 6 to 14 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and the alkanediyl group may have a substituent). A group composed of an alkanediyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-) and an adamantanediyl group (wherein -CH2- contained in the adamantanediyl group may be replaced by -O- or -CO-) (the group may have a substituent), or An alkandiyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkandiyl group may be replaced by -O- or -CO-), an adamantandiyl group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and the group may have a substituent.

[0043] Specifically, X 2 is preferably a group represented by formula (X 2 -1), a group represented by formula (X 2 -2), a group represented by formula (X 2 -3), or a group represented by formula (X 2 -4). TIFF0007704571000025.tif34158[wherein, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x each independently represent an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by 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. * represents the bonding position with X a and X b .] The combined group may be a combination of one alkyl group and one alicyclic hydrocarbon group as described above, or a group formed by combining two or more of either or both. In this case, the carbon number of the combined group is 39 or less, preferably 37 or less.

[0044] 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 (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -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 a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent). Preferably, it is a methoxy group, an adamantyl group (wherein -CH2- contained in the adamantyl group may be replaced by -O- or -CO-, and the adamantyl group may have a substituent), or a group formed by combining an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) and an adamantyl group (the group may have a substituent). More preferably, it is such a group.

[0045] 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 a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, 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. L BWhen -CH2- contained in the alkanediyl group is replaced by -O-, -S-, -CO- or -SO2-, the total carbon number before replacement is defined as the total carbon number of the alkanediyl group. The alkanediyl group may have a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), an alkanediyl-oxy group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -O-CO-), an alkanediylcarbonyl group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -CO-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), an alkanediylcarbonyl-oxy group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -CO-O-), an alkanediylthio group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -S-), or an alkanediylsulfonyl group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -SO2-). Examples of the thiol group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group, and alkylsulfonyl group are the same as those described above. Examples of the alkanediyl oxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyl oxy group, a butanediyl oxy group, a pentanediyl oxy group, and the like. Examples of the alkanediyl thio group include a methylene thio group, an ethylene thio group, a propanediyl thio group, a butanediyl thio group, a pentanediyl thio group, and the like. Examples of the alkanediyl sulfonyl group include a methylene sulfonyl group, an ethylene sulfonyl group, a propanediyl sulfonyl group, a butanediyl sulfonyl group, a pentanediyl sulfonyl group, and the like. Examples of the alkanediyl oxycarbonyl group include a methylene oxycarbonyl group, an ethylene oxycarbonyl group, a propanediyl oxycarbonyl group, a butanediyl oxycarbonyl group, and the like. Examples of the alkanediyl carbonyl group include a methylene carbonyl group, an ethylene carbonyl group, a propanediyl carbonyl group, a butanediyl carbonyl group, a pentanediyl carbonyl group, and the like. Examples of the alkanediyl carbonyl oxy group include a methylene carbonyl oxy group, an ethylene carbonyl oxy group, a propanediyl carbonyl oxy group, a butanediyl carbonyl oxy group, and the like. L A Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L include aromatic hydrocarbon groups such as arylene groups such as a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 10, more preferably 6. L A Examples of the halogen atom that L may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. L A Examples of the perfluoroalkyl group having 1 to 4 carbon atoms that L may have include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like. L Ais preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably an alkanediyl group having 1 to 3 carbon atoms having a fluorine atom or a phenylene group which may have a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 3 carbon atoms. L B is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0046] R A Examples of the hydrocarbon group in include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group and an alicyclic hydrocarbon group), an aromatic hydrocarbon group and a group 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 and the like. The number of carbon atoms of 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 even more preferably 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group, an isooctynyl group, a nonenyl group. 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, a nonynyl group and the like. Examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -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, an alkylsulfonyl group and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, the alkylcarbonyloxy group and the alkylthio group include, for example, 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 alkylthio group having 1 to 17 carbon atoms, and an alkylsulfonyl group having 1 to 17 carbon atoms, and groups similar to the above-described groups. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the like. Specific examples of the alicyclic hydrocarbon group and the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include the groups represented by the above formulas (y1) to (y71) and the like. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, still more preferably 3 to 18, even 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 and the like. The carbon number of 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 even more preferably 6 to 10. In the case of a combined group, groups having different valences (alkanediyl groups, alkanetriyl groups, cycloalkanediyl groups, cycloalkanetriyl groups, etc.) may be included in the above-mentioned groups. Examples of the group formed by combination include a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), and a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * represents a bonding site. Examples of the aromatic hydrocarbon group-alkanediyl group-* include aralkyl groups such as a benzyl group and a 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 a cyclohexylmethyl group, a cyclohexylethyl group, a 1-(adamantan-1-yl)methyl group, and a 1-(adamantan-1-yl)-1-methylethyl. 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 alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. Also, any group may be bonded to L B at any position. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include, in addition to the groups described above, a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, and the like. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include aromatic hydrocarbon group-carbonyl-oxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. When -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more.

[0047] R A Examples of the substituent that the hydrocarbon group of R may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-). Examples of the halogen atom include the same groups as those described above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those described above. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group include an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyloxy group having 2 to 11 carbon atoms. For example, the same groups as those described above can be mentioned. R A The hydrocarbon group in A may have one substituent or a plurality of substituents.

[0048] R A Examples of the hydrocarbon group in A include an alkyl group having 1 to 12 carbon atoms which may have a substituent (however, -CH2- contained in the alkyl group may be replaced by -O-, -S-, -CO- or -SO2-), or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). Preferably, it is 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 (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-).

[0049] Examples of the cyclic hydrocarbon group include a cyclic hydrocarbon group such as a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. Examples of the alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as those described above. In the combination, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be combined with two or more of each. Also, any group may be bonded to L B B .

[0050] 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 -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). 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 (wherein -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, More preferably, it 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 (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-). As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, the following groups (the bonding site is at an arbitrary position) are preferable, and as the aromatic hydrocarbon group, a phenyl group and a naphthyl group are preferable. TIFF0007704571000026.tif1687

[0051] Examples of the carboxylic acid anion in the carboxylate represented by the formula (I) include the carboxylic acid anions described below. TIFF0007704571000027.tif136157

[0052] TIFF0007704571000028.tif76130

[0053] TIFF0007704571000029.tif167141

[0054] TIFF0007704571000030.tif79157

[0055] TIFF0007704571000031.tif155143

[0056] TIFF0007704571000032.tif218160

[0057] TIFF0007704571000033.tif120162

[0058] TIFF0007704571000034.tif110153

[0059] Specific examples of the carboxylate (I) include salts obtained by arbitrarily combining the above-mentioned cations and carboxylate anions. Specific examples of the carboxylate (I) are shown in the following table. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned carboxylate anion or cation, and "~" indicates that each of the carboxylate (I) and the anion (I) corresponds. For example, the carboxylate (I-1) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-1), the carboxylate (I-2) is a salt composed of the anion represented by the formula (I-a-2) and the cation represented by the formula (I-c-1), and the carboxylate (I-96) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-2). TIFF0007704571000035.tif26126 [Table 1] TIFF0007704571000037.tif57147

[0060] Among them, as the carboxylate (I), a salt formed by combining an anion represented by any one of the formulas (I-a-1) to (I-a-5), (I-a-10) to (I-a-21), and (I-a-57) to (I-a-66) with a cation represented by any one of the formulas (I-c-1) to (I-c-40) is preferable. 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) to carboxylate (I-290), carboxylate (I-295) to carboxylate (I-306), carboxylate (I-342) to carboxylate (I-351), carboxylate (I-381) to carboxylate (I-385), carboxylate (I-390) to carboxylate (I-401), carboxylate (I-437) to carboxylate (I-446), carboxylate (I-476) to carboxylate (I-480), carboxylate (I-485) to carboxylate (I-496), carboxylate (I-532) to carboxylate (I-541), carboxylate (I-571) to carboxylate (I-575), carboxylate (I-580) to carboxylate (I-591), carboxylate (I-627) to carboxylate (I-636), carboxylate (I-666) to carboxylate (I-670), carboxylate (I-675) to carboxylate (I-686), carboxylate (I-722) to carboxylate (I-731), carboxylate (I-761) to carboxylate (I-765), carboxylate (I-770) to carboxylate (I-781), carboxylate (I-817) to 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) to Carboxylate (I-1111), Carboxylate (I-1141) to Carboxylate (I-1145), Carboxylate (I-1150) to Carboxylate (I-1161), Carboxylate (I-1197) to Carboxylate (I-1206), Carboxylate (I-1236) to Carboxylate (I-1240), Carboxylate (I-1245) to Carboxylate (I-1256), Carboxylate (I-1292) to Carboxylate (I-1301), Carboxylate (I-1331) to Carboxylate (I-1335), Carboxylate (I-1340) to Carboxylate (I-1351), Carboxylate (I-1387) to Carboxylate (I-1396), Carboxylate (I-1426) to Carboxylate (I-1430), Carboxylate (I-1435) to Carboxylate (I-1446), Carboxylate (I-1482) to Carboxylate (I-1491), Carboxylate (I-1521) to Carboxylate (I-1525), Carboxylate (I-1530) to Carboxylate (I-1541), Carboxylate (I-1577) to Carboxylate (I-1586), Carboxylate (I-1616) to Carboxylate (I-1620), Carboxylate (I-1625) to Carboxylate (I-1636), Carboxylate (I-1672) to Carboxylate (I-1681), Carboxylate (I-1711) to Carboxylate (I-1715), Carboxylate (I-1720) to Carboxylate (I-1731), Carboxylate (I-1767) to Carboxylate (I-1776), Carboxylate (I-1806) to Carboxylate (I-1810), Carboxylate (I-1815) to Carboxylate (I-1826), Carboxylate (I-1862) to Carboxylate (I-1871), Carboxylate (I-1901) to Carboxylate (I-1905), Carboxylate (I-1910) to Carboxylate (I-1921), Carboxylate (I-1957) to Carboxylate (I-1966), Carboxylate (I-1996) to Carboxylate (I-2000), Carboxylate (I-2005) to Carboxylate (I-2016), Carboxylate (I-2052) to Carboxylate (I-2061), Carboxylate (I-2091) to Carboxylate (I-2095), Carboxylate (I-2100) to Carboxylate (I-2111)Carboxylate (I-2147) to Carboxylate (I-2156), Carboxylate (I-2186) to Carboxylate (I-2190), Carboxylate (I-2195) to Carboxylate (I-2206), Carboxylate (I-2242) to Carboxylate (I-2251), Carboxylate (I-2281) to Carboxylate (I-2285), Carboxylate (I-2290) to Carboxylate (I-2301), Carboxylate (I-2337) to Carboxylate (I-2346), Carboxylate (I-2376) to Carboxylate (I-2380), Carboxylate (I-2385) to Carboxylate (I-2396), Carboxylate (I-2432) to Carboxylate (I-2441), Carboxylate (I-2471) to Carboxylate (I-2475), Carboxylate (I-2480) to Carboxylate (I-2491), Carboxylate (I-2527) to Carboxylate (I-2536), Carboxylate (I-2566) to Carboxylate (I-2570), Carboxylate (I-2575) to Carboxylate (I-2586), Carboxylate (I-2622) to Carboxylate (I-2631), Carboxylate (I-2661) to Carboxylate (I-2665), Carboxylate (I-2670) to Carboxylate (I-2681), Carboxylate (I-2717) to Carboxylate (I-2726), Carboxylate (I-2756) to Carboxylate (I-2760), Carboxylate (I-2765) to Carboxylate (I-2776), Carboxylate (I-2812) to Carboxylate (I-2821), Carboxylate (I-2851) to Carboxylate (I-2855), Carboxylate (I-2860) to Carboxylate (I-2871), Carboxylate (I-2907) to Carboxylate (I-2916), Carboxylate (I-2946) to Carboxylate (I-2950), Carboxylate (I-2955) to Carboxylate (I-2966), Carboxylate (I-3002) to Carboxylate (I-3011), Carboxylate (I-3041) to Carboxylate (I-3045), Carboxylate (I-3050) to Carboxylate (I-3061), Carboxylate (I-3097) to Carboxylate (I-3106), Carboxylate (I-3136) to Carboxylate (I-3140), Carboxylate (I-3145) to Carboxylate (I-3156), Carboxylate (I-3192) to Carboxylate (I-3201), Carboxylate (I-3231) to Carboxylate (I-3235)Carboxylic acid salt (I-3240)~Carboxylic acid salt (I-3251), Carboxylic acid salt (I-3287)~Carboxylic acid salt (I-3296), Carboxylic acid salt (I-3326)~Carboxylic acid salt (I-3330), Carboxylic acid salt (I-3335)~Carboxylic acid salt (I-3346), Carboxylic acid salt (I-3382)~Carboxylic acid salt (I-3391), Carboxylic acid salt (I-3421)~Carboxylic acid salt (I-3425), Carboxylic acid salt (I-3430)~Carboxylic acid salt (I-3441), Carboxylic acid salt (I-3477)~Carboxylic acid salt (I-3486), Carboxylic acid salt (I-3516)~Carboxylic acid salt Carboxylic salt (I-3520), carboxylic salt (I-3525) to carboxylic salt (I-3536), carboxylic salt (I-3572) to carboxylic salt (I-3581), carboxylic salt (I-3611) to carboxylic salt (I-3615), carboxylic salt (I-3620) to carboxylic salt (I-3631), carboxylic salt (I-3667) to carboxylic salt (I-3676), carboxylic salt (I-3706) to carboxylic salt (I-3710), carboxylic salt (I-3715) to carboxylic salt (I-3726), and carboxylic salt (I-3762) to carboxylic salt (I-3771) are preferred.

[0061] <Method for producing salt (I)> The salt (I) can be produced by reacting a salt represented by the formula (Ia) with a salt represented by the formula (Ib) in a solvent. TIFF0007704571000038.tif62163 [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 together to form an aromatic ring. D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.] Examples of the solvent 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.

[0062] The salt represented by formula (I-b) can be synthesized with reference to the methods described in JP-A-2011-39502 and JP-A-2014-88367, and examples thereof include salts represented below. TIFF0007704571000039.tif133164

[0063] In salt (I-a), R 1 and R 2 are -O-L 1 -CO-O-R 10 The salt (the salt represented by formula (I-a1)) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d) in a solvent in the presence of a base catalyst. TIFF0007704571000040.tif61158 [In the formula, all symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0064] Examples of the compound represented by formula (I-d) include compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704571000041.tif1377

[0065] The salt represented by formula (I-c) can be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f1), and the compound represented by formula (I-f2) in a solvent in the presence of a catalyst. TIFF0007704571000042.tif70161 [In the formula, all symbols have the same meanings as described above.] Examples of the catalyst include potassium carbonate, sodium hydride and the like. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like. The reaction temperature is generally 15°C to 100°C, and the reaction time is generally 0.5 to 24 hours.

[0066] Examples of the salt represented by formula (I-e) include salts represented by the following formula, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704571000043.tif41153

[0067] Examples of the compound represented by formula (I-f1) and the compound represented by formula (I-f2) include compounds represented below, which can be easily obtained from the market. TIFF0007704571000044.tif20104

[0068] The salt represented by formula (I-c) can also be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f4), and the compound represented by formula (I-f5) in a solvent in the presence of potassium carbonate and then performing acid treatment. TIFF0007704571000045.tif76154[In the formula, all symbols have the same meanings as described above. R ac represents an acid-labile group.] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like. The reaction temperature is generally 15°C to 100°C, and the reaction time is generally 0.5 to 24 hours. Examples of the acid include p-toluenesulfonic acid, hydrochloric acid and the like.

[0069] Examples of the compound represented by formula (I-f4) and the compound represented by formula (I-f5) include compounds represented below, which can be easily obtained from the market. TIFF0007704571000046.tif84154

[0070] In salt (I-a), R 1 and R 2 are -O-R 10 The salt represented by formula (I-a2) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d2) in a solvent in the presence of a base catalyst. TIFF0007704571000047.tif63165 [In the formula, all the symbols have the same meanings as described 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.

[0071] Examples of the compound represented by formula (I-d2) include the compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007704571000048.tif1366

[0072] In salt (I-a), R 1 and R 2 are -O-CO-O-R 10 The salt represented by formula (I-a3) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d2) in a solvent in the presence of carbonyldiimidazole. TIFF0007704571000049.tif63161 [In the formula, all the symbols have the same meanings as described 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.

[0073] In salt (I-a), R1 and R 2 and is -O-CO-R 10 The salt (the salt represented by formula (I-a4)) which is as follows can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d4) in a solvent in the presence of a base catalyst. TIFF0007704571000050.tif68162[In the formula, all the symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is usually from 15°C to 80°C, and the reaction time is usually from 0.5 to 24 hours.

[0074] Examples of the compound represented by formula (I-d4) include the compounds represented below, and they can be easily obtained from the market, and can also be easily produced by known production methods. TIFF0007704571000051.tif1318

[0075] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylate (I). The carboxylate (I) of the present invention can act as an acid generator in a resist composition. When the carboxylate (I) is used as the acid generator in the resist composition, the acid generator may contain only one kind or two or more kinds of carboxylates (I). In addition, as described later, the carboxylic acid generator of the present invention may further contain an acid generator known in the resist field other than the carboxylate (I) (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator known in the resist field other than the carboxylate (I). The acid generator (B) may be used alone or in combination of two or more. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the content of the carboxylate (I) to the acid generator (B) or the like (mass ratio; carboxylate (I): acid generator (B)) 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.

[0076] 〔Resist Composition〕 The resist composition contains a carboxylic acid generator containing the carboxylate (I) of the present invention, an acid generator (B) other than the carboxylate (I), and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" means a group having a leaving group, and when the leaving group is eliminated by contact with an acid, a hydrophilic group (for example, a hydroxy group or a carboxy group) is formed. The resist composition preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)").

[0077] <Acid Generator (B)> Either a nonionic or ionic acid generator (B) may be used. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid generators include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0078] As the acid generator (B), compounds that generate an acid upon irradiation, 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, US Patent No. 3,779,778, US Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Further, compounds produced by known methods may also be used. Two or more acid generators (B) may be used in combination.

[0079] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007704571000052.tif2962[In the 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, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation.]

[0080] Q b1 and Q b2Examples of the perfluoroalkyl group represented by include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. Q b1 and Q b2 and Q are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0081] L b1 Examples of the divalent saturated hydrocarbon group in include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups. Specifically, 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 an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups that are cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group; Examples thereof include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, and the like.

[0082] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by any of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent bonding positions, and * represents the bonding position with -Y.

[0083] TIFF0007704571000053.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, 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 replaced by -O- or -CO-. However, b2 the total number of carbon atoms of L b3 and L 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, 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 replaced by -O- or -CO-. However, b4 the total number of carbon atoms of L b5The total number of carbon atoms with [the relevant group] 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b6 and L b7 is 23 or less.

[0084] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same ones as the divalent saturated hydrocarbon group of L b1 .

[0085] 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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0086] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by b1 is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable.

[0087] Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8), respectively. TIFF0007704571000054.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. 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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b9 and b10 The total number of carbon atoms of L 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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b11 and b12The total carbon number 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 by -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 replaced by a fluorine atom or a hydroxy group. However, the total carbon number of L b13 to L b15 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 by -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 replaced by a fluorine atom or a hydroxy group. However, the total carbon number of L b16 to L b18 is 19 or less.

[0088] 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, 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, 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, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0089] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11). TIFF0007704571000055.tif23140 [In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, the total number of carbon atoms of L b19 and L b20 is 23 or less. In the formula (b1-10), L b21represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b21 、L b22 and L b23 The total number of carbon atoms of 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b24 、L b25 and L b26 The total number of carbon atoms of is 21 or less.]

[0090] In addition, in the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with alkylcarbonyloxy groups, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group.

[0091] Examples of the alkyloxycarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

[0092] Examples of the group represented by formula (b1-4) include the following. TIFF0007704571000056.tif16154

[0093] Examples of the group represented by formula (b1-5) include the following. TIFF0007704571000057.tif68152

[0094] Examples of the group represented by formula (b1-6) include the following. TIFF0007704571000058.tif32164

[0095] Examples of the group represented by formula (b1-7) include the following. TIFF0007704571000059.tif57146

[0096] Examples of the group represented by formula (b1-8) include the following. TIFF0007704571000060.tif23150

[0097] Examples of the group represented by formula (b1-2) include the following. TIFF0007704571000061.tif31161

[0098] Examples of the group represented by formula (b1-9) include the following. TIFF0007704571000062.tif44137

[0099] Examples of the group represented by formula (b1-10) include the following. TIFF0007704571000063.tif92165

[0100] Examples of the group represented by formula (b1-11) include the following. TIFF0007704571000064.tif84164

[0101] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO2- or -CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). TIFF0007704571000065.tif84169

[0102] The alicyclic hydrocarbon group represented by Y is preferably a group represented by any of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and even more preferably a group 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 formula (Y28) to formula (Y35), formula (Y39) to formula (Y40), formula (Y42) or formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

[0103] Examples of the substituent of the methyl group represented by Y include 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-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein 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 group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the 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.). Examples of the substituent 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 by a hydroxy group (the -CH2- contained in the alkyl group may be replaced by -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-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein 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 group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the 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.).

[0104] 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, an adamantyl group, and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. 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. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-methylphenyl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.). The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. 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, and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even 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 the group in which -CH2- contained in the alkyl group is replaced by -O-, -SO2-, -CO- or the like include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group or a group combining these. 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 still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group and a propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyl group include, for example, an acetyl group, a propionyl group and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyloxy group include, for example, an acetyloxy group, a propionyloxy group and a butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the combined group include, for example, 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, 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 methoxymethyl group, methoxyethyl group, ethoxyethyl group, ethoxy methyl group, etc. The number of carbon atoms of the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkoxy group include alkoxyalkoxy groups such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, etc. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as methoxyacetyl group, methoxypropionyl group, ethoxyacetyl group, ethoxypropionyl group, etc. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and still more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, ethoxypropionyloxy group, etc. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and still more preferably 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43), etc.

[0105] Examples of Y include the following. TIFF0007704571000066.tif160165

[0106] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, even more preferably an adamantyl group which may have a substituent, and -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -SO2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by formula (Y42), formula (Y100) to formula (Y114).

[0107] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and 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), formula (B1-A-47) to formula (B1-A-59) is more preferable. TIFF0007704571000067.tif154161

[0108] TIFF0007704571000068.tif65159

[0109] TIFF0007704571000069.tif101155

[0110] TIFF0007704571000070.tif64162

[0111] TIFF0007704571000071.tif111141

[0112] TIFF0007704571000072.tif123166

[0113] TIFF0007704571000073.tif68133 Here, R i2 ~R i7 is, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R 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. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q 1 and Q 2 represent the same meaning as described above. Specific examples of the anion represented by the formula (I-A) include the anions described in JP-A-2010-204646.

[0114] Preferred anions in the salt represented by the formula (B1) include the anions represented by the formulas (B1a-1) to (B1a-38), respectively. TIFF0007704571000074.tif89152

[0115] TIFF0007704571000075.tif93139

[0116] TIFF0007704571000076.tif142156

[0117] TIFF0007704571000077.tif63150

[0118] Among them, an anion represented by any one of the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-38) is preferred.

[0119] 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. Specifically, cations represented by any of formula (b2-1) to formula (b2-4) (hereinafter may be referred to as "cation (b2-1)" etc. according to the formula number) can be mentioned. TIFF0007704571000078.tif46165In formula (b2-1) to formula (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the 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, and the 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 the 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 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, 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 any of 0 to 5. When m2 is 2 or more, a plurality of R b7 may be the same or different, and when n2 is 2 or more, a plurality of 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 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -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 the hydrogen atom contained in the chain hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by 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 -CH-CO- to which they are bonded, and the -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 any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 are the same or different, and when p2 is 2 or more, the plurality of R b14are the same or different, and when q2 is 2 or more, a plurality of Rs b15 are the same or different, and when r2 is 2 or more, a plurality of Rs b16 are the same or different, and when s2 is 2 or more, a plurality of Rs b17 are the same or different, and when t2 is 2 or more, a plurality of Rs b18 are the same or different. The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, the R b9 ~R b12 chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. TIFF0007704571000079.tif10159In particular, the R b9 ~R b12 alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group, and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms with a fluorine atom, and examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl, etc. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) etc. are mentioned. In addition, when the aromatic hydrocarbon group contains a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group with 1 to 18 carbon atoms and an alicyclic hydrocarbon group with 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group etc. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group etc. Examples of the alkylcarbonyl group include acetyl group, propionyl group and butyryl group etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom etc. 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 The ring formed by R and R being bonded to each other together with the sulfur atom to which they are bonded may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings, and examples thereof include the following rings. * represents a bonding position. TIFF0007704571000080.tif23144R b9 and R b10 The ring formed by R and R together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. 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 R and R together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

[0120] Among the cations (b2-1) to (b2-4), preferably, it is the cation (b2-1). Examples of the cation (b2-1) include the following cations. TIFF0007704571000081.tif73149

[0121] TIFF0007704571000082.tif109166

[0122] Examples of the cation (b2-2) include the following cations and the like. TIFF0007704571000083.tif18150

[0123] Examples of the cation (b2-3) include the following cations and the like. TIFF0007704571000084.tif25122

[0124] Examples of the cation (b2-4) include the following cations and the like. TIFF0007704571000085.tif62164

[0125] TIFF0007704571000086.tif70158

[0126] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. Preferred examples of the acid generator (B) include a combination of an anion represented by any of Formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) to Formula (B1a-38) and the cation (b2-1), the cation (b2-3) or the cation (b2-4).

[0127] Preferred examples of the acid generator (B) include those represented by Formula (B1-1) to Formula (B1-56). Among them, those containing an arylsulfonium cation are preferred, and those represented by Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14), Formula (B1-20) to Formula (B1-26), Formula (B1-29), Formula (B1-31) to Formula (B1-56) are particularly preferred. TIFF0007704571000087.tif98161

[0128] TIFF0007704571000088.tif152165

[0129] TIFF0007704571000089.tif92158

[0130] TIFF0007704571000090.tif144161

[0131] TIFF0007704571000091.tif63168

[0132] TIFF0007704571000092.tif92158

[0133] In the resist composition of the present invention, the content of the carboxylate (I) is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and still more preferably 1% by mass or more and 25% by mass or less with respect to the solid content of the resist composition. In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and still more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds thereof.

[0134] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)")), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0135] 〈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 the formula (1) (hereinafter also referred to as group (1)) and / or a group represented by the formula (2) (hereinafter also referred to as group (2)). TIFF0007704571000093.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 these, or R a1 and R a2 are bonded 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 bonding position.] TIFF0007704571000094.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 a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and the -CH2- 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.]

[0136] R a1 、R a2 and R a3Examples 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 a3 Examples of the alkenyl group in include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group, an isooctynyl group, and a nonenyl group. 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. TIFF0007704571000095.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group in 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 (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, etc. Preferably, ma is 0 and na is 1. R a1 and R a2 when they are bonded to each other to form an alicyclic hydrocarbon group, -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 to -O-. TIFF0007704571000096.tif31135

[0137] R a1’ , R a2’ and R a3’ Examples of the hydrocarbon group in R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. a1 , R a2 and R a3 are the same as those mentioned above. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl group (e.g., benzyl group), aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), alicyclic hydrocarbon group having an aromatic hydrocarbon group (phenylcyclohexyl group, etc.). R a2’ and R a3’ when they are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-X-R a3’ includes the following groups. * represents the bonding position. TIFF0007704571000097.tif21142R a1’ and R a2’ Among them, at least one is preferably a hydrogen atom. na’ is preferably 0.

[0138] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferable. 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, R a3 is an adamantyl group, ma = 0, and na = 1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007704571000098.tif170163

[0139] Specific examples of the group (2) include the following groups. * represents a bonding position. TIFF0007704571000099.tif68162

[0140] 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.

[0141] Among the (meth)acrylic monomers having an acid-labile group, preferably those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms can be mentioned. If 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.

[0142] As the structural unit derived from the (meth)acrylic monomer having the group (1), a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as the structural unit (a1-2)) can be mentioned. Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007704571000100.tif43143[In the formula (a1-0), the formula (a1-1) and the formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or * -O-(CH2) k1 -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 a7each 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 any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.]

[0143] R a01 R a4 and R a5 are preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 L a1 and L a2 are preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1), more preferably an oxygen atom. R a02 R a03 and R a04 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these in R a1 ~R a3 are the same groups as those exemplified for the groups of R R a6 and R a7 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these in R a1 R a2 and R a3 are the same groups as those exemplified for the groups of R R a02 R a03 and R a04 The alkyl group in R R a6 and R a7The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and still more preferably an ethyl group, an isopropyl group or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group. R a02 、R a03 and R a04 The number of carbon atoms of the alicyclic hydrocarbon group of and is preferably 5 to 12, more preferably 5 to 10. R a02 、R a03 、R a04 、R a6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group of and is preferably 6 to 12, more preferably 6 to 10. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and alicyclic hydrocarbon group is 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and aromatic hydrocarbon group is 18 or less. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, 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, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7is 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 still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.

[0144] Examples of the structural unit (a1-0) include structural units represented by any of the formulas (a1-0-1) to (a1-0-18) and a methyl group corresponding to R in the structural unit (a1-0) a01 which is replaced with a hydrogen atom, a halogen atom, a haloalkyl group (an alkyl group having a halogen atom), or another alkyl group. Structural units represented by any of the formulas (a1-0-1) to (a1-0-10), (a1-0-13), and (a1-0-14) are preferred. TIFF0007704571000101.tif100167

[0145] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, structural units represented by any of the formulas (a1-1-1) to (a1-1-7) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-1) a4 is replaced with a hydrogen atom are preferred, and structural units represented by any of the formulas (a1-1-1) to (a1-1-4) are more preferred. TIFF0007704571000102.tif39167

[0146] Examples of the structural unit (a1-2) include structural units represented by any of the formulas (a1-2-1) to (a1-2-14) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-2) a5Examples of the structural unit in which the methyl group corresponding thereto is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group include structural units represented by any of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-14), and a structural unit represented by any of them is preferable. TIFF0007704571000103.tif67163

[0147] When the resin (A) contains the structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% with respect to all the structural units of 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%, still more preferably 20 to 80 mol%, and even more preferably 20 to 75 mol% with respect to all the structural units of the resin (A).

[0148] Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by formula (a1-4) (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF0007704571000104.tif3854[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 represents a single bond or * -X a31 -(A a32 -X a32 ) ncrepresents -, and * is -R a32 represents the bonding site with the carbon atom to which a32 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 any integer from 0 to 4. When la is any integer of 2 or more, a plurality of R a33 may be the same as or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.

[0149] R a32 and R a33 Examples of the halogen atom in R and R include a fluorine atom, a chlorine atom, a bromine atom and the like. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R 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 a32is 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 a33 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 a33 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. R a33 Examples of the alkoxyalkyl group in a33 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 a33 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, more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in a33 include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33Examples of the alkylcarbonyloxy group 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.

[0150] *-X a31 -(A a32 -X a32 ) nc Examples of - include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32 -O-CO- are included. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0151] 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.

[0152] A a30is a single bond, *-CO-O- or *-CO-O-A a32 -CO-O- is preferred, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0153] 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 combining these groups. 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, an octyl group and the like. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bonding site). TIFF0007704571000105.tif10151 Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group and the like. Examples of the combined group include a group combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cyclohexyl group such as a phenylcyclohexyl group, and the like. In particular, R a36Examples thereof 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 groups.

[0154] 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 of 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 groups, 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. R a36 The alkyl group and the alicyclic hydrocarbon group in are preferably unsubstituted. R a36 The aromatic hydrocarbon group in preferably has an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0155] -OC(R a34 )(R a35 )-O-R a36 is eliminated by contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0156] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by the formulas (a1-4-1) to (a1-4-18) and R in the structural unit (a1-4) a32Examples of the structural unit in which the hydrogen atom corresponding to is replaced with a halogen atom, a haloalkyl group, or an alkyl group include, more preferably, structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), and formula (a1-4-14). TIFF0007704571000106.tif100166When the resin (A) has the structural unit (a1-4), its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol% with respect to the total of all the structural units of the resin (A).

[0157] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include a structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007704571000107.tif4354In formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of 1 to 4, and * represents the bonding position with L 51 . L 51 , L 52 , L 53 and L 54 each independently represent -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0158] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is 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 them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably any integer from 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0159] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by formulas (a1-5-1) to (a1-5-4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. When the resin (A) has the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0160] In addition, examples of the structural unit (a1) include the following structural units. When the resin (A) contains the above structural unit, its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 40 mol% based on all the structural units of the resin (A).

[0161] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. As the structural unit(s), it is preferable to have a hydroxy group or a lactone ring. By using a resin having a structural unit having a hydroxy group and not having an acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and not having an 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 the adhesion to the substrate can be improved.

[0162] 〈Structural unit (a2)〉 The hydroxy group that the structural unit (a2) has may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam or EUV (extreme ultraviolet light) as the exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. Further, when using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be contained alone or in two or more kinds.

[0163] Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007704571000110.tif4349[In the 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 a51represents 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 - and * represents the bonding position with the carbon atom to which -R a50 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 any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R a51 may be the same as or different from each other.

[0164] R a50 and R a51 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom and the like. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in 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 a50is 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 a51 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 a51 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 a51 Examples of the alkoxyalkyl group in a51 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 a51 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, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in a51 include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a51Examples of the alkylcarbonyloxy group 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, 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 ethoxyethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0165] *-X a51 -(A a52 -X a52 ) nb Examples of - include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO-, etc. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A 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-O-A a52It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-. 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-position or para-position of the benzene ring, and more preferably bonded to the para-position.

[0166] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include structural units represented by formula (a2-2-1) to formula (a2-2-16), and structural units in which the methyl group corresponding to R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-16) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or an alkyl group. The structural unit (a2-A) is preferably a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formula (a2-2-12) to formula (a2-2-14), and the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formula (a2-2-12) to formula (a2-2-14). a50 Examples thereof include structural units in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or an alkyl group. The structural unit (a2-A) is preferably a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formula (a2-2-12) to formula (a2-2-14), and the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formula (a2-2-12) to formula (a2-2-14). a50 Examples thereof include structural units in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or an alkyl group. The structural unit (a2-A) is preferably a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), the structural units 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), the structural units represented by formula (a2-2-12) to formula (a2-2-14). a50It is more preferable that the structural unit is one in which the methyl group corresponding to is replaced by a hydrogen atom. In the structural unit represented by the formula (a2-2-8) and the structural unit represented by the formula (a2-2-8), R in the structural unit (a2-A) a50 It is even more preferable that the structural unit is one in which the methyl group corresponding to is replaced by a hydrogen atom. When the resin (A) contains the structural unit (a2-A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all the structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like, the structural unit (a2-A) can be incorporated into the resin (A) by treating with an alkali such as tetramethylammonium hydroxide.

[0167] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include the structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). In the formula (a2-1), L a3 represents -O- or * -O-(CH2) k2 -CO-O-, k2 represents any integer from 1 to 7. * represents the bonding position to -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents any integer from 0 to 10.

[0168] In the formula (a2-1), La3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), 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, more preferably 0 or 1.

[0169] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of formula (a2-1-1) to formula (a2-1-6) is preferable, the structural unit represented by any of formula (a2-1-1) to formula (a2-1-4) is more preferable, and the structural unit represented by formula (a2-1-1) or formula (a2-1-3) is further preferable. When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, further preferably 2 to 20 mol%, and even more preferably 2 to 10 mol% based on all the structural units of the resin (A).

[0170] 〈Structural unit (a3)〉 The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, adamantane lactone ring, or bridged ring containing a γ-butyrolactone ring structure (for example, the structural unit represented by the following formula (a3-2)) can be mentioned. The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). These may be contained alone or in combination of two or more. TIFF0007704571000114.tif51161 [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 any of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -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 a halogen atom, 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 Ra21 , R a22 , R a23 and / or R a25 may be the same as or different from each other.]

[0171] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in R include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, and tert-butyl group. R a24 Examples of the halogen atom in R include fluorine atom, chlorine atom, bromine atom, and iodine atom. R a24 Examples of the alkyl group in R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, alkyl groups having 1 to 4 carbon atoms are included, and more preferably, methyl group or ethyl group is included. R a24 Examples of the alkyl group having a halogen atom in R include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, etc.

[0172] L a8 and L a9 Examples of the alkanediyl group in L include 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, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group, etc.

[0173] In formulas (a3-1) to (a3-3), L a4 ~L a6 is each independently preferably -O- or, *-O-(CH2) k3 -CO-O-, where k3 is an integer from 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, 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 are each independently preferably an integer from 0 to 2, more preferably 0 or 1.

[0174] 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, 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 *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)’. TIFF0007704571000115.tif4051 (wherein R a24 , L a7 represent the same meaning as above.)

[0175] Examples of the structural unit (a3) include structural units derived from the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include structural units represented by any of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3-1), formula (a3-3-2), and formula (a3-4-1) to formula (a3-4-12), and in the said structural units, R in formula (a3-1) to formula (a3-4) a18 、R a19 、R a20 and R a24 are preferably structural units in which the methyl groups corresponding to are replaced with hydrogen atoms. TIFF0007704571000116.tif117165

[0176] When the resin (A) contains the structural unit (a3), the total content is usually 1 to 70 mol%, preferably 1 to 65 mol%, more preferably 1 to 60 mol% based on all the structural units of the resin (A). Also, 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%, still more preferably 1 to 50 mol% based on all the structural units of the resin (A).

[0177] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007704571000117.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a fluorine atom with 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.] R 42The saturated hydrocarbon group represented by is exemplified by a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

[0178] 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 group (* represents the bonding position). Examples of the group formed by combination include a group 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, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

[0179] Examples of the structural unit (a4) include a structural unit represented by at least one selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3), and formula (a4-4). TIFF0007704571000119.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.]

[0180] L4a Examples of the alkanediyl group in [0] include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, etc., and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0181] L 3a Examples of the perfluoroalkanediyl group in [6] include difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2-diyl group, 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, perfluorooctane-4,4-diyl group, etc. L 3a Examples of the perfluorocycloalkanediyl group in

[10] include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, perfluoroadamantanediyl group, etc.

[0182] L 4a is preferably a single bond, methylene group or ethylene group, more preferably a single bond or methylene group. L 3ais preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0183] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R 5a in the structural unit (a4-0) is replaced by a hydrogen atom. TIFF0007704571000120.tif98165

[0184] TIFF0007704571000121.tif4461[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 by -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). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007704571000122.tif1383[In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent 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 represent -O-, -CO-, -CO-O- or -O-CO-. However, A a42 、A a43 、A a44 、X a41 and Xa42 The total number of carbon atoms is 7 or less. * represents a bonding position, and the * on the right is -O-CO-R a42 and is the bonding position with.

[0185] R a42 Examples of the saturated hydrocarbon group in R include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0186] 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; polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding position). TIFF0007704571000123.tif11160Examples of the group formed by combination include a group 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, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0187] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the 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. TIFF0007704571000124.tif752[In the formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. Aa45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * is R a42 represents the bonding position with.] However, in R a42 -X a43 -A a45 when R a42 has no halogen atom, A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and having at least one halogen atom.

[0188] A a45 Examples of the aliphatic hydrocarbon group in include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding position). TIFF0007704571000125.tif11160

[0189] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42When it 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 the perfluoroalkyl group 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 the perfluorocycloalkyl group include a perfluorocyclohexyl group. R a42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the number of carbon atoms contained in the group represented by the formula (a-g3), R a42 preferably has a total number of carbon atoms of 15 or less, and more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0190] R a42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF0007704571000126.tif874 [In the 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 the bonding position with A a46 ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A a46 , A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents the bonding position with the carbonyl group.

[0191] A a46 The number of carbon atoms in the saturated hydrocarbon group of A is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms in the aliphatic hydrocarbon group of A is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0192] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007704571000127.tif13161

[0193] A a41 Examples of the alkanediyl group in A include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. A a41 Examples of the substituent in the alkanediyl group represented by A 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.

[0194] A in the group represented by the formula (a-g1) a42 、A a43 and A a44Examples of the divalent saturated hydrocarbon group represented by include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, and groups formed by combining alkanediyl groups and divalent alicyclic hydrocarbon groups, etc. 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, a 2-methylpropane-1,2-diyl group, etc. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula (1) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0195] In the group represented by formula (a-g1), X a42 Examples of the group in which is -O-, -CO-, -CO-O-, or -O-CO- include the following groups. In the following examples, * and ** each represent a bond position, and ** represents -O-CO-R a42 This is the bonding position with. TIFF0007704571000128.tif48153

[0196] 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 In the structural unit, a methyl group corresponding to the above formula is replaced with a hydrogen atom. TIFF0007704571000129.tif100142

[0197] TIFF0007704571000130.tif123141

[0198] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). TIFF0007704571000131.tif3353[In formula (a4-2), R f5represents 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 by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. However, L 44 and R f6 The upper limit of the total number of carbon atoms is 21.

[0199] L 44 The alkanediyl group of may be the same group as exemplified by A a41 R f6 The saturated hydrocarbon group of may be the same group as exemplified by R a42 L 44 As the alkanediyl group in, an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

[0200] Examples of the structural unit represented by the formula (a4-2) include the structural units represented by the formulas (a4-1-1) to (a4-1-11), respectively. The structural unit in which the methyl group corresponding to R f5 in the structural unit (a4-2) is replaced by a hydrogen atom is also included as the structural unit represented by the formula (a4-2).

[0201] TIFF0007704571000132.tif5164 [In the 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 have a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding position with A f13 .). A f14represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total number of carbon atoms of L 5 , A f13 and A f14 is 20.

[0202] Examples of the alkanediyl group in L 5 include the same groups as those exemplified for the alkanediyl group of A a41 . Examples of the divalent saturated hydrocarbon group which may have a fluorine atom in A f13 preferably include a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have 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 methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexanediyl group and perfluorocyclohexanediyl group. Examples of the polycyclic group include adamantanediyl group, norbornanediyl group, perfluoroadamantanediyl group.

[0203] The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom in A f14 are R a42Groups similar to those exemplified above can be mentioned. Among them, alkyl fluoride groups such as trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group, etc. are preferable.

[0204] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of 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 of 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. Among them, A f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group.

[0205] Examples of the structural unit represented by formula (a4-3) include structural units respectively represented by formulas (a4-1'-1) to (a4-1'-11). R in structural unit (a4-3)f7 A structural unit in which a methyl group corresponding to f7 is replaced by a hydrogen atom can also be cited as a structural unit represented by formula (a4-3).

[0206] As the structural unit (a4), a structural unit represented by formula (a4-4) can also be cited. TIFF0007704571000133.tif4061[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom.

[0207] R f22 The saturated hydrocarbon group of is the same as the saturated hydrocarbon group represented by R a42 . R f22 is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom. In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0208] As the structural unit represented by formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, a structural unit in which a methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom can be cited. f21 When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0209] 〈Structural unit (a5)〉 Examples of the non-detachable hydrocarbon group contained in the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1). TIFF0007704571000135.tif3972[In the 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 the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 represents 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 by -O- or -CO-.]

[0210] R 52 The alicyclic hydrocarbon group in R may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include 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, an octyl group, and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. R52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

[0211] L 55 Examples of the divalent saturated hydrocarbon group in L include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent chain saturated hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include alkane diyl groups such as a methylene group, an ethylene group, a propane diyl group, a butane diyl group and a pentane diyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkane diyl groups such as a cyclopentane diyl group and a cyclohexane diyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantane diyl group and a norbornane diyl group.

[0212] L 55 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L is replaced by -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents the bonding position with L x1 .). 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, the total number of carbon atoms of L x1 and L x2 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, the total number of carbon atoms in L x3 and L x4 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, the total number of carbon atoms in L x5 L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 each 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, the total number of carbon atoms in L x8 L x9 and W x1 is 15 or less.

[0213] 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 x6is 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.

[0214] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007704571000137.tif54134

[0215] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF0007704571000138.tif24131

[0216] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF0007704571000139.tif15145

[0217] Examples of the group represented by the formula (L1-4) include the following divalent groups. TIFF0007704571000140.tif26114L 55 is preferably a single bond or a group represented by the formula (L1-1).

[0218] Examples of the structural unit (a5-1) include the following structural units and R in the structural unit (a5-1) in the following structural units 51Examples thereof include structural units in which a methyl group corresponding thereto is replaced with a hydrogen atom. TIFF0007704571000141.tif110150 When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 3 to 15 mol% based on all the structural units of the resin (A).

[0219] 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0220] Examples of the sultone ring include the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and examples thereof include the rings represented by formula (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a hetero atom in addition to -SO2-O- as an atomic group constituting the ring, like the ring represented by formula (T 1 -2). Examples of the hetero atom include an oxygen atom, a sulfur atom or a nitrogen atom, and preferably an oxygen atom. TIFF0007704571000142.tif3290

[0221] 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 and the like.

[0222] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 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, 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 perfluoro sec-butyl group, a perfluoro tert-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 hydroxyalkyl group such as 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. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0223] From the viewpoint of easy production of the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferred. As the sultone ring, a ring represented by the following formula (T1') is preferred. TIFF0007704571000143.tif3064[In the formula (T1'), 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 any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R 41 Examples of R are the same as those of the substituent of 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.

[0224] As the sultone ring, a ring represented by the formula (T1) is more preferred. TIFF0007704571000144.tif2743[In the formula (T1), R 8represents 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 any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.]

[0225] R 8 is the same as those of R 41 and the like can be mentioned. ma in formula (T1’) and m in formula (T1) are preferably 0 or 1, more preferably 0.

[0226] Examples of the ring represented by formula (T1’) and the ring represented by formula (T1) include the following rings. The bonding site is at an arbitrary position. TIFF0007704571000145.tif54164

[0227] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007704571000146.tif50162

[0228] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group and the like. Among them, the monomer leading to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0229] The structural unit (a6) is preferably a structural unit represented by the formula (Ix). TIFF0007704571000147.tif4956[In the formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents 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 may be replaced by -O-, -CO- or -N(R d )-. 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 any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0230] Examples of the halogen atom of R x include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group of R x include, for example, 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, etc., preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R xExamples 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 still more preferably a hydrogen atom or a methyl group.

[0231] A x Examples of the divalent saturated hydrocarbon group of A include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination of two or more of these groups may also be used. Specifically, linear alkanediyl groups such as 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 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, 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 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; monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group; Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group, and the like.

[0232] R 41 , X 11 and ma are the same as those in formula (T1'). Examples of the sultone ring include those described above, and among them, those with a specific bonding position are preferred.

[0233] Examples of the structural unit (a6) include the following structural units. TIFF0007704571000148.tif104168

[0234] Among them, the 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 the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferred. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and still more preferably 3 to 30 mol% based on all the structural units of the resin (A).

[0235] <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 preferably a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain.

[0236] The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007704571000149.tif36104[In formula (II-2-A’), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -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 by 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.]

[0237] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A 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, a 2-methylbutane-1,4-diyl group and the like. A x1Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be replaced include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group and the like. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof may also be acceptable. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like can be mentioned. Examples of the group in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the carbon number before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formula, * represents a bond with A x1 and. TIFF0007704571000150.tif145161

[0238] X3 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 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0239] ZA in formula (II-2-A’) + is the same as the cation Z1 in the acid generator (B1). + Examples thereof include the same ones.

[0240] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007704571000151.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + represent the same meanings as described above. z2A represents any integer from 0 to 6. R III2 and R III4 each independently represent 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 represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R III2 , R III4 , Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented byb1 Examples thereof include the same perfluoroalkyl groups having 1 to 6 carbon atoms represented by b1 .

[0241] The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1). TIFF0007704571000152.tif5578[In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b and ZA + have the same meanings as described above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents any integer from 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 a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by III5 include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by I2 include the same ones as the divalent saturated hydrocarbon group represented by III3 . III3

[0242] As the structural unit represented by formula (II-2-A-1), a structural unit represented by formula (II-2-A-2) is more preferable. TIFF0007704571000153.tif5288[In formula (II-2-A-2), R III3 、R III5 and ZA +represents the same meaning as described above. mA and nA each independently represent 1 or 2.

[0243] Examples of the structural unit represented by the formula (II-2-A') include the following structural units, R III3 structural units in which the group corresponding to the methyl group of is replaced by a hydrogen atom, a halogen atom (for example, a fluorine atom), or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group, etc.), and the structural units described in WO 2012 / 050015. ZA + represents an organic cation. TIFF0007704571000154.tif86163

[0244] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1). TIFF0007704571000155.tif3791 [In the 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 represent a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. 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 include a phenylene group and a naphthylene group, etc. R II2 and R II3Examples of the hydrocarbon group represented by 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 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by include the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by . a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by include the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by . A II1 Examples of the divalent linking group represented by include, for example, 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-. Specifically, examples include the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by . III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by include the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by .

[0245] Examples of the structural unit containing a cation in formula (II-1-1) include a structural unit represented by the following and a structural unit in which a group corresponding to the methyl group of is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. II4 Examples of the structural unit containing a cation in formula (II-1-1) include a structural unit represented by the following and a structural unit in which a group corresponding to the methyl group of is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. TIFF0007704571000156.tif84130

[0246] A - Examples of the organic anion represented by include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. - The organic anion represented by is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1).

[0247] A - Examples of the sulfonylimide anion represented by include the following. TIFF0007704571000157.tif33137

[0248] Examples of the sulfonylmethide anion include the following. TIFF0007704571000158.tif29123

[0249] Examples of the carboxylic acid anion include the following. TIFF0007704571000159.tif42154

[0250] Examples of the structural unit represented by formula (II-1-1) include the structural units represented below and the like. TIFF0007704571000160.tif90153 When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0251] The resin (A) may have structural units other than the above-described structural units, and examples of such structural units include structural units well known in the art.

[0252] 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, and still 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 the structural unit represented by formula (a2-A) or the structural unit represented by formula (a2-1). The structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by formula (a3-1), the structural unit represented by formula (a3-2), and the structural unit represented by formula (a3-4).

[0253] Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that leads to these structural units. The content rate of each structural unit of the resin (A) can be adjusted by the amount of the 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, still more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, still 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.

[0254] <Resin other than resin (A)> The resist composition of the present invention may also use a resin other than the resin (A) in combination. Examples of the resin other than the resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, as the resin (X), a resin containing the structural unit (a4) is preferable. In the resin (X), the content rate of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more with respect to the total of all the structural units of the resin (X). Examples of the structural unit 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 them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that leads to these structural units. The content rate of each structural unit of the resin (X) can be adjusted by the amount of the 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 measuring means for the weight average molecular weight of resin (X) is the same as that for resin (A). When the resist composition contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass with respect to 100 parts by mass of resin (A).

[0255] The content rate of resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, with respect to the solid content of the resist composition. When containing a resin other than resin (A), the total content rate of resin (A) and the resin other than resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, with respect to the solid content of the resist composition. The solid content of the resist composition and the content rate of the resin with respect thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0256] <Solvent (E)> The content rate of solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content rate of solvent (E) can be measured by known analysis 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; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0257] <Quencher (C)> The quencher (C) includes basic nitrogen-containing organic compounds or salts that generate an acid having a lower acidity than the acid generated from the acid generator (B) (however, carboxylates represented by the formula (I) are excluded). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass based on the solid content of the resist composition. Examples of the basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of the amines include aliphatic amines and aromatic amines. Examples of the aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropyl aniline, 2-, 3- or 4-methyl aniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, 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, 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'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine and the like. Aromatic amines such as diisopropyl aniline are preferable, and 2,6-diisopropyl aniline is more preferable. 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.

[0258] The acidity of a salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). A salt that generates an acid with a lower 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 -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and 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 with a lower acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid with a lower 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). TIFF0007704571000161.tif94163

[0259] Examples of the weak acid inner salt (D) include the following salts. TIFF0007704571000162.tif72165

[0260] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes 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, dyes, etc., can be used.

[0261] 〈Preparation of Resist Composition〉 The resist composition of the present invention can be prepared by mixing the carboxylate (I), the resin (A), the acid generator (B), and, if necessary, a resin other than the resin (A), the solvent (E), the quencher (C), and the other components (F). The mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40 °C according to the type of resin, etc., and the solubility of the resin, etc., in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is also not particularly limited, and stirring and mixing, etc., can be used. After mixing the components, it is preferable to filter using a filter with a pore size of about 0.003 to 0.2 μm.

[0262] 〈Method for Manufacturing Resist Pattern〉 The method for manufacturing a resist pattern of the present invention (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer. To apply the resist composition onto a substrate, it can be performed by a commonly used device such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be washed, or an antireflection film, etc., may be formed on the substrate. By drying the coated composition, the solvent is removed to form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during vacuum drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F2 excimer laser (wavelength 157 nm), those that convert the laser light from a solid laser light source (such as a YAG or semiconductor laser) into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emit it, those that irradiate electron beams, extreme ultraviolet light (EUV), etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure". During exposure, usually, exposure is performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The exposed composition layer is heat-treated (so-called post-exposure bake) to promote the deprotection reaction at the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. The heated composition layer is usually developed using a developing solution with a developing device. Examples of the developing method include the dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When producing a positive resist pattern 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. For example, aqueous solutions of tetramethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline), etc. may be mentioned. The alkaline developer may contain a surfactant. After development, it is preferable to wash the resist pattern with ultrapure water and then remove the water remaining on the substrate and the pattern. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic-based developer") is used as the developer. Examples of the organic solvent contained in the organic-based developer 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; aromatic hydrocarbon solvents such as anisole, etc. In the organic-based developer, the content of the organic solvent 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 them, as the organic-based developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic-based developer, the total content of butyl acetate and 2-heptanone 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-based developer may contain a surfactant. Also, the organic-based developer may contain a trace amount of water. During development, development may be stopped by substituting with a solvent of a different type from the organic-based developer. It is preferable to wash the developed resist pattern with a rinse solution. The rinse solution is not particularly limited 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 washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0263] <Usage> 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, particularly as a resist composition for ArF excimer laser exposure, and is useful for semiconductor microfabrication.

Examples

[0264] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent 1100 type, MASS is Agilent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0265] Example 1: Synthesis of the salt represented by formula (I-1617) 20 parts of the compound represented by formula (I-1617-a), 2.28 parts of the compound represented by formula (I-1617-c), 100 parts of ethyl acetate and 15 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 6.55 parts of the compound represented by formula (I-1617-b) was added and stirred at 23°C for 18 hours. To the resulting reaction mass, 20 parts of n-heptane and 70 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then separated to take out the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23°C for 30 minutes, and then separated to take out the organic layer. This water washing operation was repeated 4 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by 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 the compound represented by formula (I-1617-d). 0.95 part of the compound represented by formula (I-1617-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.14 part of sodium hydride was added. To the resulting mixture, 1.01 parts of the salt represented by formula (I-1617-e) was added and stirred at 5°C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23°C and stirred at 23°C for 6 hours. To the resulting mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then separated to take out the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.24 parts of the salt represented by formula (I-1617-f). 0.62 part of the salt represented by TIFF0007704571000165.tif50148 (I-1617-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75°C. To the resulting mixture, 0.45 part of the compound represented by formula (I-1617-g) was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.73 part of the salt represented by formula (I-1617-h) was obtained. 0.77 part of the salt represented by TIFF0007704571000166.tif60164 (I-1617-h), 0.27 part of the salt represented by formula (I-1617-i), and 20 parts of chloroform were added and stirred at 23°C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.78 part of the salt represented by formula (I-1617) was obtained. MASS(ESI(+)Spectrum):M + 809.2 MASS(ESI(-)Spectrum):M - 193.1

[0266] Example 2: Synthesis of the salt represented by formula (I-1619) 0.77 part of the salt represented by formula (I-1617-h), 0.40 part of the salt represented by formula (I-1619-i) and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.93 part of the salt represented by formula (I-1619) was obtained. MASS(ESI(+)Spectrum):M + 809.2 MASS(ESI(-)Spectrum):M - 337.1

[0267] Example 3: Synthesis of the salt represented by formula (I-667) 3.80 parts of the compound represented by formula (I-667-a) and 6.40 parts of Oxone® were mixed, stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 23.56 parts of sulfuric acid was added, and then stirred at 5 °C for 30 minutes. To the resulting mixture, a mixed solution of 3.68 parts of the compound represented by formula (I-667-b) and 18.40 parts of chloroform was added, stirred at 5 °C for 30 minutes, and then further stirred at 23 °C for 2 hours. The obtained mixed solution was added to 120 parts of methanol, stirred at 23 °C for 30 minutes, and then filtered. After concentrating the obtained filtrate, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, stirred at 23 °C for 30 minutes, then 60 parts of 5% hydrochloric acid was added and stirred at 23 °C for 30 minutes, and then the layers were separated and the organic layer was taken out. 40 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 °C for 30 minutes, and then the layers were separated and the organic layer was taken out. This water washing operation was repeated 3 times. The obtained organic layer was concentrated, 45 parts of tert-butyl methyl ether was added to the concentrated mixture, stirred at 23 °C for 30 minutes, and then filtered to obtain 2.37 parts of the salt represented by formula (I-667-c). 0.95 part of the compound represented by TIFF0007704571000169.tif42138 (I-1617-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C, and 0.14 part of sodium hydride was added. To the resulting mixture, 2.32 parts of the salt represented by formula (I-667-c) was added, and the mixture was stirred at 5°C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23°C, and the mixture was stirred at 23°C for 6 hours. To the resulting mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated to extract the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 2.19 parts of the salt represented by formula (I-667-f). 1.37 parts of the salt represented by TIFF0007704571000170.tif33159 (I-667-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes, then 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75°C. To the resulting mixture, 0.45 part of the compound represented by formula (I-1617-g) was added, and the mixture was stirred at 75°C for 5 hours, then cooled to 23°C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, then separated to extract the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, then separated to extract the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.12 parts of the salt represented by formula (I-667-g) was obtained. 0.60 part of the salt represented by formula (I-667-g), 0.27 part of the salt represented by formula (I-1617-i), and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was carried out to take out the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.61 part of the salt represented by formula (I-667) was obtained. MASS(ESI(+)Spectrum):M + 615.2 MASS(ESI(-)Spectrum):M - 193.1

[0268] Example 4: Synthesis of the salt represented by formula (I-669) 0.60 part of the salt represented by formula (I-667-g), 0.40 part of the salt represented by formula (I-1619-i), and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was carried out to take out the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.72 part of the salt represented by formula (I-669) was obtained. MASS(ESI(+)Spectrum):M + 615.2 MASS(ESI(-)Spectrum):M - 337.1

[0269] Example 5: Synthesis of the salt represented by formula (I-2759) 6.57 parts of the compound represented by formula (I-2759-a), 0.23 parts of the compound represented by formula (I-1617-c), 30 parts of ethyl acetate and 15 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes. To the obtained mixed solution, 0.66 parts of the compound represented by formula (I-1617-b) was added and stirred at 23 °C for 18 hours. To the obtained reaction mass, 100 parts of n-heptane and 20 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. 20 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. This water washing operation was repeated 4 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by 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 6.28 parts of the compound represented by formula (I-2759-d). 2.26 parts of the compound represented by formula (I-2759-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. To the obtained mixture, 2.32 parts of the salt represented by formula (I-667-c) was added and stirred at 5 °C for 3 hours. To the obtained mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the obtained mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.01 parts of the salt represented by formula (I-2759-f). 1.00 part of the salt represented by formula (I-2759-f) and 30 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes. Then, 0.08 part of potassium carbonate and 0.03 part of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 0.43 part of the compound represented by formula (I-1617-g) was added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was carried out to take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.12 parts of the salt represented by formula (I-2759-b) were obtained. 0.82 part of the salt represented by formula (I-2759-b), 0.40 part of the salt represented by formula (I-1619-i) and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was carried out to take out the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.94 part of the salt represented by formula (I-2759) was obtained. MASS(ESI(+)Spectrum):M + 867.0 MASS(ESI(-)Spectrum):M - 337.1

[0270] Example 6: Synthesis of the salt represented by formula (I-3709) 2.26 parts of the compound represented by formula (I-2759-d), 0.78 part of the salt represented by formula (I-1617-e), and 30 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes, and then the temperature was raised to 90 °C. To the obtained mixture, 1.44 parts of potassium carbonate was added, and the mixture was stirred at 90 °C for 3 hours. To the obtained mixture, 6.30 parts of 1N hydrochloric acid was added, and then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the obtained mixture, 50 parts of chloroform and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain the organic layer. To the obtained organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain the organic layer. This water washing operation was repeated 3 times. After concentrating the obtained organic layer, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes, and then the supernatant was removed and concentrated to obtain 1.63 parts of the salt represented by formula (I-3709-f). 1.21 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, and then 0.16 part of potassium carbonate and 0.05 part of potassium iodide were added, and the temperature was raised to 75 °C. To the obtained mixture, 0.90 part of the compound represented by formula (I-1617-g) was added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the obtained mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes, and then separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.23 parts of the salt represented by formula (I-3709-h) was obtained. 1.23 parts of the salt represented by formula (I-3709-h), 0.40 parts of the salt represented by formula (I-1619-i), and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.43 parts of the salt represented by formula (I-3709) was obtained. MASS(ESI(+)Spectrum):M + 1312.8 MASS(ESI(-)Spectrum):M - 337.1

[0271] Example 7: Synthesis of the salt represented by formula (I-2664) 0.58 parts of the salt represented by formula (I-667-f) and 30 parts of chloroform were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 0.19 parts of the compound represented by formula (I-2664-a) was added, and further stirred at 50 °C for 2 hours. To the resulting mixed solution, 0.13 parts of the compound represented by formula (I-2664-b) was added, and further stirred at 50 °C for 3 hours and then cooled to 23 °C. To the obtained mixture, 15 parts of 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then the layers were separated and the organic layer was taken out. To the obtained organic layer, 15 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 0.62 parts of the salt represented by formula (I-2664-h). 0.58 part of the salt represented by TIFF0007704571000181.tif51155 (I-2664-h), 0.40 part of the salt represented by formula (I-1619-i), and 20 parts of chloroform were added and stirred at 23 °C for 3 hours. To the resulting reaction product, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. To the obtained organic layer, 15 parts of ion-exchanged water was added, and after stirring at 23 °C for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.75 part of the salt represented by formula (I-2664) was obtained. MASS(ESI(+)Spectrum):M + 601.1 MASS(ESI(-)Spectrum):M - 337.1

[0272] Synthesis of Resin 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. TIFF0007704571000182.tif43144

[0273] Synthesis Example 1: Synthesis of Resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-1) and monomer (a3-4-2) were used, and they were mixed so that the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-1): monomer (a3-4-2)] was 45:14:2.5:38.5. Propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer amount was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in amounts of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resulting 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, and this resin was filtered. This reprecipitation operation was performed twice to obtain resin A1 having a weight average molecular weight of 7.8×10 3 in a yield of 69%. This resin A1 has the following structural units. TIFF0007704571000183.tif36126

[0274] Synthesis Example 2: Synthesis of Resin X1 As monomers, monomer (a5-1-1) and monomer (a4-0-12) were used, and they were mixed so that the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] was 50:50. Methyl isobutyl ketone in an amount 1.2 times the total monomer amount was added to form a solution. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol% based on the total monomer amount, and it was heated at 70 °C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered to obtain resin X1 having a weight average molecular weight of 1.0×10 4 in a yield of 91%. This resin X1 has the following structural units. TIFF0007704571000184.tif3082

[0275] <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

[0276] <Resin> A1, X1: Resin A1, Resin X1 <Acid generator (B)> B1-21: Salt represented by formula (B1-21) B1-22: Salt represented by formula (B1-22) TIFF0007704571000186.tif2896<Carboxylate (I)> I-667: Salt represented by formula (I-667) I-669: Salt represented by formula (I-669) I-1617: Salt represented by formula (I-1617) I-1619: Salt represented by formula (I-1619) I-2664: Salt represented by formula (I-2664) I-2759: Salt represented by formula (I-2759) I-3709: Salt represented by formula (I-3709) <Salt (IX)> IX-1 IX-2 IX-3 IX-4 IX-5 TIFF0007704571000187.tif77155<Solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-Heptanone 20 parts γ-Butyrolactone 3.5 parts

[0277] <Manufacture and evaluation of resist pattern> An organic antireflection film composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205°C for 60 seconds to form an organic antireflection film with a thickness of 78 nm. Next, the above resist composition was spin-coated onto the above organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, this silicon wafer was pre-baked on a direct hot plate at the temperature described in the "PB" column of Table 2 for 60 seconds to form a composition layer on the silicon wafer. On the composition layer formed on the silicon wafer, an ArF excimer laser stepper for immersion lithography [XT:1900Gi; manufactured by ASML, NA = 1.35, Annular σ out = 0.85 σ in = 0.65 XY-pol. illumination] was used to perform exposure while gradually changing the exposure dose using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm). Note that ultrapure water was used as the immersion medium. After exposure, post-exposure baking was performed on a hot plate at the temperature described in the "PEB" column of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed at 23°C for 20 seconds by the dynamic dispense method using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer to produce a negative resist pattern.

[0278] In the obtained resist pattern, the exposure dose at which the width of the trench pattern becomes 40 nm was defined as the effective sensitivity.

[0279] <Line Edge Roughness Evaluation (LER)> For the obtained resist pattern, the amplitude of the unevenness of the wall surface was observed and measured with a scanning electron microscope. The results are shown in Table 3. The numerical values in the table indicate the amplitude (nm).

Table 3

Industrial Applicability

[0280] The carboxylate of the present invention and the resist composition containing the carboxylate are suitable for semiconductor microfabrication and extremely useful industrially because a resist pattern having good line edge roughness (LER) can be obtained.

Claims

1. A carboxylate represented by formula (I). [In formula (I), R １ and R ２ are each independently, -O-R １０ , -O-CO-R １０ , -O-CO- O-R １０ , -O-L １ -CO-O-R １０ represents. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R ４ 、 R ５ 、 R ７ and R ８ are each independently a halogen atom, a fluorinated An alkyl group or an alkyl group having 1 to 6 carbon atoms (wherein -CH 2 - included in the alkyl group may be replaced by -O- or -CO-). R １０ represents a group represented by the formula (IC). X １ and X ２ each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. m5 represents any integer from 0 to 4, and when m5 is 2 or more, the plurality of Rs ５ may be the same as or different from each other. m7 represents any integer from 0 to 4. When m7 is 2 or more, a plurality of Rs ７ may be the same as or different from each other. m8 represents any integer from 0 to 5, and when m8 is 2 or more, the plurality of Rs ８ may be the same as or different from each other. However, 1 ≤ m1 + m7 ≤ 5 and 0 ≤ m2 + m8 ≤ 5. X ０ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (in the alicyclic hydrocarbon group, -CH ２ - may be replaced by -O- or -CO-.), an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a group combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms and a chain hydrocarbon group having 1 to 12 carbon atoms (in the alicyclic hydrocarbon group and the chain hydrocarbon group, -CH ２ - may be replaced by -O-, -S-, -CO- or -SO ２ -).] [In formula (IC), R Ａ represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of Rs Ａ are either identical or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L ２ represents a hydrocarbon group having 1 to 36 carbon atoms which may have a single bond or a substituent. * represents a bonding site.]

2. X １ and X ２ The carboxylate according to claim 1, wherein X and X are oxygen atoms.

3. L ２ The carboxylate according to claim 1 or 2, wherein L is a methylene group.

4. m2 is 0, m8 is 1, and R ８ is a branched alkyl group having 3 or 4 carbon atoms, the carboxylate according to any one of claims 1 to 3.

5. R ４ or R ５ is an iodine atom, a fluorine atom or a trifluoromethyl group, the carboxylate according to any one of claims 1 to 4.

6. R in the benzene ring ４ is bonded to X １ at the ortho or meta position, or R ５ in the benzene ring is bonded to X ２ at the ortho or meta position relative to X, the carboxylate according to claim 5.

7. X ０ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (in the alicyclic hydrocarbon group, -CH ２ - may be replaced by -O- or -CO-), or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, the carboxylate according to any one of claims 1 to 6.

8. X ０ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom or a hydroxy group (in the alicyclic hydrocarbon group, -CH 2 - may be replaced by -O- or -CO-).) or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. The carboxylate according to any one of claims 1 to 7.

9. X ０ is a group represented by formula (y1) to formula (y26), formula (y28) to formula (y49), formula (y51), formula (y55), formula (y56), formula (y59), formula (y60), formula (y62) to formula (y66), formula (y68), formula (y71) (in the following groups, it may have a substituent, and the bonding site with the carbon atom of the carbonyl group may be at any position). The carboxylate according to claim 7.

10. A carboxylic acid generator containing the carboxylate according to any one of Claims 1 to 9.

11. A resist composition containing the carboxylic acid generator according to Claim 10, an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

12. The resist composition according to Claim 11, wherein the resin having an acid-labile group contains 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). [In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH ２ ) k1 -CO-O-, k1 represents any integer from 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 group combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3.]

13. The resist composition according to Claim 11 or 12, further containing a resin containing a structural unit having a fluorine atom.

14. (1) A step of applying the resist composition according to any one of Claims 11 to 13 on a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including these steps.

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