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

Abstract

To provide a carboxylate capable of producing a resist pattern with good line edge roughness and a resist composition containing the carboxylate.SOLUTION: The carboxylate is represented by formula (IA) or formula (IB).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 salt represented by the following formula and a resist composition containing the salt as an acid generator. TIFF0007716844000001.tif30104 Patent Document 2 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007716844000002.tif2641 Patent Document 3 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007716844000003.tif2643

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a salt capable of producing a resist pattern with better line edge roughness (LER) than a resist pattern formed from a resist composition containing the above salt.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A carboxylate represented by formula (IA) or formula (IB). TIFF0007716844000004.tif69144[In formula (IA) and formula (IB), R 1 , R 2 , R 3 and R 4 each independently 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-. R 1 and R 2 , and R 3 and R 4 may be bonded to each other to form a ring having 3 to 24 carbon atoms together with the sulfur atom to which they are bonded, and -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R 5 , R 6 , R 7 , R 8 and R 9 each independently represents a halogen atom, a hydroxy group, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkyl group may be replaced by -O- or -CO-. m5 represents any integer from 0 to 4, and when m5 is 2 or more, a plurality of R 5 may be the same as or different from each other. m6 represents any integer from 0 to 4, and when m6 is 2 or more, a plurality of R 6 may be the same as or different from each other. m7 represents any integer from 0 to 4, and when m7 is 2 or more, a plurality of R 7 may be the same as or different from each other. m8 represents any integer from 0 to 4, and when m8 is 2 or more, a plurality of R 8 may be the same as or different from each other. X 1 and X 2each independently represents a single bond, an oxygen atom, a sulfur atom, or an alkanediyl group having 1 to 6 carbon atoms, and the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. X 01 , X 02 and X 03 each independently represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. [2]R 1 , R 2 , R 3 and R 4 are each independently a phenyl group which may have a substituent, the carboxylate according to [1]. [3]X 01 , X 02 and X 03 are each independently an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, the -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, the carboxylate according to [1] or [2]. [4]X 01 , X 02 and X 03 are each independently an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group and the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), or an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, the carboxylate according to any one of [1] to [3]. [5]A carboxylic acid generator containing the carboxylate according to any one of [1] to [4]. A resist composition containing the carboxylic acid generator described in [6] [5], an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group. [7] The resist composition according to [6], 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). TIFF0007716844000005.tif46102[In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents an integer from 1 to 7, and * represents the bonding position to -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 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. ] [8] The resist composition according to [6] or [7], wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). TIFF0007716844000006.tif4459[In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 represents a single bond or * -X a51 -(Aa52 -X a52 ) nb - represents, and * is -R a50 represents the bonding position with the carbon atom to which it is bonded. A a52 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. [9](1) A step of applying the resist composition according to any one of [6] to [8] 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, which is a method for manufacturing a resist pattern. [Advantages of the Invention]

[0006] By using the resist composition using the salt of the present invention, a resist pattern can be manufactured with good line edge roughness (LER). [Modes for Carrying Out the Invention]

[0007] In this specification, “(meth)acrylic monomer” means “at least one of acrylic monomer and 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 of them. “Combined group” means a group formed by combining two or more of the exemplified groups with their valences appropriately changed. “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, “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.

[0008] <Carboxylate represented by formula (IA) or formula (IB)> The present invention relates to a carboxylate represented by formula (IA) (hereinafter sometimes referred to as “carboxylate (IA)”) and a salt represented by formula (IB) (hereinafter sometimes referred to as “carboxylate (IB)”). Among carboxylate (IA) and carboxylate (IB), the side having a negative charge may be referred to as “anion (I)”, and the side having a positive charge may be referred to as “cation (IA)” or “cation (IB)”. TIFF0007716844000007.tif69144[In formulas (IA) and (IB), all symbols have the same meanings as described above.] Carboxylate (IA) and carboxylate (IB) can also be represented as follows. TIFF0007716844000008.tif84162[In formulas (IA) and (IB), all symbols have the same meanings as described above.]

[0009] R 1 、R 2 、R 3 and R 4Examples of the hydrocarbon group in [description] include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups formed by combining chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. R 1 , R 2 , R 3 and R 4 When -CH2- contained in the hydrocarbon group in [description], R, R, R, and R 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. 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, and nonyl group. The number of carbon atoms of the alkyl 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 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, and 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, and nonynyl group. When -CH2- contained in a chain 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 chain hydrocarbon group. For example, groups in which -CH2- at any position contained in an alkyl group is replaced by -O- or -CO- include a hydroxy group (a group in which -CH2- at any position contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- at any position contained in an ethyl group is replaced by -O-CO-), 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-), and the like. In addition, the replacement in an alkenyl group or an 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 replacement in the above-mentioned alkyl 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, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group and the like. The number of carbon atoms of the alkoxy group is from 1 to 11, preferably from 1 to 6, and more preferably from 1 to 4. An alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group 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 include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, etc. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. The number of carbon atoms in the alkoxycarbonyl group is, for example, 2 to 11, preferably 2 to 6, more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyl group is, for example, 2 to 12, preferably 2 to 6, more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyloxy group is, for example, 2 to 11, preferably 2 to 6, more preferably 2 to 4. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spiro, 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, a cyclododecyl group, etc., and polycyclic cycloalkyl groups such as a norbornyl group, an adamantyl group, etc. Specifically, examples of the alicyclic hydrocarbon group include groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38), etc. Further, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -CO-, or -SO2- include groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43), etc. * represents a bonding site. Among them, the alicyclic hydrocarbon group is preferably a group represented by any of the formulas (Y1) to (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), and 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) or formula (Y43). 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. TIFF0007716844000009.tif83168

[0010] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, fluorenyl group, etc. Phenyl group, naphthyl group and anthryl group are preferred, phenyl group and naphthyl group are more preferred, and phenyl group is still more preferred. 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.

[0011] Examples of the combined group include a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (such as an alkyl group, alkenyl group and / or alkynyl group, etc.) (the -CH2- contained in the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.) and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (such as an alkyl group, alkenyl group, alkynyl group, etc.) (the -CH2- contained in the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.) may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, the alicyclic hydrocarbon group, the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.), and the aromatic hydrocarbon group may be combined with two or more of each. Further, in the above groups, groups having different valences (divalent or trivalent groups (chain hydrocarbon group, alicyclic saturated hydrocarbon group, aromatic hydrocarbon group), etc.) may be included. Further, any of the groups may be bonded to a sulfur atom. Specific examples of the combined groups include alicyclic hydrocarbon group-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-), such as adamantylmethyl group, cyclohexylmethyl group, etc. chain hydrocarbon group-alicyclic hydrocarbon group-* (the -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as methyladamantyl group, etc. chain hydrocarbon group-aromatic hydrocarbon group-* (the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as tolyl group, xylyl group, etc. chain hydrocarbon group-alicyclic hydrocarbon group-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-), such as methylcyclohexylmethyl group, etc. aromatic hydrocarbon group-chain hydrocarbon group-* (the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as benzyl group, etc. chain hydrocarbon group-aromatic hydrocarbon group-chain hydrocarbon group-* (the -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as tolylmethyl group, etc. aromatic hydrocarbon group-alicyclic hydrocarbon group-* (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as phenyladamantyl group, etc. Examples thereof include alicyclic hydrocarbon group-aromatic hydrocarbon group- such as cyclohexylphenyl group and adamantylphenyl group (*-CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). Here, * represents the bonding position with a sulfur atom.

[0012] R 1 、R 2 、R 3 And R 4 Examples of the substituents of the hydrocarbon groups of R 1 、R 2 、R 3 And R 4 When the hydrocarbon group in R has a substituent, the total number of carbon atoms before substitution is defined as the total carbon number of the hydrocarbon group. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O- or -CO- 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-), an alkoxy group (a group in which any -CH2- contained in the alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which any -CH2-CH2- contained in the alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which any -CH2- contained in the alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which any -CH2-CH2- contained in the alkyl group is replaced by -CO-O-), etc.

[0013] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc. Examples of the perfluoroalkyl group 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, and the like. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 4, more preferably 1 to 3. Examples of the alkyl group include alkyl groups such as 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. 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. Examples of the alkoxy group 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 number of carbon atoms in the alkoxy group is from 1 to 11, preferably 1 to 6, and more preferably 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group 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 include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and the like. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, and the like. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like. The number of carbon atoms in the alkoxycarbonyl group is from 2 to 11, preferably 2 to 6, and more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyl group is from 2 to 12, preferably 2 to 6, and more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyloxy group is from 2 to 11, preferably 2 to 6, and more preferably 2 to 4.

[0014] R 1 、R2 and R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, or R 1 and R 2 and, R 3 and R 4 are preferably bonded to each other to form a ring having 3 to 12 carbon atoms together with the sulfur atom to which they are bonded (wherein -CH2- contained in the ring may be replaced by -O-, -S- or -CO-), more preferably a methyl group, a cyclohexyl group or a phenyl group which may have a substituent, still more preferably a phenyl group which may have a substituent, even more preferably a phenyl group which may have a halogen atom, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), yet even more preferably a phenyl group which may have a halogen atom, and particularly preferably a phenyl group which may have a fluorine atom.

[0015] R 5 and R 6 and R 7 and R 8 and R 9 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms for R R 5 and R 6 and R 7 and R 8 and R 9Examples of the alkyl group having 1 to 12 carbon atoms 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 and the like. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4. R 5 、R 6 、R 7 、R 8 and R 9 When -CH2- contained in the alkyl group in is replaced by -O- or -CO-, the total number of carbon atoms before replacement is defined as the total number of carbon atoms of the alkyl group. R 5 、R 6 、R 7 and R 8 Examples of the group in which -CH2- contained in the alkyl group in is replaced by -O- or -CO- 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-), 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-) and the like. Specific examples thereof include the same ones as those described above. R 5 、R 6 、R 7 and R 8 are each independently preferably a halogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms, more preferably a fluorine atom, a hydroxy group or a methyl group, and still more preferably a fluorine atom or a hydroxy group. m5, m6, m7 and m8 are each independently preferably any integer from 0 to 2, and more preferably 0 or 1. R 9 is preferably a halogen atom, a hydroxy group or a C1-C6 perfluoroalkyl group, more preferably a halogen atom or a hydroxy group, and even more preferably a fluorine atom or a hydroxy group.

[0016] X 1 and X 2 Examples of the C1-C6 alkanediyl group for and X 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 ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1-4, and more preferably 1-3. X 1 and X 2 are each independently preferably a single bond, an oxygen atom, a sulfur atom, a methylene group or an ethylene group, more preferably an oxygen atom or a sulfur atom, and even more preferably an oxygen atom. X 1 and X 2 The bonding position of and X may be any of the ortho, meta, and para positions with respect to the bonding position of I. Among them, it is preferably bonded to the para or meta position with respect to the bonding position of I, and more preferably bonded to the para position. + of I + is preferably bonded to the para or meta position with respect to the bonding position of I, and more preferably bonded to the para position.

[0017] Examples of the cation (IA) include, for example, the following cations. TIFF0007716844000010.tif205169

[0018] TIFF0007716844000011.tif140168

[0019] Examples of the cation (IB) include the following cations. TIFF0007716844000012.tif84153

[0020] TIFF0007716844000013.tif227166

[0021] In formula (I), X 01 , X 02 and X 03 Examples of the hydrocarbon group represented by 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, and nonyl group. 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 ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, and 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, and nonynyl group. Examples of groups in which -CH2- contained in a chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include 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-), 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 alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), and the like. Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group include an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, and an alkylcarbonyloxy group having 2 to 17 carbon atoms, and groups similar to those 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 replacement in an alkenyl group or an alkynyl group may be any group containing a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the examples of the replacement 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. 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- specifically include the following groups etc. The bonding site can be at any position. TIFF0007716844000014.tif130161As the alicyclic hydrocarbon group or the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the groups represented by formulas (y1) to (y71) are preferable, the groups represented by any one of formulas (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), and formulas (y39) to (y71) are more preferable, and the groups represented by formula (y3), (y4), formula (y9), formula (y11), formula (y14), formula (y15), formula (y16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), and formulas (y49) to (y58) and formulas (y62) to (y71) are further preferable. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, further preferably 3 to 18, still more preferably 3 to 16.

[0022] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group, etc. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, further 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, alkane tetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkane tetrayl group, etc.) may be included in the above-mentioned groups.

[0023] 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 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-), and A group combining an aliphatic cyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the aliphatic cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, two or more kinds of the alicyclic hydrocarbon group, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be combined respectively. Specifically, as the combined group, An alicyclic hydrocarbon group - aliphatic hydrocarbon group - * such as an adamantylmethylene group or a cyclohexylmethylene group, (alicyclic hydrocarbon group)2 - aliphatic hydrocarbon group - * (wherein -CH2- contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An aliphatic hydrocarbon group - alicyclic hydrocarbon group - * such as a methyladamantyl group or a dimethyladamantyl group, (aliphatic hydrocarbon group)2 - alicyclic hydrocarbon group - * (wherein -CH2- contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An aliphatic hydrocarbon group - aromatic hydrocarbon group - * such as a tolyl group or a xylyl group (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An aliphatic hydrocarbon group - alicyclic hydrocarbon group - aliphatic hydrocarbon group - * such as a methylcyclohexylmethylene group, (aliphatic hydrocarbon group)2 - alicyclic hydrocarbon group - aliphatic hydrocarbon group - *, (aliphatic hydrocarbon group - alicyclic hydrocarbon group)2 - aliphatic hydrocarbon group - * (wherein -CH2- contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), An aromatic hydrocarbon group - aliphatic hydrocarbon group - * such as a benzyl group (wherein -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Chain hydrocarbon group such as a trimethyl group - aromatic hydrocarbon group - chain hydrocarbon group - *(wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), Chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - * such as methyladamantane methylene adamantyl group, di(methyladamantane methylene)adamantyl group, etc., (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.

[0024] X01 and X 02 and X 03 When -CH2- contained in the hydrocarbon group represented by is replaced by -O-, -S-, -CO- or -SO2-, the carbon number before replacement is defined as the total carbon number of the hydrocarbon group. Also, X 01 and X 02 and X 03 When a substituent is bonded to the hydrocarbon group represented by, the carbon number before substitution is defined as the total carbon number of the hydrocarbon group. X 01 and X 02 and X 03 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, and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group 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, 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. 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. TIFF0007716844000015.tif17162 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group and a naphthyl group. Examples of the combined groups 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, 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 a hydroxymethyl group and a 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 a benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as a tolyl group and a xylyl group. Examples of the group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include a cyclohexylphenyl group and the like.

[0025] X 0 The hydrocarbon group represented by is 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-), an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, a group represented by formula (aa) or a group represented by formula (bb). More preferably, it is an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom (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 or a hydroxy group), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), 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 hydroxy group or a fluorine atom. * represents the bonding position with 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 or a hydroxy group. * represents the bonding position with 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 or a hydroxy group. * represents the bonding position with the carbon atom of -COO - ). It is an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, it is a polycyclic alicyclic hydrocarbon group (wherein -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 hydroxy group or a fluorine atom. * is -COO - represents the bonding position with the carbon atom of). A polycyclic alicyclic hydrocarbon group - a chain hydrocarbon group (wherein -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of). A chain hydrocarbon group - a polycyclic alicyclic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of). It is an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), Particularly preferably, it is an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), a group represented by formula (Y30F), a phenyl group having a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb). 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. TIFF0007716844000016.tif26125[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position with the carbon atom of the carbonyl group.] [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom. 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 A represents 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 the bonding position with the carbon atom of the carbonyl group.]

[0026] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0027] 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. In addition, -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 without substituents and without replacement.

[0028] X 1a Examples of the aliphatic hydrocarbon group of include chain hydrocarbon groups such as an alkanetriyl group, alicyclic hydrocarbon groups, or groups 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.

[0029] 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 benzenetriyl group, a naphthalenetriyl group, an anthracenetriyl group, and the like. In the case of a combined group, groups having different valences in the above-mentioned groups (alkyl group, alkanediyl group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkanetetrayl group, etc.) may be included.

[0030] X 1a The hydrocarbon group represented by is a hydrocarbon group having 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 include the same groups as described above.

[0031] X 1a The hydrocarbon group represented by 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). TIFF0007716844000017.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 the bonding position.

[0032] 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 more preferably 10 to 38. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of an unsubstituted and un-replaced hydrocarbon group.

[0033] 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.

[0034] 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; Mono-cyclic alicyclic hydrocarbon groups which are mono-cyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Poly-cyclic alicyclic hydrocarbon groups which are poly-cyclic 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, etc. may 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 groups 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 (e.g., -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 (e.g., -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 (e.g., -aliphatic hydrocarbon group - alicyclic hydrocarbon group - aliphatic hydrocarbon group, -aliphatic hydrocarbon group -(alicyclic hydrocarbon group - aliphatic hydrocarbon group)2, etc.).

[0035] X 2a As the hydrocarbon group in an aliphatic hydrocarbon group having 2 to 18 carbon atoms (wherein -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 (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 combining an aliphatic hydrocarbon group having 1 to 12 carbon atoms (wherein -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 (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) (the group may have a substituent) is preferable, an aliphatic hydrocarbon group having 4 to 18 carbon atoms (wherein -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 formed by 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 preferred. 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 formed by 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 more preferred.

[0036] Specifically, the hydrocarbon group in X 2a is as follows: 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 preferable. 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 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) is more preferable. 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 a group composed of these (the group may have a substituent) is more preferable.

[0037] Specifically, X 2a is 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), which is preferable. TIFF0007716844000018.tif34157 [In the formula, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining two or more of these groups. -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.

[0038] 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.

[0039] 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. When -CH2- contained in the alkanediyl group is replaced by -O- or -CO-, the total number of carbon atoms before replacement is defined as the total number of carbon atoms 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-), 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-), or an alkanediylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -CO-O-). Examples of the alkanediyl-oxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyl-oxy group, a butanediyl-oxy group, and a pentanediyl-oxy group. Examples of the alkanediyl-oxycarbonyl group include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanediyl-oxycarbonyl group, and a butanediyl-oxycarbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group, an ethylenecarbonyl group, a propanediylcarbonyl group, a butanediylcarbonyl group, a pentanediylcarbonyl group, and the like. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, a butanediylcarbonyloxy group, and the like. L A is preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, and more preferably an alkanediyl group having 1 to 3 carbon atoms having a fluorine atom. 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.

[0040] R A Examples of the hydrocarbon group in R 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 still 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 octenyl group, an isooctenyl group, a nonenyl group, and the like. 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 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 hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group and 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, and an alkylthio 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 cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, 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 number of carbon atoms 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 phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, and binaphthyl group. 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. In the case of a combined group, groups having different valences (such as alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) in the above-mentioned groups may be included. 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 benzyl group and phenethyl group. Examples of the alkyl group - aromatic hydrocarbon group - * include tolyl group, xylyl group, cumenyl group, etc. Examples of the alicyclic hydrocarbon group - alkanediyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, and 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include phenyladamantyl group, etc. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include adamantylphenyl group, etc. In the combination, the alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may each be combined with two or more kinds. Also, any of the groups may be bonded to L B either. 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 above-described groups, 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 total 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.

[0041] R A 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-, -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, the alkoxycarbonyl group, the alkylcarbonyl group, and the 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 R may have one substituent or a plurality of substituents.

[0042] R A The hydrocarbon group in R is preferably 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-). It is preferably a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-).

[0043] 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, the aromatic hydrocarbon group, and the combined group are the same as those described above. In the combination, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may each be combined with two or more kinds. Also, any group may be bonded to L B and may be bonded.

[0044] 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 ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or, 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 is preferable, an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms ( -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-) is more preferable. 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, a naphthyl group are preferable. TIFF0007716844000019.tif1687

[0045] Examples of the anion (I) include carboxylic acid anions described below. TIFF0007716844000020.tif98162

[0046] TIFF0007716844000021.tif118134

[0047] TIFF0007716844000022.tif126139

[0048] TIFF0007716844000023.tif124154

[0049] TIFF0007716844000024.tif155143

[0050] TIFF0007716844000025.tif218160

[0051] TIFF0007716844000026.tif192163

[0052] Specific examples of the carboxylate (IA) and the carboxylate (IB) include salts formed by arbitrarily combining the above-mentioned cations and anions. Specific examples of the carboxylate (IA) and the carboxylate (IB) are shown in the following table. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation. For example, the carboxylate (IA-1) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (IA-c-1), and the carboxylate (IB-1) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (IB-c-1), representing the salts shown below. TIFF0007716844000027.tif62129 [Table 1] TIFF0007716844000029.tif223166 TIFF0007716844000030.tif223166 TIFF0007716844000031.tif223166 TIFF0007716844000032.tif223166 TIFF0007716844000033.tif223166 TIFF0007716844000034.tif223166 TIFF0007716844000035.tif125165

[0053] [Table 2] TIFF0007716844000037.tif223165 TIFF0007716844000038.tif223165 TIFF0007716844000039.tif223165 TIFF0007716844000040.tif223165 TIFF0007716844000041.tif47155

[0054] Among them, the carboxylate (IA) is preferably carboxylate (IA-1) to carboxylate (IA-5), carboxylate (IA-30) to carboxylate (IA-34), carboxylate (IA-59) to carboxylate (IA-63), carboxylate (IA-88) to carboxylate (IA-92), carboxylate (IA-117) to carboxylate (IA-121), carboxylate (IA-146) to carboxylate (IA-150), carboxylate (IA-187) to carboxylate (IA-257), carboxylate (IA-282) to carboxylate (IA-292), and the carboxylate (IB) is preferably carboxylate (IB-1) to carboxylate (IB-5), carboxylate (IB-30) to carboxylate (IB-34), carboxylate (IB-59) to carboxylate (IB-63), carboxylate (IB-88) to carboxylate (IB-92), carboxylate (IB-125) to carboxylate (IB-173), carboxylate (IB-198) to carboxylate (IB-208).

[0055] <Method for Producing Carboxylate (IA)> The carboxylate (IA) can be produced by reacting a salt represented by the formula (I-a) and a salt represented by the formula (I-b) in a solvent in the presence of a base catalyst. TIFF0007716844000042.tif75152[Wherein all the symbols have the same meanings as described above.] Examples of the base include potassium carbonate and the like. Examples of the solvent include chloroform, dimethylformamide, acetonitrile, and the like. The reaction temperature is generally 15°C to 140°C, and the reaction time is generally 0.5 to 24 hours.

[0056] Examples of the salt represented by formula (I-a) include compounds represented by the following formula, and they can be easily obtained from the market. In addition, these salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000043.tif184151

[0057] Examples of the salt represented by formula (I-b) include salts represented by the following formula, and they can be easily obtained from the market. In addition, these salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2012-224611, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000044.tif167145

[0058] The carboxylate (IA) can also be produced by reacting the salt represented by formula (I-c) and the salt represented by formula (I-d) in a solvent in the presence of a base catalyst. TIFF0007716844000045.tif71150[In the formula, all symbols have the same meanings as described above.] Examples of the base include potassium carbonate and the like. Examples of the solvent include chloroform, dimethylformamide, acetonitrile, and the like. The reaction temperature is generally 15°C to 140°C, and the reaction time is generally 0.5 to 24 hours.

[0059] Examples of the salt represented by formula (I-c) include compounds represented by the following formula, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000046.tif209167

[0060] Examples of the salt represented by formula (I-d) include salts represented by the following formula, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2012-224611, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000047.tif223165

[0061] <Method for producing carboxylate (IB)> Carboxylate (IB) can be produced by reacting the salt represented by formula (I-a), the salt represented by formula (I-b1), and the salt represented by formula (I-a1) in a solvent in the presence of a base catalyst. TIFF0007716844000048.tif79166[In the formula, all symbols have the same meanings as described above.] Examples of the base include potassium carbonate. Examples of the solvent include chloroform, dimethylformamide, and acetonitrile. The reaction temperature is usually 15°C to 140°C, and the reaction time is usually 0.5 to 24 hours.

[0062] Examples of the salt represented by formula (I-a1) include compounds represented by the following formula, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000049.tif208163

[0063] Examples of the salt represented by the formula (I-b1) include salts represented by the following formulas, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2012-224611, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000050.tif178165

[0064] The carboxylate (IB) can also be produced by reacting the salt represented by the formula (I-c), the salt represented by the formula (I-d1), and the salt represented by the formula (I-c1) in a solvent in the presence of a base catalyst. TIFF0007716844000051.tif76165[In the formula, all the symbols have the same meanings as described above.] Examples of the base include potassium carbonate and the like. Examples of the solvent include chloroform, dimethylformamide, acetonitrile, and the like. The reaction temperature is usually 15°C to 140°C, and the reaction time is usually 0.5 to 24 hours.

[0065] Examples of the salt represented by the formula (I-c1) include compounds represented by the following formulas, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000052.tif203164

[0066] Examples of the salt represented by the formula (I-d1) include salts represented by the following formulas, and they can be easily obtained from the market. These salts can also be obtained with reference to the methods described in JP-A-2011-39502, JP-A-2012-224611, JP-A-2014-88367, and JP-A-2013-200561. TIFF0007716844000053.tif219170

[0067] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylate (I). The carboxylic acid generator may contain only one type or two or more types of carboxylates (I). The carboxylate (I) of the present invention can act as an acid generator in a resist composition. The carboxylic acid generator of the present invention may contain carboxylates known in the resist field other than the carboxylate (I). In this case, the ratio (mass ratio) of the content of the carboxylate (I) to the carboxylate other than the carboxylate (I) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and still more preferably 5:95 to 95:5.

[0068] [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 contacted with an acid, the leaving group leaves to form a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition may further contain a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). In the resist composition of the present invention, the content rate 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.

[0069] [Acid generator (B)] When the resist composition of the present invention contains an acid generator (B) or the like, the ratio of the contents of the carboxylate (I) and the acid generator (B) (mass ratio; carboxylate (I): acid generator (B) or the like) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and even more preferably 5:95 to 95:5. Further, when the resist composition of the present invention contains an acid generator (B) or the like, the total content ratio of the carboxylate (I) and the acid generator (B) or the like is preferably 1 part by mass or more (more preferably 3 parts by mass or more) and preferably 55 parts by mass or less (more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less) with respect to 100 parts by mass of the resin (A).

[0070] As the acid generator (B), either a nonionic or an ionic one may be used. Examples of the nonionic acid generator 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), and the like. Representative examples of the ionic acid generator 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, and the like.

[0071] As the acid generator (B), compounds that generate an acid by radiation described in, for example, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, and the like can be used. Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more.

[0072] 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)"). TIFF0007716844000054.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, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the 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-, -S(O)2- or -CO-. Z1 + represents an organic cation.]

[0073] Q b1 and Q b2 Examples 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, and a perfluorohexyl group. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0074] 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 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, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group; 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 divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, 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.

[0075] L b1 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 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.

[0076] TIFF0007716844000055.tif26117[In formula (b1-1), L b2represents 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. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 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 b2 and L b3 is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 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 b4 and L b5 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.

[0077] In the groups represented by formulas (b1-1) to (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L b1 as described below. L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L 1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by the formula is replaced by -O- or -CO-, the group represented by the formula (b1-1) or the formula (b1-3) is preferable.

[0078] Examples of the group represented by the formula (b1-1) include the groups represented by the formulas (b1-4) to (b1-8), respectively. TIFF0007716844000056.tif48120 [In the formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b9 and L b10 is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b11 and L b12 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 number of carbon atoms of L b13 ~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 b17represents 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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. 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 b12 is 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.

[0079] Examples of the group represented by formula (b1-3) include groups represented by formulas (b1-9) to (b1-11). TIFF0007716844000057.tif23139[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms in b19 L b20 and In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms in b21 L b22 and b23 is 21 or less. In formula (b1-11), L b24represents 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. -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.]

[0080] In addition, in the group represented by the formula (b1-9) to the group represented by the 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 taken as the number of carbon atoms of the saturated hydrocarbon group.

[0081] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0082] Examples of the group represented by the formula (b1-4) include the following. TIFF0007716844000058.tif16153

[0083] Examples of the group represented by the formula (b1-5) include the following. TIFF0007716844000059.tif68151

[0084] Examples of the group represented by the formula (b1-6) include the following. TIFF0007716844000060.tif31164

[0085] Examples of the group represented by formula (b1-7) include the following. TIFF0007716844000061.tif57145

[0086] Examples of the group represented by formula (b1-8) include the following. TIFF0007716844000062.tif23150

[0087] Examples of the group represented by formula (b1-2) include the following. JPEG0007716844000063.jpg31161

[0088] Examples of the group represented by formula (b1-9) include the following. TIFF0007716844000064.tif44137

[0089] Examples of the group represented by formula (b1-10) include the following. TIFF0007716844000065.tif92165

[0090] Examples of the group represented by formula (b1-11) include the following. TIFF0007716844000066.tif84164

[0091] 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-, -S(O)2- 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). * represents the bonding position to L b1 represents the bonding position to TIFF0007716844000067.tif83168

[0092] 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 containing an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, 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.

[0093] 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, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom. ja represents an integer of any of 0 to 4.). 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 (wherein -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, -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom. ja represents any integer from 0 to 4.).

[0094] 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 phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms include 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. Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms include p-cyclohexylphenyl group, 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. The number of carbon atoms of the alkyl 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 alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group and hydroxyethyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, etc. Examples of the group in which -CH2- contained in the alkyl group is replaced with -O-, -S(O)2- or -CO- etc. include alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group or a group combining these. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The number of carbon atoms of 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 an acetyl group, a propionyl group, a butyryl group and the like. 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. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms of 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 a group formed by combining an alkoxy group and an alkyl group, a group formed by combining an alkoxy group and an alkoxy group, a group formed by combining an alkoxy group and an alkylcarbonyl group, a group formed by combining an alkoxy group and an alkylcarbonyloxy group and the like. Examples of the group formed by combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group and the like. 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 formed by combining an alkoxy group and an alkoxy group include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group and the like. 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 formed by combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group and the like. 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, and ethoxypropionyloxy group. 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-, -S(O)2-, -CO-, etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0095] Examples of Y include the following. JPEG0007716844000068.jpg156170

[0096] 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-, -S(O)2- 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).

[0097] Examples of the anion in the salt represented by formula (B1) include 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]. 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.

[0098] TIFF0007716844000069.tif111143

[0099] TIFF0007716844000070.tif128167

[0100] TIFF0007716844000071.tif93145

[0101] TIFF0007716844000072.tif137140

[0102] TIFF0007716844000073.tif84163

[0103] JPEG0007716844000074.jpg90150 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, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L A4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

[0104] Preferred anions in the salt represented by formula (B1) include the anions represented by formula (B1a-1) to formula (B1a-38), respectively. TIFF0007716844000075.tif122158

[0105] TIFF0007716844000076.tif95145

[0106] TIFF0007716844000077.tif167156

[0107] Among them, anions represented by any of Formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), and Formula (B1a-22) to Formula (B1a-38) are preferable.

[0108] Z1 + Examples of the organic cation of [Z1] 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 preferable, and arylsulfonium cations are more preferable. 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. TIFF0007716844000078.tif48169In 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, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5They may combine with each other to form a ring together with the sulfur atom to which they are attached, and the -CH2- contained in the ring may be replaced by -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 any integer from 0 to 5. When m2 is 2 or more, the plurality of R b7 may be the same or different, and when n2 is 2 or more, the plurality of R b8 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 combine with each other to form a ring together with the sulfur atom to which they are attached, 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 combine with each other to form a ring including the -CH-CO- to which they are attached, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18Each independently represents a hydroxy group, an aliphatic hydrocarbon 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 b14 are the same or different, and when q2 is 2 or more, the plurality of R b15 are the same or different, and when r2 is 2 or more, the plurality of R b16 are the same or different, and when s2 is 2 or more, the plurality of R b17 are the same or different, and when t2 is 2 or more, the plurality of R 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 chain hydrocarbon group of R b9 ~R b12 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. TIFF0007716844000079.tif10159In particular, the alicyclic hydrocarbon group of R b9 ~R b12 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 a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornil group, an 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. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenylyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include a p-cyclohexylphenyl group and a p-adamantylphenyl group. When the aromatic hydrocarbon group contains a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl 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 alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, and the like. 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 monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. 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. For example, the following rings can be mentioned. * represents the bonding position. TIFF0007716844000080.tif23143R b9 and R b10 The ring formed by R and R together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. For example, thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, and the like can be mentioned. R b11 and R b12 The ring formed by R and R together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring, and the like.

[0109] Among cations (b2-1) to (b2-4), preferably, it is cation (b2-1). Examples of cation (b2-1) include the following cations. TIFF0007716844000081.tif38158

[0110] TIFF0007716844000082.tif140154

[0111] Examples of the cation (b2-2) include the following cations. TIFF0007716844000083.tif18150

[0112] Examples of the cation (b2-3) include the following cations. TIFF0007716844000084.tif26139

[0113] Examples of the cation (b2-4) include the following cations. TIFF0007716844000085.tif85169

[0114] 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 the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), (B1a-22) to (B1a-38) and the cation (b2-1) or the cation (b2-3).

[0115] Preferred examples of the acid generator (B) include those represented by the formulas (B1-1) to (B1-56). Among them, those containing an arylsulfonium cation are preferred, and those represented by the formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), (B1-31) to (B1-56) are particularly preferred. TIFF0007716844000086.tif119149

[0116] JPEG0007716844000087.jpg77147

[0117] JPEG0007716844000088.jpg147146

[0118] JPEG0007716844000089.jpg64163

[0119] TIFF0007716844000090.tif168168

[0120] <Resin (A)> Resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). Resin (A) preferably further contains a structural unit other than structural unit (a1). Examples of the structural unit other than 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 structural unit (a1) and 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 a structural unit derived from other monomers known in the art, etc.).

[0121] 〈Structural unit (a1)〉 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 Resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter also referred to as group (2)). TIFF0007716844000091.tif2397[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 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 site.] TIFF0007716844000092.tif2379[In formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and 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 ring 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 ring may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bonding site.]

[0122] R a1 、R a2 and R a3 Examples of the alkyl group in include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. R a1 、R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bonding site.). The carbon number of the alicyclic hydrocarbon group of R a1 、R a2 and R a3 is preferably 3 to 16. As the group combining a 10150 alkyl group and an alicyclic hydrocarbon group, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornil group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornylethyl group, etc. can be mentioned. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form a non-aromatic hydrocarbon ring, examples of -C(R a1 )(R a2 )(R a3 ) include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents the bonding position to -O-. TIFF0007716844000094.tif30139

[0123] R a1’ 、R a2’ and R a3’ Examples of the hydrocarbon group in R The alkyl group and the alicyclic hydrocarbon group are the same as those mentioned for R a1 、R a2 and R a3 . Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include the group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (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-cycloalkyl group such as a phenylcyclohexyl group, etc. R a2’ and R a3’ are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-X-R a3’ includes the following rings. * represents the bonding position. TIFF0007716844000095.tif19130R a1’ and R a2’ at least one of them is preferably a hydrogen atom. na’ is preferably 0.

[0124] 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. The tert-butoxycarbonyl group is preferred as the group. In formula (1), R a1 , R a2 together with the carbon atom to which they are bonded form an adamantyl group, 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 the bonding position. TIFF0007716844000096.tif78168

[0125] Specific examples of the group (2) include the following groups. * represents the bonding position. TIFF0007716844000097.tif74154

[0126] 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.

[0127] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferably 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 the resist composition, the resolution of the resist pattern can be improved.

[0128] As the structural unit derived from the (meth)acrylic monomer having the group (1), a structural unit represented by the formula (a1-0) (hereinafter, may be referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter, may be referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter, may be referred to as the structural unit (a1-2)) is 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. TIFF0007716844000098.tif43145[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 the bonding position with -CO-. R a01 、R a4 and R a5 each independently represents a hydrogen atom or a methyl group. 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, or a group combining these. R a6 and Ra7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 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.]

[0129] R a01 、R a4 and R a5 are preferably methyl groups. 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), and more preferably an oxygen atom. R a02 、R a03 、R a04 、R a6 and R a7 Examples of the alkyl group, alicyclic hydrocarbon group, and the group formed by combining these in R a1 、R a2 and R a3 include the same groups as those exemplified for R R a02 、R a03 、and R a04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and even more preferably an ethyl group or an isopropyl group. R a02 、R a03 and R a04 The alicyclic hydrocarbon group of preferably has 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms. The group combining an alkyl group and an alicyclic hydrocarbon group preferably has a total carbon number of 18 or less when these alkyl group and alicyclic hydrocarbon group are combined. R a02 and R a03 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl 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 a7 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, still more preferably an ethyl group or an isopropyl 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.

[0130] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-0) is replaced by a hydrogen atom, and structural units represented by any of formula (a1-0-1) to formula (a1-0-10) are preferred. a01 The structural unit (a1-1) includes, for example, structural units derived from the monomers described in JP-A-2010-204646. Among them, structural units represented by any of formula (a1-1-1) to formula (a1-1-4) and structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and structural units represented by any of formula (a1-1-1) to formula (a1-1-4) are more preferred. TIFF0007716844000099.tif66158

[0131] 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 formula (a1-1-1) to formula (a1-1-4) and structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and structural units represented by any of formula (a1-1-1) to formula (a1-1-4) are more preferred. a4 The structural unit (a1-1) includes, for example, structural units derived from the monomers described in JP-A-2010-204646. Among them, structural units represented by any of formula (a1-1-1) to formula (a1-1-4) and structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and structural units represented by any of formula (a1-1-1) to formula (a1-1-4) are more preferred. TIFF0007716844000100.tif44114

[0132] The structural unit (a1-2) includes a structural unit represented by any one of formulas (a1-2-1) to (a1-2-6) and R a5 and a structural unit represented by formula (a1-2-2), (a1-2-5) or (a1-2-6) is preferred. TIFF0007716844000101.tif36161

[0133] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 60 mol %, preferably 5 to 50 mol %, and more preferably 10 to 40 mol %, based on all structural units in the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, even more preferably 20 to 80 mol%, and still more preferably 20 to 75 mol%, based on all structural units in the resin (A).

[0134] An example of the structural unit (a1) having the group (2) is a structural unit represented by formula (a1-4) (hereinafter, sometimes referred to as "structural unit (a1-4)"). TIFF0007716844000102.tif3867[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 alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of Ra33 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-.

[0135] R a32 and R a33 Examples of the alkyl group for R and R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 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 a32 and R a33 Examples of the halogen atom for R and R include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable. Alkylcarbonyl groups include acetyl, propionyl and butyryl groups. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. R a34 , R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these groups are combined. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, and norbornyl groups, as well as the following groups (* indicates a bonding site): TIFF0007716844000103.tif10151 Examples of aromatic hydrocarbon groups include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (such as a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, or a 2-methyl-6-ethylphenyl group), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (such as a p-cyclohexylphenyl group or a p-adamantylphenyl group), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. a36 Examples of the group include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these.

[0136] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 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. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, 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, 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. The alkyl group and alicyclic hydrocarbon group in R a36 are preferably unsubstituted. The aromatic hydrocarbon group in R a36 preferably has an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0137] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) is eliminated by contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, structural units represented by formula (a1-4-1) to formula (a1-4-12) and structural units in which the hydrogen atom corresponding to R a32 is replaced by a methyl group are included, and more preferably, structural units represented by formula (a1-4-1) to formula (a1-4-5) and formula (a1-4-10) are included. When the resin (A) has the structural units (a1-4), its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol% based on the total of all the structural units of the resin (A).

[0138] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) include the structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007716844000105.tif4354In the 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 any integer from 1 to 4, and * represents the bonding position with L 51 . L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents any integer from 1 to 3. s1' represents any integer from 0 to 3.

[0139] 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 the 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 L53 Among them, it is preferable that one is -O- and the other is -S-. For s1, 1 is preferable. For s1’, any integer from 0 to 2 is preferable. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0140] Examples of the structural unit (a1-5) include structural units derived from the monomers described in JP-A-2010-61117. Among them, the structural units represented by Formula (a1-5-1) to Formula (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 still more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0141] Examples of the structural unit (a1) include a structural unit represented by Formula (a1-0X) (hereinafter sometimes referred to as the structural unit (a1-0X)). TIFF0007716844000107.tif3961[In Formula (a1-0X), R x1 represents a hydrogen atom or a methyl group. R x2 and R x3 each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar x1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.

[0142] R x2 and R x3 Examples of the saturated hydrocarbon group of include an alkyl group, an alicyclic 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, a pentyl group, and a hexyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Ar x1 Examples of the aromatic hydrocarbon group include aryl groups having 6 to 36 carbon atoms, such as a phenyl group, a naphthyl group, and an anthryl group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably has 6 to 18 carbon atoms, and is even more preferably a phenyl group. Ar x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. R x1 , R x2 and R x3 are each independently preferably a methyl group or an ethyl group, more preferably a methyl group.

[0143] The structural unit (a1-0X) includes the following structural units and R in the structural unit (a1-0X): x1 In this case, the structural unit (a1-0X) is preferably a structural unit (a1-0X-1) to a structural unit (a1-0X-3). TIFF0007716844000108.tif34161 When the resin (A) has the structural unit (a1-0X), the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on all monomers in the resin (A). The resin (A) may contain two or more types of structural units (a1-0X).

[0144] Further, 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 even more preferably 10 to 40 mol% based on all the structural units of the resin (A).

[0145] 〈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 from which the structural unit(s) is derived, a monomer having no acid-labile group known in the resist field can be used. The structural unit(s) preferably has a hydroxy group or a lactone ring. When a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0146] 〈Structural unit (a2)〉 The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, 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 preferred, and it is more preferred 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 preferred, and it is more preferred to use the structural unit (a2-1) described later. The structural unit (a2) may be contained alone or in combination of two or more.

[0147] 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)"). TIFF0007716844000110.tif4551[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 a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bonding position with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same as or different from each other.]

[0148] R a50 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, and a bromine atom, etc. R a50Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include 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 and perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. R a51 Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group and tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is still more preferable. R a51 Examples of the alkylcarbonyl group include acetyl group, propionyl group and butyryl group. R a51 Examples of the alkylcarbonyloxy group include acetyloxy group, propionyloxy group and butyryloxy group. R a51 is preferably a methyl group.

[0149] *-X a51 -(A a52 -X a52 ) nb Examples of *-X- 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- and the like can be mentioned. 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, a 2-methylbutane-1,4-diyl group, and the like. A a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-O-A a52 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 the para position of the benzene ring, and more preferably bonded to the para position.

[0150] Examples of the structural unit (a2-A) include structural units derived from the monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include the structural units represented by formula (a2-2-1) to formula (a2-2-6), and R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-6). a50The structural unit (a2-A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula (a2-2-6), in which R in the structural unit (a2-A) is substituted with a hydrogen atom. a50 It is preferable that the structural unit is a structural unit in which a methyl group corresponding to the following formula is substituted with a hydrogen atom: TIFF0007716844000111.tif42166 When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, even more preferably 15 to 65 mol %, still more preferably 20 to 65 mol %, and particularly preferably 25 to 55 mol %, based on all structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into the resin (A) by polymerizing the structural unit (a1-4) and then treating with an alkali such as tetramethylammonium hydroxide.

[0151] An example of the structural unit (a2) having an alcoholic hydroxy group is a structural unit represented by formula (a2-1) (hereinafter, sometimes referred to as "structural unit (a2-1)"). TIFF0007716844000112.tif3957 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding position with —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16Each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents any integer from 0 to 10.

[0152] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents any integer from 1 to 4), and more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably any integer from 0 to 3, more preferably 0 or 1.

[0153] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. A structural unit represented by any of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. 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%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol% based on all the structural units of the resin (A).

[0154] 〈Structural unit (a3)〉 The lactone ring contained in the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, an adamantanlactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a 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. TIFF0007716844000114.tif51162[In formula (a3-1), formula (a3-2), formula (a3-3), and formula (a3-4), L a4 、L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -CO-O- (where k3 represents an integer from 1 to 7). L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding position 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 any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 、R a22 、R a23 and / or R a25 may be the same as or different from each other.

[0155] R a21 、R a22 、R a23 and R a25 Examples of the aliphatic hydrocarbon group in R a24 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 a24 include fluorine atom, chlorine atom, bromine atom and iodine atom.

[0156] La8 and L a9 Examples of the alkanediyl group in 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, a 2-methylbutane-1,4-diyl group, and the like.

[0157] In formulas (a3-1) to (a3-3), L a4 ~L a6 is each independently preferably -O- or, *-O-(CH2) k3 -CO-O- wherein 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.

[0158] 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)'. TIFF0007716844000115.tif3845(wherein R a24 , L a7 represents the same meaning as described above.)

[0159] 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 above structural units, structural units in which the methyl groups corresponding to R a18 , R a19 , R a20 and R a24 are replaced by hydrogen atoms are preferred. TIFF0007716844000116.tif115165When the resin (A) contains the structural unit (a3), the total content thereof 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). Further, 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), respectively.

[0160] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007716844000117.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing fluorine atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon group represented by includes a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these, etc.

[0161] 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; 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, etc.

[0162] 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). TIFF0007716844000119.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 3arepresents 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.

[0163] L 4a Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group.

[0164] L 3a Examples of the perfluoroalkanediyl group in the formula (I) include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3 ,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, and perfluorooctane-4,4-diyl group. L 3a Examples of the perfluorocycloalkanediyl group in the formula (I) include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

[0165] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0166] Examples of the structural unit (a4-0) include the following structural units and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a4-0) is replaced by a hydrogen atom. 5a TIFF0007716844000120.tif95165

[0167] TIFF0007716844000121.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced 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. TIFF0007716844000122.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 represents -O-, -CO-, -CO-O- or -O-CO-. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms of is 7 or less. ] * is a bonding position, and the * on the right is the bonding position with -O-CO-R a42 . ]

[0168] R a42 Examples of the saturated hydrocarbon group in include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0169] 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). Examples of the group formed by the combination of TIFF0007716844000123.tif10160 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, and -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, etc.

[0170] R a42 Examples of the substituent that 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 preferable. TIFF0007716844000124.tif752[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, **-O-CO- or **-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * is the bonding position with R a42 .] However, in R a42 -X a43 -A a45 , when R a42 does not have a halogen atom, A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

[0171] A a45 Examples of the aliphatic hydrocarbon group in A include alkyl groups such as 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 and octadecyl group; 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.). TIFF0007716844000125.tif10160Examples of the group formed by the combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0172] 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 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 R 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 carbon number 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.

[0173] R a42 When R 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). TIFF0007716844000126.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.

[0174] 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.

[0175] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007716844000127.tif13161

[0176] 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, hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 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.

[0177] 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 a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and a group formed by combining an alkanediyl group with a divalent alicyclic hydrocarbon group. Specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. Preferably, s is 0.

[0178] In the group represented by formula (a-g1), X a42 In the following examples, * and ** each represent a bond position, and ** represents -O-CO-R a42 This is the bonding position with TIFF0007716844000128.tif48153

[0179] The structural unit represented by formula (a4-1) includes the structural units shown below and R in the structural unit represented by formula (a4-1) in the structural units shown below. a41 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007716844000129.tif100142

[0180] TIFF0007716844000130.tif123140

[0181] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). TIFF0007716844000131.tif3354[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 with fluorine atoms. However, 44 L f6 and

[0182] L 44 The alkanediyl group of a41 includes the same groups as those exemplified by A R f6 The saturated hydrocarbon group of a42 includes the same groups as those exemplified by R L 44 As the alkanediyl group in

[0183] As the structural unit represented by formula (a4-2), for example, the structural units represented by formulas (a4-1-1) to (a4-1-11) can be mentioned. The structural unit in which the methyl group corresponding to R f5 in structural unit (a4-2) is replaced by a hydrogen atom is also mentioned as the structural unit represented by formula (a4-2).

[0184] TIFF0007716844000132.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may 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.

[0185] As the alkanediyl group in L 5 , groups similar to those exemplified as the alkanediyl group of A a41 can be mentioned. As the divalent saturated hydrocarbon group which may have a fluorine atom in A f13 , preferably 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, 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.

[0186] The saturated hydrocarbon group of A f14 and the saturated hydrocarbon group which may have a fluorine atom are R a42Examples of the group are the same as those exemplified above. 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 and the like are preferable.

[0187] 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, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

[0188] Examples of the structural unit represented by formula (a4-3) include structural units represented by formula (a4-1'-1) to formula (a4-1'-11), respectively. R in structural unit (a4-3)f7 The structural unit in which the methyl group corresponding to it is replaced by a hydrogen atom is also cited as the structural unit represented by the formula (a4-3).

[0189] As the structural unit (a4), the structural unit represented by the formula (a4-4) is also cited. TIFF0007716844000133.tif4061[In the 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 of any one of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom.]

[0190] 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 the 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.

[0191] As the structural unit represented by the formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, the structural unit in which the methyl group corresponding to R f21 in the structural unit (a4-4) is replaced by a hydrogen atom is cited. 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).

[0192] 〈Structural unit (a5)〉 Examples of the non-detachable hydrocarbon group 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). TIFF0007716844000135.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-.]

[0193] 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.

[0194] 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.

[0195] 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 the 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, x1 the total carbon number of L x2 and L 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 represent 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 represent 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.

[0196] 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.

[0197] Examples of the group represented by formula (L1-1) include the following divalent groups. TIFF0007716844000137.tif55134

[0198] Examples of the group represented by formula (L1-2) include the following divalent groups. TIFF0007716844000138.tif24131

[0199] Examples of the group represented by formula (L1-3) include the following divalent groups. TIFF0007716844000139.tif15145

[0200] Examples of the group represented by formula (L1-4) include the following divalent groups. TIFF0007716844000140.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0201] 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. TIFF0007716844000141.tif110150 When the resin (A) has a structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol% with respect to all the structural units of the resin (A).

[0202] <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.

[0203] The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by the formula (II-2-A'). TIFF0007716844000142.tif36104 [In the 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 replaced 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.

[0204] R III3 Examples of the halogen atom represented by III3 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by III3 include the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by a8 . a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by a8 include the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by III3 . A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by x1 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 x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted with x1 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. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination thereof may also be possible. 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, etc. are included. Examples of those 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 number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formulae, * and ** represent bonding positions, and * represents the bonding position with A x1 and represents the bonding position with A. TIFF0007716844000143.tif145161

[0205] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0206] ZA in formula (II-2-A’) + is the same as the cation Z1 in the acid generator (B1). + Examples thereof include the same ones.

[0207] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007716844000144.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 by b1 are the same as those of the perfluoroalkyl group having 1 to 6 carbon atoms represented by the aforementioned Q

[0208] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007716844000145.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Qb and ZA + represents the same meaning 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 R 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 X include the same as those of the divalent saturated hydrocarbon group represented by X III3 represented by.

[0209] As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable. TIFF0007716844000146.tif5287 [In the formula (II-2-A-2), R III3 R III5 and ZA + represent the same meaning as described above. m and n each independently represent 1 or 2.

[0210] Examples of the structural unit represented by the formula (II-2-A') include, for example, the following structural units, a group corresponding to the methyl group of R III3 wherein the group corresponding to the methyl group of R 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 unit described in International Publication No. 2012 / 050015. ZA+ represents an organic cation. TIFF0007716844000147.tif85163

[0211] 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). TIFF0007716844000148.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 combine with each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion.] R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group and a naphthylene group. R II2 and R II3 Examples 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. R II4 Examples of the halogen atom represented by R 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 R include the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 A II1 ​Examples of the divalent linking group represented by include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, X III3 include the same ones as the divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by .

[0212] Examples of the structural unit containing a cation in formula (II-1-1) include the structural unit represented by the following and a structural unit in which a group corresponding to the methyl group of R II4 is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. JPEG0007716844000149.jpg85130

[0213] A - Examples of the organic anion represented by include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, etc. A - 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).

[0214] A - Examples of the sulfonylimide anion represented by include the following. TIFF0007716844000150.tif38135

[0215] Examples of the sulfonylmethide anion include the following. TIFF0007716844000151.tif29123

[0216] Examples of the carboxylic acid anion include the following. TIFF0007716844000152.tif39136

[0217] Examples of the structural unit represented by formula (II-1-1) include the structural unit represented by the following, etc. 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% based on all the structural units of the resin (A).

[0218] The resin (A) may have structural units other than the above-described structural units. Examples of such structural units include structural units well-known in the art.

[0219] 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), and more preferably at least two kinds. The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-A) or a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4).

[0220] 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 the monomers that lead to these structural units. The content of each structural unit of the resin (A) can be adjusted by the amount of the monomers 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.

[0221] <Resin other than resin (A)> The resist composition of the present invention may be used in combination with a resin other than the resin (A). 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, the resin containing the structural unit (a4) is preferable as the resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 45 mol% or more based on 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 the structural unit 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 the monomers that induce these structural units. The content of each structural unit of the resin (X) can be adjusted by the amount of the monomers used in the polymerization. The weight average molecular weight of the 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 the resin (X) is the same as that of the resin (A). When the resist composition contains the 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, particularly preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A).

[0222] The content rate of the 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 the resist composition contains a resin other than the resin (A), the total content rate of the resin (A) and the resin other than the 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.

[0223] <Solvent (E)> The content rate of the 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 the 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.

[0224] <Quencher (C)> The quencher (C) can be a basic nitrogen-containing organic compound or a salt that generates an acid with a weaker acidity than the acid generated from the acid generator (B) (excluding the carboxylate salt represented by formula (I)). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15 mass%, more preferably about 0.1 to 10 mass%, even more preferably about 0.1 to 5 mass%, and even more preferably about 0.1 to 3 mass%, based on the solids content of the resist composition. The basic nitrogen-containing organic compound includes amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, 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, etc. Aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropylaniline 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.

[0225] The acidity of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) include the salt represented by the following formula, the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. As the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B), preferably, it is a salt that generates a carboxylic acid weaker in acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably, it is the weak acid inner salt (D). TIFF0007716844000154.tif85165

[0226] Examples of the weak acid inner salt (D) include the following salts. TIFF0007716844000155.tif72165

[0227] 〈Other Components〉 The resist composition of the present invention may, if necessary, contain components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0228] 〈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 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 respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0229] 〈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 carried out by a commonly used apparatus 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 applied 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), an F2 excimer laser (wavelength 157 nm), those that convert 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, those that irradiate 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 in 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, the paddle method, the spray method, the 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.

[0230] <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 electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for semiconductor microfabrication.

Examples

[0231] 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”.

[0232] Example 1: Synthesis of the salt represented by formula (IA-31) 4.72 parts of the salt represented by formula (IA-31-a), 5.10 parts of the salt represented by formula (IA-31-b), 30 parts of dimethylformamide, and 0.69 part of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the obtained reaction mixture, 60 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 take out the organic layer. To the recovered 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 take out the organic layer. This water washing operation was repeated 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 0.48 part of the salt represented by formula (IA-31). MASS(ESI(+)Spectrum):M 2+ 288.0(M / 2) MASS(ESI(-)Spectrum):M - 193.1

[0233] Example 2: Synthesis of the salt represented by formula (IB-2) 4.72 parts of the salt represented by formula (IA-31-a), 2.55 parts of the salt represented by formula (IA-31-b), 30 parts of dimethylformamide, and 1.38 parts of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the obtained reaction mixture, 60 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 take out the organic layer. To the recovered 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 take out the organic layer. This water washing operation was repeated 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 0.79 part of the salt represented by formula (IB-2). MASS(ESI(+)Spectrum):M 3+ 278.4(M / 3) MASS(ESI(-)Spectrum): M - 193.1

[0234] Example 3: Synthesis of the salt represented by formula (IA-33) 6.16 parts of the salt represented by formula (IA-33-a), 6.54 parts of the salt represented by formula (IA-33-b), 30 parts of dimethylformamide, and 0.69 part of potassium carbonate were mixed and stirred at 120°C for 4 hours, and then cooled to 23°C. To the obtained reaction mixture, 60 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 recovered 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 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 0.51 part of the salt represented by formula (IA-33). MASS(ESI(+)Spectrum): M 2+ 288.0 (M / 2) MASS(ESI(-)Spectrum): M - 337.1

[0235] Example 4: Synthesis of the salt represented by formula (IB-4) 6.16 parts of the salt represented by formula (IA-33-a), 3.27 parts of the salt represented by formula (IA-33-b), 30 parts of dimethylformamide, and 1.38 parts of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the obtained reaction mixture, 60 parts of chloroform and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. To the recovered organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 0.88 part of the salt represented by formula (IB-4). MASS(ESI(+)Spectrum):M 3+ 278.4(M / 3) MASS(ESI(-)Spectrum):M - 337.1

[0236] Example 5: Synthesis of the salt represented by formula (IA-201) A solution obtained by mixing 4.49 parts of pyridine, 14.67 parts of the compound represented by formula (IA-201-b), and 25 parts of tetrahydrofuran was added dropwise to a solution obtained by mixing 10 parts of the compound represented by formula (IA-201-a) and 10 parts of tetrahydrofuran at 0 °C. The obtained mixture was stirred at 23 °C for 1 hour. 30 parts of ion-exchanged water was added to the reaction mixed solution, and the mixture was extracted with ethyl acetate. After the extracted organic layer was concentrated under reduced pressure, n-heptane was added and stirring was carried out for 1 hour. The mixed solution was settled, the supernatant was removed, and dried to obtain 22.91 parts of the salt represented by formula (IA-201-c). 2.50 parts of the salt represented by formula (IA-201-c), 50 parts of chloroform, and 12.50 parts of ion-exchanged water were added, and then stirred at 23 °C for 30 minutes. After adding 1.29 parts of the salt represented by formula (IA-201-d) to the obtained mixture, it was stirred at 23 °C for 3 hours, and the organic layer was taken out by liquid separation. 20 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 °C for 30 minutes, and then the organic layer was taken out by liquid separation. This water washing operation was repeated 5 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was charged into the obtained concentrate, stirred at 23 °C for 30 minutes, then the supernatant was removed and dried to obtain 3.08 parts of the salt represented by formula (IA-201-e). 2.50 parts of the salt represented by formula (IA-201-c), 50 parts of chloroform, and 12.50 parts of ion-exchanged water were added, and then stirred at 23 °C for 30 minutes. After adding 1.44 parts of the salt represented by formula (IA-201-f) to the obtained mixture, it was stirred at 23 °C for 3 hours, and the organic layer was taken out by liquid separation. 20 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 °C for 30 minutes, and then the organic layer was taken out by liquid separation. This water washing operation was repeated 5 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was charged into the obtained concentrate, stirred at 23 °C for 30 minutes, then the supernatant was removed and dried to obtain 3.12 parts of the salt represented by formula (IA-201-g). 1.01 parts of the salt represented by formula (IA-201-e), 1.06 parts of the salt represented by formula (IA-201-g), 30 parts of dimethylformamide, and 0.09 part of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the resulting reaction mixture, 60 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 recovered 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 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 1.18 parts of the salt represented by formula (IA-201). MASS(ESI(+)Spectrum):M 2+ 288.0(M / 2) MASS(ESI(-)Spectrum):M - 531.1

[0237] Example 6: Synthesis of the salt represented by formula (IB-128) 1.01 parts of the salt represented by formula (IA-201-e), 0.53 part of the salt represented by formula (IA-201-g), 30 parts of dimethylformamide, and 0.17 part of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the resulting reaction mixture, 60 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 recovered 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 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 1.04 parts of the salt represented by formula (IB-128). MASS(ESI(+)Spectrum):M 3+ 278.4(M / 3) MASS(ESI(-)Spectrum):M - 531.1

[0238] Example 7: Synthesis of the salt represented by formula (IA-256) 7.54 parts of the salt represented by formula (IA-256-a), 6.50 parts of the salt represented by formula (IA-256-b), 30 parts of dimethylformamide, and 0.69 part of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the obtained reaction mixture, 60 parts of chloroform and 30 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then liquid separation was carried out to take out the organic layer. To the recovered organic layer, 30 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then liquid separation was carried out to take out the organic layer. This water washing operation was repeated 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 1.48 parts of the salt represented by formula (IA-256). MASS(ESI(+)Spectrum):M 2+ 355.0 (M / 2) MASS(ESI(-)Spectrum):M - 337.1

[0239] Example 8: Synthesis of the salt represented by formula (IB-172) 7.54 parts of the salt represented by formula (IA-256-a), 3.25 parts of the salt represented by formula (IA-256-b), 30 parts of dimethylformamide, and 1.38 parts of potassium carbonate were mixed and stirred at 120 °C for 4 hours, and then cooled to 23 °C. To the resulting reaction mixture, 60 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 recovered 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 8 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: chloroform / methanol = 1 / 1) to obtain 1.59 parts of the salt represented by formula (IB-172). MASS(ESI(+)Spectrum):M 3+ 369.0(M / 3) MASS(ESI(-)Spectrum):M - 337.1

[0240] Synthesis of Resin The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007716844000167.tif3896

[0241] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used, and they were mixed so that the molar ratio [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] was 38:24:38. Further, 1.5 times the mass of methyl isobutyl ketone based on the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and a resin A1 (copolymer) having a weight average molecular weight of about 5.3×10 3 was obtained in a yield of 78%. This resin A1 has the following structural units. TIFF0007716844000168.tif28125

[0242] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used, and they were mixed so that the molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62. Further, 1.5 times the mass of methyl isobutyl ketone based on the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and a resin A2 (copolymer) having a weight average molecular weight of about 5.4×10 3 was obtained in a yield of 89%. This resin A2 has the following structural units. TIFF0007716844000169.tif2887

[0243] <Preparation of Resist Composition> As shown in Table 3, each of the following components was mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

[0244]

Table 3

[0245] <Resin> A1, A2: Resin A1, Resin A2 <Acid Generator (B)> B1-25: Salt represented by formula (B1-25); synthesized by the method described in JP-A-2011-126869 TIFF0007716844000171.tif2667<Carboxylate (I)> IA-31: Salt represented by formula (IA-31) IB-2: Salt represented by formula (IB-2) IA-33: Salt represented by formula (IA-33) IB-4: Salt represented by formula (IB-4) IA-201: Salt represented by formula (IA-201) IB-128: Salt represented by formula (IB-128) IA-256: Salt represented by formula (IA-256) IB-172: Salt represented by formula (IB-172) <Quencher (C)> IX-1 IX-2 IX-3 TIFF0007716844000172.tif72108<Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0246] (Electron Beam Exposure Evaluation of Resist Composition) A 6-inch silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90 °C for 60 seconds. A resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Thereafter, it was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 3 on a direct hot plate to form a composition layer. Using an electron beam lithography machine ["HL-800D 50keV" manufactured by Hitachi, Ltd.], a line and space pattern was directly drawn on the composition layer formed on the wafer by changing the exposure dose stepwise. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 3 on a hot plate, and further paddle development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure dose at which the line width and space width of the 60-nm line and space pattern became 1:1 was defined as the effective sensitivity.

[0247] Line edge roughness evaluation (LER): The fluctuation width of the unevenness on the side wall surface of the resist pattern manufactured with the effective sensitivity was measured with a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 4.

Table 4

Industrial Applicability

[0248] The carboxylate salt of the present invention and the resist composition containing the carboxylate salt have good line edge roughness and are useful for fine processing of semiconductors.

Claims

1. A carboxylate represented by formula (IA) or formula (IB). [In formula (IA) and formula (IB), R １ , R ２ , R ３ and R ４ each independently represents a phenyl group which may have a substituent. R ５ 、 R ６ 、 R ７ 、 R ８ and R ９ each independently represents a halogen atom, a hydroxy group, a C1-C6 perfluoroalkyl group or a C1-C12 alkyl group, and the -CH ２ - in the alkyl group may be replaced by -O- or -CO-. m5 represents 0 or 1. m6 represents 0 or 1. m7 represents 0 or 1. m8 represents 0 or 1. X １ and X ２ each independently represents an oxygen atom or a sulfur atom, and the bonding positions of X １ and X ２ are in the p-position or m-position relative to the bonding position of I ＋ . X ０１ , X ０２ and X ０３ each independently represents an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (wherein -CH ２ - included in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or an alicyclic hydrocarbon group having 3 to 24 carbon atoms - a chain hydrocarbon group having 1 to 18 carbon atoms - (wherein -CH ２ - included in the alicyclic hydrocarbon group and the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a substituent).]

2. X ０１ , X ０２ and X ０３ is each independently an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (wherein -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or an alicyclic hydrocarbon group - chain hydrocarbon group - (wherein -CH 2 - contained in the alicyclic hydrocarbon group and the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group). The carboxylate according to claim 1.

3. A carboxylic acid generator containing the carboxylate according to Claim 1 or 2.

4. A resist composition containing the carboxylic acid generator according to Claim 3, an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

5. The resist composition according to Claim 4, 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 an integer from 1 to 7, and * represents the bonding position with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 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. ]

6. The resist composition according to Claim 4 or 5, wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 represents a single bond or *-X a51 -(A a52 -X a52 ) nｂ -, where * represents the bonding position with the carbon atom to which -R a50 is bonded. A a52 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 Rs a51 may be the same as or different from each other.]

7. A method for manufacturing a resist pattern, comprising: (1) a step of applying the resist composition according to any one of Claims 4 to 6 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.