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

Abstract

To provide a carboxylate that can produce a resist pattern having excellent pattern collapse margins, a carboxylic acid generator and a resist composition comprising the same.SOLUTION: Specifically, the present invention discloses a carboxylate represented by e.g. formula (I-1), a carboxylic acid generator and a resist composition.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007691872000001.tif2643 Patent Document 2 describes a resist composition containing a carboxylate represented by the following formula as a carboxylic acid generator. TIFF0007691872000002.tif4343 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007691872000003.tif3491 Patent Document 4 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007691872000004.tif2687

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a carboxylate salt that forms a resist pattern with better pattern collapse resistance (PCM) than a resist pattern formed by a resist composition containing the above salt.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A carboxylate salt represented by formula (I). TIFF0007691872000005.tif76104[In formula (I), R 1 , R 2 and R 3 each independently represents -O-R 10 , -O-CO-R 10 , -O-CO-O-R 10 , -O-L 1 -CO-O-R 10 . R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have a substituent, and -CH 2 - contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 10 represents a group represented by formula (IC). X 1 , X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 0 to 5, and when m1 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m2 represents any integer from 0 to 4, and when m2 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. m3 represents any integer from 0 to 4. When m3 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. m4 represents any integer from 0 to 4. When m4 is 2 or more, the plurality of Rs 4 may be the same as or different from each other. m5 represents any integer from 0 to 4. When m5 is 2 or more, the plurality of Rs 5 may be the same as or different from each other. m6 represents any integer from 0 to 4. When m6 is 2 or more, the plurality of Rs 6 may be the same as or different from each other. m7 represents any integer from 0 to 5. When m7 is 2 or more, the plurality of Rs 7 may be the same as or different from each other. m8 represents any integer from 0 to 4. When m8 is 2 or more, the plurality of Rs 8 may be the same as or different from each other. m9 represents any integer from 0 to 4. When m9 is 2 or more, the plurality of Rs 9 may be the same as or different from each other. However, 0 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, 0 ≤ m3 + m9 ≤ 4, and at least one of m1, m2, and m3 represents an integer of 1 or more. X 4 represents a single bond, -CH 2 -, -O-, -S-, -CO-, -SO- or -SO 2 -. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. TIFF0007691872000006.tif2882 [In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of Rs Ais the same or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L 2 represents a hydrocarbon group having 1 to 36 carbon atoms which may have a single bond or a substituent, and -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -. * represents a bonding site. [2]X 1 , X 2 and X 3 are oxygen atoms, and the carboxylate salt according to [1]. [3]R 1 , R 2 and R 3 are -O-CO-O-R 10 - or -O-L 1 -CO-O-R 10 and the carboxylate salt according to [1] or [2]. [4]L 2 is a methylene group, and the carboxylate salt according to any one of [1] to [3]. [5]X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent, and the carboxylate salt according to any one of [1] to [4]. [6]X 0 is an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), or an aromatic hydrocarbon group which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms, and the carboxylate salt according to any one of [1] to [5]. A carboxylic acid generator containing the carboxylate salt according to any one of [1] to [6]. A resist composition containing the carboxylic acid generator according to [7], an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group. The resist composition according to [8], wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). TIFF0007691872000007.tif46102[In the formula (a1-1) and the formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH 2 ) k1 -CO-O-, k1 represents an integer of any one of 1 to 7, and * represents the bonding position with -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents an integer of any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1' represents an integer of any one of 0 to 3.] The resist composition according to [8] or [9], further containing a resin containing a structural unit having a fluorine atom.

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

[10] onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including.

Advantages of the Invention

[0006] By using the resist composition containing the carboxylate of the present invention, a resist pattern can be produced with good pattern collapse resistance (PCM).

Embodiments for Carrying Out the Invention

[0007] In this specification, the “(meth)acrylic monomer” means “at least one of an acrylic monomer and a methacrylic monomer”. Notations 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. For -CH 2 - when replaced by -O-, -S-, -CO- or -SO 2 -, the same examples shall apply to each group. The “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of those groups may be appropriately changed depending on the bonding form. “Derived from” or “induced from” means that the polymerizable C═C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0008] 〔Carboxylate represented by formula (I)〕 The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as “salt (I)”). Among salts (I), the side having a negative charge may be referred to as “anion (I)”, and the side having a positive charge may be referred to as “cation (I)”. TIFF0007691872000008.tif76104[Wherein all the symbols have the same meanings as described above.]

[0009] In formula (I), R 1 , R2 and R 3 The L contained in 1 Examples of the alkanediyl group in include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group; and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. can be mentioned. L 1 is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0010] R 1 、R 2 and R 3 The R contained in 10 is a group represented by formula (IC). TIFF0007691872000009.tif2882[In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of R A are the same or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L 2 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH 2 - contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. * represents a bonding site.]

[0011] L 2Examples of the hydrocarbon group having 1 to 36 carbon atoms include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, and alkynediyl groups, and monocyclic or polycyclic alicyclic hydrocarbon groups), aromatic hydrocarbon groups, etc., and a hydrocarbon group formed by combining two or more of these groups may also be used. L 2 In the hydrocarbon group in 2 , -CH 2 - may be replaced by -O-, -S-, -CO- or -SO - Examples of the alkanediyl group include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group etc. The number of carbon atoms of the alkanediyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenediyl group include ethenediyl group, propenediyl group, isopropenediyl group, butenediyl group, isobutenediyl group, tert-butenediyl group, pentenediyl group, hexenediyl group, heptenediyl group, octenediyl group, isooctenediyl group, nonenediyl group. Examples of the alkynediyl group include ethynediyl group, propynediyl group, isopropynediyl group, butynediyl group, isobutynediyl group, tert-butynediyl group, pentynediyl group, hexynediyl group, octynediyl group, nonynediyl group, etc. -CH 2- is a group replaced by -O-, -S-, -CO- or -SO 2 Examples of the group replaced by - include a hydroxy group (-CH included in a methyl group 2 - replaced by -O-), a carboxy group (-CH included in an ethyl group 2 -CH 2 - replaced by -O-CO-), a thiol group (-CH included in a methyl group 2 - replaced by -S-), an alkanediyl-oxy group (-CH at any position included in an alkanediyl group 2 - replaced by -O-), an alkanediyl-oxycarbonyl group (-CH at any position included in an alkanediyl group 2 -CH 2 - replaced by -O-CO-), an alkanediyl-carbonyl group (-CH at any position included in an alkanediyl group 2 - replaced by -CO-), an alkanediyl-carbonyl-oxy group (-CH at any position included in an alkanediyl group 2 -CH 2 - replaced by -CO-O-), an alkanediyl-thio group (-CH at any position included in an alkanediyl group 2 - replaced by -S-), an alkanediyl-sulfonyl group (-CH at any position included in an alkanediyl group 2 - is a group replaced by -SO 2 -), etc. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 17 carbon atoms, such as a methylene-oxy group, an ethylene-oxy group, a propanediyl-oxy group, a butanediyl-oxy group, a pentanediyl-oxy group, a hexanediyl-oxy group, an octanediyl-oxy group, a 2-ethylhexanediyl-oxy group, a nonanediyl-oxy group, a decanediyl-oxy group, an undecanediyl-oxy group, etc. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 17 carbon atoms, such as a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propanediyl-oxycarbonyl group, a butanediyl-oxycarbonyl group, a pentanediyl-oxycarbonyl group, a hexanediyl-oxycarbonyl group, an octanediyl-oxycarbonyl group, a 2-ethylhexanediyl-oxycarbonyl group, a nonanediyl-oxycarbonyl group, a decanediyl-oxycarbonyl group, an undecanediyl-oxycarbonyl group, and the like. Examples of the alkanediyl-carbonyl group include alkanediyl-carbonyl groups having 2 to 18 carbon atoms, such as a methylene-carbonyl group, an ethylene-carbonyl group, a propanediyl-carbonyl group, a butanediyl-carbonyl group, a pentanediyl-carbonyl group, a hexanediyl-carbonyl group, an octanediyl-carbonyl group, a 2-ethylhexanediyl-carbonyl group, a nonanediyl-carbonyl group, a decanediyl-carbonyl group, an undecanediyl-carbonyl group, and the like. Examples of the alkanediyl-carbonyloxy group include alkanediyl-carbonyloxy groups having 2 to 17 carbon atoms, such as a methylene-carbonyloxy group, an ethylene-carbonyloxy group, a propanediyl-carbonyloxy group, a butanediyl-carbonyloxy group, a pentanediyl-carbonyloxy group, a hexanediyl-carbonyloxy group, an octanediyl-carbonyloxy group, a 2-ethylhexanediyl-carbonyloxy group, a nonanediyl-carbonyloxy group, a decanediyl-carbonyloxy group, an undecanediyl-carbonyloxy group, and the like. Examples of the alkanediyl-thio group include alkanediyl-thio groups having 1 to 17 carbon atoms, such as a methylene-thio group, an ethylene-thio group, a propanediyl-thio group, a butanediyl-thio group, a pentanediyl-thio group, a hexanediyl-thio group, a heptanediyl-thio group, an octanediyl-thio group, a nonanediyl-thio group, a decanediyl-thio group, an undecanediyl-thio group, a dodecanediyl-thio group, a 2-methylpropanediyl-thio group, and the like. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, a propylenesulfonyl group, and the like. In addition, substitutions in the alkenediyl group and the alkynediyl group can include a carbon-carbon double bond or a carbon-carbon triple bond at any position in the examples of substitutions in the above-described alkanediyl group.

[0012] Examples of the monocyclic alicyclic hydrocarbon group include the following groups. The bonding site can be at any position. Specifically, monocyclic cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene-3,6-diyl group, a cyclooctane-1,5-diyl group, and the like; examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkanediyl groups such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, a 5-norbornene-2,3-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group, and the like. TIFF0007691872000010.tif44168 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12. In addition, -CH 2 - in the alicyclic hydrocarbon group replaced by -O-, -S-, -CO- or -SO 2 - Examples of the group include the groups represented below. The positions of -O- or CO- in the groups represented below may each be replaced by -S- or -SO 2 -. The bonding site can be at any position. TIFF0007691872000011.tif47158 Examples of the aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, a phenanthrylene group, and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. -CH contained in the hydrocarbon group2 - is replaced by -O-, -S-, -CO- or -SO 2 When replaced, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more. Examples of the hydrocarbon group formed by combining two or more types include a group formed by combining an alkanediyl group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group. In the combination, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. For example, -alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-alicyclic hydrocarbon group-, -alkanediyl group-alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkanediyl group-, etc. Any of these groups may be bonded to an oxygen atom.

[0013] L 2 Examples of the substituent of the hydrocarbon group of L include a halogen atom, a cyano group, a hydroxy group, a carboxy group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc.; examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, a butyryl group, etc.; and examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. L 2 The hydrocarbon group in 2 may have one substituent or a plurality of substituents.

[0014] L 2 L is a single bond, an alkanediyl group having 1 to 6 carbon atoms (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group combining an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH 2 - in the alkanediyl group and the alicyclic hydrocarbon group may be replaced by -O- or -CO-). Preferably, it is an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms, still more preferably a methylene group.

[0015] It is preferable that s1 is 1, it is preferable that t1 is 1, and it is preferable that the sum of s1 and t1 is 2. The group represented by formula (IC) is preferably a group represented by the following. TIFF0007691872000012.tif2395

[0016] In the group represented by formula (IC), when u1 is 1 and R A is a group bonded to the carbon atom adjacent to L 2 , it is represented by the following formula. TIFF0007691872000013.tif3144R AExamples of the saturated hydrocarbon group include chain saturated hydrocarbon groups such as alkyl groups, alicyclic saturated hydrocarbon groups, and groups formed by combining two or more of these. R A Examples of the alkyl group of A include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. The alicyclic saturated hydrocarbon group may be monocyclic, polycyclic, or spirocyclic. Examples of the alicyclic saturated hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc., and polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, etc. The combined group may be a group formed by combining one alkyl group and one alicyclic saturated hydrocarbon group as described above, or a group formed by combining two or more of either or both. R 1 R 2 and R 3 are preferably -O-CO-R 10 -O-CO-O-R 10 -O-L 1 -CO-O-R 10 and more preferably -O-CO-O-R 10 or -O-L 1 -CO-O-R 10 R 1 R 2 and R 3 The bonding positions of are each preferably ortho, meta, or para to the bonding positions of X 1 X 2 and X 3 Among them, it is preferably bonded at the para position to the bonding positions of X 1 X 2 and X 3

[0017] R 4 R​​5 , R 6 , R 7 , R 8 and R 9 Examples of the halogen atoms of R, R, R, and R include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 The C1-C12 fluoroalkyl group of R, R, R, R, R, R, and R represents an alkyl group having 1 to 12 carbon atoms with a fluorine atom, and examples thereof include a C1-C12 perfluoroalkyl group (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms of the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the C1-C18 hydrocarbon group of R, R, R, R, R, R, and R include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. The number of carbon atoms 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. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples thereof include the groups represented below. The bonding site can be at any position. Specifically, examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the like. 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. TIFF0007691872000014.tif44168Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group - alkane diyl 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 - alkane diyl 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 the bonding site. Examples of the aromatic hydrocarbon group - alkane diyl 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 and the like. Examples of the alicyclic hydrocarbon group - alkane diyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl and the like. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include a phenylcyclohexyl group. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include a cyclohexylphenyl group. In addition, in the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined with each other. Further, -CH 2 - in the cyclic hydrocarbon group and the chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO- or -SO 2 -. Any of the combined groups may be bonded to the benzene ring. -CH 2 - in the hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO 2 - Examples of the group in which - is replaced include a hydroxy group (a group in which -CH 2 - in the methyl group is replaced with -O-), a carboxy group (a group in which -CH 2 -CH 2 - in the ethyl group is replaced with -O-CO-), a thiol group (a group in which -CH 2 - in the methyl group is replaced with -S-), an alkoxy group (a group in which -CH 2 - at any position in the alkyl group is replaced with -O-), an alkylthio group (a group in which -CH 2 - at any position in the alkyl group is replaced with -S-), an alkoxycarbonyl group (a group in which -CH 2 -CH 2 - at any position in the alkyl group is replaced with -O-CO-), an alkylsulfonyl group (a group in which -CH 2 - at any position in the alkyl group is replaced with -SO 2 -), and an alkylcarbonyl group (a group in which -CH 2- is a group replaced by -CO-, an alkyloxycarbonyloxy group (any -CH at any position contained in the alkyl group) 2 -CH 2 - is a group replaced by -CO-O-, a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group -carbonyloxy group, a group formed by combining two or more of these groups, etc. Examples of the alkoxy group include an alkoxy group having 1 to 17 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, etc. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as cyclohexyloxy group and the like. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as cyclohexylmethoxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include aromatic hydrocarbon group-carbonyl-oxy groups having 7 to 17 carbon atoms, such as benzoyloxy group and the like. In addition, -CH 2 - contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO 2Examples of the group replaced by - include the groups represented below. The positions of -O- or -CO- in the groups represented below may each be replaced by -S- or -SO 2 - and may be at any position of the bonding site. TIFF0007691872000015.tif47158 In the hydrocarbon group, -CH 2 - is replaced by -O-, -CO-, -S or -SO 2 - when replaced, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the hydrocarbon group. Also, the number may be one or two or more. R 4 、R 5 、R 6 、R 7 、R 8 and R 9 The substituents that the hydrocarbon groups of R 2 、R 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. As the substituent, -CH 2 - in the alkyl group is replaced by -O- or -CO-, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the alkyl group. Examples of the replaced group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, etc. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group include the same groups as those described above. The hydrocarbon group may have one substituent or a plurality of substituents.

[0018] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X3 is preferably an oxygen atom. X 1 X 2 and X 3 The bonding positions of + may be any of the ortho, meta, and para positions with respect to the bonding position of S + . Among them, it is preferably bonded to the para or meta position with respect to the bonding position of S , and more preferably bonded to the para position. m1 is preferably 0, 1, or 2, and more preferably 1. m2 is preferably 0 or 1. m3 is preferably 0 or 1. When m1 is 0, it is preferable that both m2 and m3 are 1. m4 is preferably 0, 1, 2, or 4, and more preferably 0. When m4 is 1 or 2, the bonding position of at least one R 4 is preferably bonded to the ortho position with respect to the bonding position of X 1 . When m4 is 2, the bonding position of one R 4 is bonded to the ortho position with respect to the bonding position of X 1 , and the bonding position of the other R 4 is preferably bonded to the meta position with respect to the bonding position of X 1 . m5 is preferably 0 or 1, and more preferably 0. When m5 is 1 or 2, the bonding position of at least one R 5 is preferably bonded to the ortho position with respect to the bonding position of X 2 . When m5 is 2, the bonding position of one R 5 is bonded to the ortho position with respect to the bonding position of X 2 , and the bonding position of the other R 5 is preferably bonded to the meta position with respect to the bonding position of X 2 . m6 is preferably 0 or 1, and more preferably 0. When m6 is 1 or 2, the bonding position of at least one R 6 is preferably bonded to the ortho position with respect to the bonding position of X 3It is preferably bonded to the ortho position with respect to the bonding position of 6 , and when m6 is 2, the bonding position of one R 3 is preferably bonded to the ortho position with respect to the bonding position of X 6 , and the bonding position of the other R 3 is preferably bonded to the meta position with respect to the bonding position of X m7 is preferably 0, 1 or 2, and more preferably 0. m8 is preferably 0 or 1, and more preferably 0. m9 is preferably 0 or 1, and more preferably 0. In addition, when m1 + m2 + m3 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. That is, when there are a plurality of X 1 ~X 3 , and when there are a plurality of R 1 ~R 3 , and when there are a plurality of R 4 ~R 6 , these may all be the same as or different from each other. R 4 , R 5 and R 6 are each independently a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (the -CH 2 - contained in the alkyl group may be replaced by -O- or -CO-).), and more preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms (the -CH 2 - contained in the alkyl group may be replaced by -O- or -CO-).), and even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group or an alkyl group having 1 to 4 carbon atoms. R 7 , R 8 and R 9 are each independently a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (the -CH 2- may be replaced by -O- or -CO). It is preferably a halogen atom, a C1-C4 fluoroalkyl group or a C1-C4 alkyl group (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO). It is more preferably a fluorine atom, an iodine atom, a C1-C4 perfluoroalkyl group or a C1-C4 alkyl group (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO). It is even more preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxy group or a methoxy group. R 7 、R 8 and R 9 The bonding positions of are not particularly limited. When m2 is 0, the bonding position of R 8 may be at the ortho, meta or para position with respect to the bonding position of S + , and among them, it is more preferably bonded to the para position with respect to the bonding position of S + . When m3 is 0, the bonding position of R 9 may be at the ortho, meta or para position with respect to the bonding position of S + , and among them, it is more preferably bonded to the para position with respect to the bonding position of S + . X 4 is preferably a single bond, -CH 2 -, -O-, -CO-, more preferably a single bond, -CH 2 -, and even more preferably a single bond.

[0019] Examples of the cation of salt (I) include cations represented by the following formulas (I-c-1) to (I-c-46). TIFF0007691872000016.tif241144

[0020] TIFF0007691872000017.tif249150

[0021] JPEG0007691872000018.jpg182160

[0022] TIFF0007691872000019.tif238163

[0023] TIFF0007691872000020.tif130139

[0024] In formula (I), X 0 Examples of the hydrocarbon group represented by include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these. The -CH 2 - contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO 2 -. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group. 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, nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, nonynyl group, etc. Examples of the group in which -CH 2 - contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO 2 - include a hydroxy group (a group in which -CH 2 - contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH 2 -CH 2- is a group replaced by -O-CO-), a thiol group (-CH contained in the methyl group) 2 - is a group replaced by -S-), an alkoxy group (-CH at any position contained in the alkyl group) 2 - is a group replaced by -O-), an alkylthio group (-CH at any position contained in the alkyl group) 2 - is a group replaced by -S-), an alkoxycarbonyl group (-CH at any position contained in the alkyl group) 2 -CH 2 - is a group replaced by -O-CO-), an alkylcarbonyl group (-CH at any position contained in the alkyl group) 2 - is a group replaced by -CO-), an alkylsulfonyl group (-CH at any position contained in the alkyl group) 2 - is a group replaced by -SO 2 -), an alkylcarbonyloxy group (-CH at any position contained in the alkyl group) 2 -CH 2 - is a group replaced by -CO-O-), an alkylthio group (-CH at any position contained in the alkyl group) 2 - is a group replaced by -S-), etc. may be mentioned. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, and alkylthio group include the same groups as described above. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, etc. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. In addition, the replacement in the alkenyl group and alkynyl group may be any one 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 either saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc., and polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, etc. The alicyclic hydrocarbon group and -CH contained in the alicyclic hydrocarbon group 2 - being replaced by -O-, -S-, -CO- or -SO 2 Specific examples of the group in which - is replaced by -O-, -S-, -CO- or -SO- include the following groups, etc. The bonding site can be at any position.

[0025] TIFF0007691872000021.tif116159 The alicyclic hydrocarbon group or -CH contained in the alicyclic hydrocarbon group 2 - being replaced by -O-, -S-, -CO- or -SO 2 As the group in which - is replaced by -O-, -S-, -CO- or -SO-, the groups represented by the formulas (y1) to (y71) are preferable, the groups represented by any one of the formulas (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), 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), formulas (y49) to (y58), formulas (y62) to (y71) are even more preferable. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16.

[0026] 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, even more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, groups with different valences in the above-mentioned groups (alkanediyl group, alkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) may be included.

[0027] The combined group means a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH 2 - in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), a group formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), and a group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -). In the combination, the alicyclic hydrocarbon group, the chain hydrocarbon group and the aromatic hydrocarbon group may each be combined with two or more kinds. Specifically, examples of the combined group include an alicyclic hydrocarbon group-chain hydrocarbon group-* such as an adamantylmethylene group or a cyclohexylmethylene group, (alicyclic hydrocarbon group) 2 -chain hydrocarbon group-* (wherein -CH 2 - in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), a chain hydrocarbon group-alicyclic hydrocarbon group-* such as a methyladamantyl group or a dimethyladamantyl group, (chain hydrocarbon group) 2 -alicyclic hydrocarbon group-* (wherein -CH 2 - in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -). Chain hydrocarbon group - aromatic hydrocarbon group such as trityl group and xylyl group - *( -CH contained in the chain hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). Chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group such as methylcyclohexylmethylene group - *(chain hydrocarbon group) 2 - alicyclic hydrocarbon group - chain hydrocarbon group - *(chain hydrocarbon group - alicyclic hydrocarbon group) 2 - chain hydrocarbon group - *( -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). Aromatic hydrocarbon group - chain hydrocarbon group such as benzyl group - *( -CH contained in the chain hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). Chain hydrocarbon group - aromatic hydrocarbon group - chain hydrocarbon group such as tolylmethyl group - *( -CH contained in the chain hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). Chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group such as methyladamantylmethyleneadamantyl group and di(methyladamantylmethylene)adamantyl group - *(chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group) 2 - alicyclic hydrocarbon group - *(chain hydrocarbon group - alicyclic hydrocarbon group) 2 - chain hydrocarbon group - alicyclic hydrocarbon group - *(chain hydrocarbon group) 2 - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - *( -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -). 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 -*(the -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group) 2 -is optionally replaced by -O-, -S-, -CO- or -SO 2 -) 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 -*(the -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group) 2 -is optionally replaced by -O-, -S-, -CO- or -SO 2 -) etc. are exemplified. Here, * represents the bonding position with the carbon atom of the carbonyl group.

[0028] X 0 In the hydrocarbon group represented by, the -CH 2 -is optionally replaced by -O-, -S-, -CO- or -SO 2 -When replaced, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the hydrocarbon group. Also, X 0 When a substituent is bonded to the hydrocarbon group represented by, the number of carbon atoms before substitution is taken as the total number of carbon atoms of the hydrocarbon group. X 0 The hydrocarbon group represented by may have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group formed by combining these groups. 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, and a butoxycarbonyl group. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents the bonding position with X 0 represents the bonding position with X. TIFF0007691872000022.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 group include a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the like. Examples of the group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 12 carbon atoms such as hydroxymethyl group and hydroxyethyl group. Examples of the group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as benzyl group, and alkylaryl groups having 7 to 22 carbon atoms such as tolyl group and xylyl group. Examples of the group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include cyclohexylphenyl group.

[0029] X 0 The hydrocarbon group represented by [X] is preferably an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (wherein -CH 2 - in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. More preferably, it is an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and -CH 2- 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 halogen atom, a hydroxy group or a C1-C4 perfluoroalkyl group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, *- an alicyclic hydrocarbon group (the -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents the bonding position to the carbon atom of -COO - ), *- an alicyclic hydrocarbon group-chain hydrocarbon group (the -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the -CH 2 - 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 to the carbon atom of -COO - ), *- a chain hydrocarbon group-alicyclic hydrocarbon group (the -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-, and the -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position to the carbon atom of -COO - ), 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, *- a polycyclic alicyclic hydrocarbon group (the -CH 2 - in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents -COO- represents the bonding position with the carbon atom of). *-polycyclic alicyclic hydrocarbon group - chain hydrocarbon group (the -CH contained in the polycyclic alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - and the -CH contained in the chain hydrocarbon group may be replaced by -O- or -CO-. The polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO 2 represents the bonding position with the carbon atom of). *-chain hydrocarbon group - polycyclic alicyclic hydrocarbon group (the -CH contained in the chain hydrocarbon group - - may be replaced by -O- or -CO-, and the -CH contained in the polycyclic alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO 2 represents the bonding position with the carbon atom of).), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, a group represented by the formula (aa) or a group represented by the formula (bb), - and particularly preferably, an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (the -CH contained in the alkyl group - may be replaced by -O- or -CO-.), a group represented by the formula (Y30F) or a phenyl group having a hydroxy group. 2 ​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. TIFF0007691872000023.tif26132[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. * represents the bonding position with the carbon atom of -COO - .] [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom, or an aromatic hydrocarbon group having 6 carbon atoms which may have a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH 2 - in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO 2 -. R Arepresents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -. * represents the bonding position with the carbon atom of -COO - .

[0030] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0031] 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 a substituent. Also, -CH 2 - in these hydrocarbon groups may be replaced by -O-, -S-, -CO- or -SO 2 -. Here, the number of carbon atoms of the hydrocarbon group means the number of carbon atoms of the hydrocarbon group without a substituent and without replacement.

[0032] X 1a Examples of the aliphatic hydrocarbon group of include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group formed by combining these. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, a butanetriyl group, a pentanetriyl group, a hexanetriyl group, a heptanetriyl group, an octanetriyl group, a nonanetriyl group, a decanetriyl group, an undecanetriyl group, a dodecanetriyl group, and the like.

[0033] 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 norbornanetril group, an adamantanetril group, and the like. Examples of the aromatic hydrocarbon group include a benzenetricarbonyl group, a naphthalenetricarbonyl group, an anthracenetril group, and the like. In the case of the combined group, groups having different valences in the above-mentioned groups (such as an alkyl group, an alkanediyl group, an alkanetetrayl group, a cycloalkyl group, a cycloalkanediyl group, a cycloalkanetetrayl group, etc.) may be included.

[0034] X 1a The hydrocarbon group represented by [X] has 1 to 24 carbon atoms and may further have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group 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.

[0035] X 1a The hydrocarbon group represented by [X] is preferably an alkanetriyl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alkanetriyl group having 1 to 6 carbon atoms or a group represented by formula (w1-1) to formula (w1-11), and even 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). TIFF0007691872000024.tif53144 [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 groups. * represents a bonding position.]

[0036] X 2a The hydrocarbon group represented by is preferably 2 to 48 carbon atoms, more preferably 4 to 48 carbon atoms, still more preferably 6 to 44 carbon atoms, even more preferably 8 to 40 carbon atoms, and even more preferably 10 to 38 carbon atoms.

[0037] 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 groups. 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 groups include the same groups as described above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by may have one substituent or a plurality of substituents.

[0038] 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 a combination of two or more of these groups may also be used. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic alicyclic hydrocarbon groups which are monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic alicyclic hydrocarbon groups which are polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group; Aromatic hydrocarbon groups such as phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group, binaphthylene group, etc. can be mentioned. In the case of a combined group, groups with different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) may be included in the above-mentioned groups. Examples of the combined group include a group combining a chain hydrocarbon group and an alicyclic hydrocarbon group, a group combining a chain hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, a group in which one or more alicyclic hydrocarbon groups are bonded to a chain hydrocarbon group (for example, -chain hydrocarbon group-alicyclic hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group) 2 etc.), a group in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (for example, -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group) 2groups such as), a group in which one or more alicyclic hydrocarbon groups and a chain hydrocarbon group are bonded to a chain hydrocarbon group (for example, -chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group, -chain hydrocarbon group - (alicyclic hydrocarbon group - chain hydrocarbon group) 2 and the like).

[0039] X 2a Examples of the hydrocarbon group in include a chain hydrocarbon group having 2 to 18 carbon atoms (wherein -CH 2 - may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent.), or a chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), and the group is preferably a group having a substituent.), a chain hydrocarbon group having 4 to 18 carbon atoms (wherein -CH 2 - may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), or a chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH 2 - may be replaced by -O-, -S-, -CO- or -SO 2 -), and the group is more preferably a group having a substituent.), A chain hydrocarbon group having 6 to 14 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent.), or A chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH 2 - in the chain hydrocarbon group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -). It is more preferable that the group is a combined group (the group may have a substituent).

[0040] Specifically, as the hydrocarbon group in X 2a There are An alkanediyl group having 2 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-), An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2 - may be replaced by -O- or -CO-. It is preferably a group consisting of), An alkanediyl group having 4 to 18 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-.), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-.), an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (the -CH contained in the alicyclic hydrocarbon group 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - may be replaced by -). A group consisting of, or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-.), an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO-.). It is more preferably a group consisting of, An alkanediyl group having 6 to 14 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-.), An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-.), an adamantanediyl group having a substituent (the -CH contained in the adamantanediyl group 2 - may be replaced by -O- or -CO-.). A group consisting of, or An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (the -CH contained in the alkanediyl group 2- may be replaced by -O- or -CO-. An adamantandiyl group which may have a substituent and an alkyl group having 1 to 12 carbon atoms which may have a substituent (the -CH 2 - may be replaced by -O- or -CO-. It is more preferably a group consisting of).

[0041] Specifically, X 2a is a group represented by the formula (X 2 -1), a group represented by the formula (X 2 -2), a group represented by the formula (X 2 -3) or a group represented by the formula (X 2 -4). TIFF0007691872000025.tif34159 [wherein, 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, and the -CH 2 - in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -, 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 any one or both of them. In this case, the carbon number of the combined group is 39 or less, preferably 37 or less.

[0042] Among them, R 1x 、R 2x 、R 3x 、R 4x 、R 5x and R 6x are each an alkyl group having 1 to 6 carbon atoms (the -CH contained in the alkyl group2 - 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 (the -CH contained in the alicyclic hydrocarbon group 2 - may be -O-, -S-, -CO- or -SO 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - may be replaced by -O- or -CO-), and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (the -CH contained in the alicyclic hydrocarbon group 2 - may be -O-, -S-, -CO- or -SO 2 - may be replaced by -O-, -S-, -CO- or -SO 2 - may be replaced by -O- or -CO-, and the adamantyl group may have a substituent.), or an alkyl group having 1 to 6 carbon atoms (the -CH contained in the alkyl group 2 - may be replaced by -O- or -CO-), and a group combined with an adamantyl group (the group may have a substituent.) is more preferable.

[0043] In formula (bb), L A and L B Examples of the alkanediyl group having 1 to 6 carbon atoms include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group; branched alkanediyl groups such as propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. 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 the -CH 2 - in the alkanediyl group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the alkanediyl group. The alkanediyl group may have a hydroxy group (a group in which -CH 2 - in a methyl group is replaced by -O-), a carboxy group (a group in which -CH 2 -CH 2 - in an ethyl group is replaced by -O-CO-), an alkoxy group (a group in which -CH 2 - at any position in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH 2 -CH 2 - at any position in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH 2 - at any position in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH 2 -CH 2 - at any position in an alkyl group is replaced by -CO-O-), an alkanediyl-oxy group (a group in which -CH 2 - at any position in an alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which -CH 2 -CH 2 - at any position in an alkanediyl group is replaced by -O-CO-), an alkanediyl-carbonyl group (a group in which -CH 2 - at any position in an alkanediyl group is replaced by -CO-), or an alkanediyl-carbonyloxy group (a group in which -CH 2 -CH 2 - at any position in an alkanediyl group is replaced by -CO-O-). Examples of the alkanediyl group include a methyleneoxy group, an ethyleneoxy group, a propanediyl-oxy group, a butanediyl-oxy group, a pentanediyl-oxy group, and the like. Examples of the alkanediylcarbonyl group include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanediyl-oxycarbonyl group, a butanediyl-oxycarbonyl group, and the like. 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 -CH 2 - may be replaced by -O- or -CO-), and more preferably a single bond, a methylene group or an ethylene group.

[0044] R A Examples of the hydrocarbon group in include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group, and an alicyclic hydrocarbon group), an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, nonynyl group and the like. -CH 2 - in the chain hydrocarbon group replaced by -O-, -S-, -CO- or -SO 2 - Examples of the group include hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylthio group, alkylsulfonyl group and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyl group and alkylthio group include an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, an alkylsulfonyl group having 1 to 17 carbon atoms and an alkylthio group having 1 to 17 carbon atoms, and the same groups as those described above. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl 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. The alicyclic hydrocarbon group and -CH 2 - in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO 2 - Examples of the resulting group specifically include the groups represented by the above formulas (y1) to (y71) and the like. 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. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms 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.

[0045] In the case of a combined group, groups with different valences (such as alkane diyl group, alkane triyl group, cycloalkane diyl group, cycloalkane triyl group, etc.) in the above-mentioned groups may be included. Examples of the group formed by combination include a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group - alkane diyl group - *, alkyl group - aromatic hydrocarbon group - *), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group - alkane diyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents a bonding site. Examples of the aromatic hydrocarbon group - alkane diyl 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 - alkane diyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl, etc. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group, etc. 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, two or more kinds of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. Also, any group may be bonded to L B Examples of the group in which -CH 2 - contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO 2 - include, in addition to the groups described above, cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, aromatic hydrocarbon group - carbonyloxy groups, and groups combining two or more of these groups.​ 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. -CH 2 - in the hydrocarbon group is replaced by -O-, -S-, -SO 2 - 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.

[0046] R A Examples of the substituent that the hydrocarbon group of R may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (where -CH 2 - in the alkyl group may be replaced by -O-, -S-, -CO- or -SO 2 -). 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. -CH 2 - in the alkyl group replaced by -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, etc. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, and alkylcarbonyloxy group include an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyloxy group having 2 to 11 carbon atoms, such as the same groups as those described above. R A The hydrocarbon group in may have one substituent or a plurality of substituents.

[0047] R A Examples of the hydrocarbon group in R include an alkyl group having 1 to 12 carbon atoms which may have a substituent (provided that -CH 2 - in the alkyl group may be replaced by -O-, -S-, -CO- or -SO 2 -), or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH 2 - in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), and 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 (provided that -CH 2 - in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -).

[0048] Examples of the cyclic hydrocarbon group include cyclic hydrocarbon groups such as monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups obtained by combining these. Examples of the alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as those described above. In the combination, two or more alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be combined respectively. Also, any of the groups may be bonded to L B .

[0049] The cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms, and -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -) is An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (the -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2 -), or It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (the -CH 2 - in the alicyclic hydrocarbon group may be replaced by -O- or -CO-). As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, the following group (the bonding site is at an arbitrary position) is preferable, and as the aromatic hydrocarbon group, a phenyl group and a naphthyl group are preferable. TIFF0007691872000026.tif1797

[0050] Examples of the carboxylate anion in the carboxylate represented by the formula (I) include the carboxylate anions described below. TIFF0007691872000027.tif100162

[0051] TIFF0007691872000028.tif154164

[0052] TIFF0007691872000029.tif72150

[0053] TIFF0007691872000030.tif175164

[0054] TIFF0007691872000031.tif50164

[0055] TIFF0007691872000032.tif190161

[0056] Specific examples of the carboxylate (I) include salts obtained by arbitrarily combining the above-mentioned cations and anions. Specific examples of the salt (I) 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, and "~" indicates that each of the carboxylate (I) and the anion (I) corresponds. For example, the carboxylate (I-1) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-1), the carboxylate (I-2) is a salt composed of the anion represented by the formula (I-a-2) and the cation represented by the formula (I-c-1), and the carboxylate (I-96) is a salt composed of the anion represented by the formula (I-a-1) and the cation represented by the formula (I-c-2). TIFF0007691872000033.tif5773 [Table 1] JPEG0007691872000035.jpg145153

[0057] Among them, as the carboxylate (I), a salt combining an anion represented by any one of the formulas (I-a-1) to (I-a-5), (I-a-10) to (I-a-21), and (I-a-57) to (I-a-66) with a cation represented by any one of the formulas (I-c-1) to (I-c-46) is preferable. Specifically, carboxylates (I-1) to (I-5), carboxylates (I-10) to (I-21), carboxylates (I-57) to (I-66), carboxylates (I-96) to (I-100), carboxylates (I-105) to (I-116), carboxylates (I-152) to (I-161), carboxylates (I-191) to (I-195), carboxylates (I-200) to (I-211), carboxylates (I-247) to (I-256), carboxylates (I-286) to (I-290), carboxylates (I-295) to (I-306), carboxylates (I-342) to (I-351), carboxylates (I-381) to (I-385), carboxylates (I-390) to (I-401), carboxylates (I-437) to (I-446), carboxylates (I-476) to (I-480), carboxylates (I-485) to (I-496), carboxylates (I-532) to (I-541), carboxylates (I-571) to (I-575), carboxylates (I-580) to (I-591), carboxylates (I-627) to (I-636), carboxylates (I-666) to (I-670), carboxylates (I-675) to (I-686), carboxylates (I-722) to (I-731), carboxylates (I-761) to (I-765), carboxylates (I-770) to (I-781), carboxylates (I-817) to (I-826), carboxylates (I-856) to (I-860), carboxylates (I-865) to (I-876), carboxylates (I-912) to (I-921).Carboxylates (I-951) to (I-955), carboxylates (I-960) to (I-971), carboxylates (I-1007) to (I-1016), carboxylates (I-1046) to (I-1050), carboxylates (I-1055) to (I-1066), carboxylates (I-1102) to (I-1111), carboxylates (I-1141) to (I-1145), carboxylates (I-1150) to (I-1161), carboxylates (I-1197) to (I-1206), carboxylates (I-1236) to (I-1240), carboxylates (I-1245) to (I-1256), carboxylates (I-1292) to (I-1301), carboxylates (I-1331) to (I-1335), carboxylates (I-1340) to (I-1351), carboxylates (I-1387) to (I-1396), carboxylates (I-1426) to (I-1430), carboxylates (I-1435) to (I-1446), carboxylates (I-1482) to (I-1491), carboxylates (I-1521) to (I-1525), carboxylates (I-1530) to (I-1541), carboxylates (I-1577) to (I-1586), carboxylates (I-1616) to (I-1620), carboxylates (I-1625) to (I-1636), carboxylates (I-1672) to (I-1681), carboxylates (I-1711) to (I-1715), carboxylates (I-1720) to (I-1731), carboxylates (I-1767) to (I-1776), carboxylates (I-1806) to (I-1810), carboxylates (I-1815) to (I-1826), carboxylates (I-1862) to (I-1871), carboxylates (I-1901) to (I-1905), carboxylates (I-1910) to (I-1921), carboxylates (I-1957) to (I-1966)Carboxylates (I-1996) to Carboxylates (I-2000), Carboxylates (I-2005) to Carboxylates (I-2016), Carboxylates (I-2052) to Carboxylates (I-2061), Carboxylates (I-2091) to Carboxylates (I-2095), Carboxylates (I-2100) to Carboxylates (I-2111), Carboxylates (I-2147) to Carboxylates (I-2156), Carboxylates (I-2186) to Carboxylates (I-2190), Carboxylates (I-2195) to Carboxylates (I-2206), Carboxylates (I-2242) to Carboxylates (I-2251), Carboxylates (I-2281) to Carboxylates (I-2285), Carboxylates (I-2290) to Carboxylates (I-2301), Carboxylates (I-2337) to Carboxylates (I-2346), Carboxylates (I-2376) to Carboxylates (I-2380), Carboxylates (I-2385) to Carboxylates (I-2396), Carboxylates (I-2432) to Carboxylates (I-2441), Carboxylates (I-2471) to Carboxylates (I-2475), Carboxylates (I-2480) to Carboxylates (I-2491), Carboxylates (I-2527) to Carboxylates (I-2536), Carboxylates (I-2566) to Carboxylates (I-2570), Carboxylates (I-2575) to Carboxylates (I-2586), Carboxylates (I-2622) to Carboxylates (I-2631), Carboxylates (I-2661) to Carboxylates (I-2665), Carboxylates (I-2670) to Carboxylates (I-2681), Carboxylates (I-2717) to Carboxylates (I-2726), Carboxylates (I-2756) to Carboxylates (I-2760), Carboxylates (I-2765) to Carboxylates (I-2776), Carboxylates (I-2812) to Carboxylates (I-2821), Carboxylates (I-2851) to Carboxylates (I-2855), Carboxylates (I-2860) to Carboxylates (I-2871), Carboxylates (I-2907) to Carboxylates (I-2916), Carboxylates (I-2946) to Carboxylates (I-2950), Carboxylates (I-2955) to Carboxylates (I-2966), Carboxylates (I-3002) to Carboxylates (I-3011)Carboxylates (I-3041) to Carboxylates (I-3045), Carboxylates (I-3050) to Carboxylates (I-3061), Carboxylates (I-3097) to Carboxylates (I-3106), Carboxylates (I-3136) to Carboxylates (I-3140), Carboxylates (I-3145) to Carboxylates (I-3156), Carboxylates (I-3192) to Carboxylates (I-3201), Carboxylates (I-3231) to Carboxylates (I-3235), Carboxylates (I-3240) to Carboxylates (I-3251), Carboxylates (I-3287) to Carboxylates (I-3296), Carboxylates (I-3326) to Carboxylates (I-3330), Carboxylates (I-3335) to Carboxylates (I-3346), Carboxylates (I-3382) to Carboxylates (I-3391), Carboxylates (I-3421) to Carboxylates (I-3425), Carboxylates (I-3430) to Carboxylates (I-3441), Carboxylates (I-3477) to Carboxylates (I-3486), Carboxylates (I-3516) to Carboxylates (I-3520), Carboxylates (I-3525) to Carboxylates (I-3536), Carboxylates (I-3572) to Carboxylates (I-3581), Carboxylates (I-3611) to Carboxylates (I-3615), Carboxylates (I-3620) to Carboxylates (I-3631), Carboxylates (I-3667) to Carboxylates (I-3676), Carboxylates (I-3706) to Carboxylates (I-3710), Carboxylates (I-3715) to Carboxylates (I-3726), Carboxylates (I-3762) to Carboxylates (I-3771), Carboxylates (I-3801) to Carboxylates (I-3805), Carboxylates (I-3810) to Carboxylates (I-3821), Carboxylates (I-3857) to Carboxylates (I-3866), Carboxylates (I-3896) to Carboxylates (I-3900), Carboxylates (I-3905) to Carboxylates (I-3916), Carboxylates (I-3952) to Carboxylates (I-3961), Carboxylates (I-3991) to Carboxylates (I-3995), Carboxylates (I-4000) to Carboxylates (I-4011), Carboxylates (I-4047) to Carboxylates (I-4056)Carboxylates (I-4086) to carboxylates (I-4090), carboxylates (I-4095) to carboxylates (I-4106), carboxylates (I-4142) to carboxylates (I-4151), carboxylates (I-4181) to carboxylates (I-4185), carboxylates (I-4190) to carboxylates (I-4201), carboxylates (I-4237) to carboxylates (I-4246), carboxylates (I-4276) to carboxylates (I-4280), carboxylates (I-4285) to carboxylates (I-4296), carboxylates (I-4332) to carboxylates (I-4341) are preferred.

[0058] <Method for producing salt (I)> Salt (I) can be produced by reacting a salt represented by formula (I-a) with a salt represented by formula (I-b) in a solvent. TIFF0007691872000036.tif83157 [In the formula, all symbols have the same meanings as described above. R A 、R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A 、R B and R C may together form an aromatic ring. R D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ]] Examples of the solvent in this reaction include chloroform, acetonitrile, ion-exchanged water, and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0059] The salt represented by formula (I-b) can be synthesized with reference to the methods described in JP-A-2011-39502 and JP-A-2014-88367, and examples include salts represented below. TIFF0007691872000037.tif100163

[0060] TIFF0007691872000038.tif41168

[0061] In salt (I-a), R 1 , R 2 and R 3 are -O-L 1 -CO-O-R 10 The salt represented by formula (I-a1) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d) in a solvent in the presence of a base catalyst. TIFF0007691872000039.tif78166 [In the formula, all symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is generally 15°C to 80°C, and the reaction time is generally 0.5 to 24 hours.

[0062] Examples of the compound represented by formula (I-d) include the compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007691872000040.tif15150

[0063] The salt represented by formula (I-c) can be produced by reacting the salt represented by formula (I-e) with the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) in a solvent in the presence of a catalyst. TIFF0007691872000041.tif79161 [In the formula, all symbols have the same meanings as described above.] Examples of the catalyst include potassium carbonate, sodium hydride and the like. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like. The reaction temperature is generally 15°C to 100°C, and the reaction time is generally 0.5 to 24 hours.

[0064] Examples of the salt represented by formula (I-e) include salts represented by the following formula, and they can be easily obtained from the market. TIFF0007691872000042.tif61158

[0065] Examples of the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) include compounds represented by the following, and they can be easily obtained from the market. TIFF0007691872000043.tif20105

[0066] The salt represented by formula (I-c) can also be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) in a solvent in the presence of potassium carbonate and then performing acid treatment. TIFF0007691872000044.tif134154[Wherein, all the symbols have the same meanings as described above. R ac represents an acid-labile group. ] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water, and the like. The reaction temperature is generally 15°C to 100°C, and the reaction time is generally 0.5 to 24 hours. Examples of the acid include p-toluenesulfonic acid, hydrochloric acid, and the like.

[0067] Examples of the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) include compounds represented by the following, and they can be easily obtained from the market. TIFF0007691872000045.tif79155

[0068] In salt (I-a), R 1 , R2 and R 3 is -O-CO-R 10 The salt (the salt represented by formula (I-a2)) in which is can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d2) in a solvent in the presence of a base catalyst. TIFF0007691872000046.tif77163 [In the formula, all symbols have the same meanings as described above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine, and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water, and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0069] Examples of the compound represented by formula (I-d2) include the compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007691872000047.tif1451

[0070] In salt (I-a), R 1 , R 2 and R 3 is -O-R 10 The salt (the salt represented by formula (I-a3)) in which is can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d3) in a solvent in the presence of a base catalyst. TIFF0007691872000048.tif75161 [In the formula, all symbols have the same meanings as described above.] Examples of the base include sodium hydroxide, potassium hydroxide, and the like. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water, and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0071] Examples of the compound represented by formula (I-d3) include compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007691872000049.tif14122

[0072] In salt (I-a), R 1 , R 2 and R 3 being -O-CO-O-R 10 The salt (the salt represented by formula (I-a4)) can be produced by reacting the salt represented by formula (I-c) with the compound represented by formula (I-d3) in a solvent in the presence of carbonyldiimidazole. TIFF0007691872000050.tif76161[In the formula, all the symbols have the same meanings as described above.] Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0073] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing carboxylate (I). Carboxylate (I) of the present invention can act as an acid generator in the resist composition. When carboxylate (I) is used as the acid generator in the resist composition, the acid generator may contain only one kind or two or more kinds of carboxylates (I). In addition, as described later, the acid generator of the present invention may further contain an acid generator known in the resist field other than carboxylate (I) (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator known in the resist field other than carboxylate (I). Acid generator (B) may be used alone or in combination of two or more. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the content of the carboxylate (I) to the acid generator (B) or the like (mass ratio; carboxylate (I): acid generator (B)) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and even more preferably 5:95 to 95:5.

[0074] 〔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 is eliminated 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 even more preferably 1% by mass or more and 25% by mass or less with respect to the solid content of the resist composition.

[0075] <Acid generator (B)> Either a nonionic or ionic acid generator (B) may be used. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid generators include onium salts containing an onium cation (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of the anion of the onium salt include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0076] As the acid generator (B), compounds that generate an acid upon irradiation as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more kinds.

[0077] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007691872000051.tif2962[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH 2 - contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO 2 - or -CO-. Z + represents an organic cation.]

[0078] Q b1 and Q b2Examples of the perfluoroalkyl group represented by [compound 1] include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0079] L b1 Examples of the divalent saturated hydrocarbon group in [compound 2] include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups. Specifically, linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; Branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups that are cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group; Examples thereof include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0080] L b1 Examples of the group in which -CH included in the divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO- include, for example, 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.

[0081] TIFF0007691872000052.tif26117 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH included in the saturated hydrocarbon group 2 - may be replaced by -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 a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH included in the saturated hydrocarbon group 2 - may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms of and 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms of and is 23 or less.]

[0082] In the groups represented by formula (b1-1) to formula (b1-3), when -CH 2 - contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same ones as the divalent saturated hydrocarbon group of L b1 .

[0083] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH 2 - in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-.

[0084] L b1 In the divalent saturated hydrocarbon group represented by, -CH 2 - replaced by -O- or -CO- is preferably a group represented by formula (b1-1) or formula (b1-3).

[0085] Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8). TIFF0007691872000053.tif48120 [In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH 2 - 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, L b9 and L b10 have a total carbon number of 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, L b11 and L b12 have a total carbon number of 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 -CH 2 - 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, L b13 to L b15 have a total carbon number of 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. However, L b16 to L b18 have a total carbon number of 19 or less.

[0086] 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 b11is 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.

[0087] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11). TIFF0007691872000054.tif23140[In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and 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. The -CH 2 - in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b19 and L b20The total carbon number is 23 or less. 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. -CH 2 - 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 carbon number of L b21 , L b22 and L b23 is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH 2 - 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 carbon number of L b24 , L b25 and L b26 is 21 or less.

[0088] In the case where a hydrogen atom contained in a saturated hydrocarbon group is substituted with an alkylcarbonyloxy group in the group represented by the formula (b1-9) to the group represented by the formula (b1-11), the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group.

[0089] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group, and the like.

[0090] Examples of the group represented by the formula (b1-4) include the following. TIFF0007691872000055.tif16154

[0091] Examples of the group represented by the formula (b1-5) include the following. TIFF0007691872000056.tif68152

[0092] Examples of the group represented by the formula (b1-6) include the following. TIFF0007691872000057.tif32164

[0093] Examples of the group represented by the formula (b1-7) include the following. TIFF0007691872000058.tif57146

[0094] Examples of the group represented by the formula (b1-8) include the following. TIFF0007691872000059.tif23150

[0095] Examples of the group represented by the formula (b1-2) include the following. TIFF0007691872000060.tif31161

[0096] Examples of the group represented by the formula (b1-9) include the following. TIFF0007691872000061.tif44137

[0097] Examples of the group represented by formula (b1-10) include the following. TIFF0007691872000062.tif92165

[0098] Examples of the group represented by formula (b1-11) include the following. TIFF0007691872000063.tif84164

[0099] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). Y 1 -CH 2 - in the alicyclic hydrocarbon group represented by - being replaced by -O-, -SO 2 - or -CO- may be 1 or more than 2. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents the bonding position with L b1 and the bonding position with

[0100] TIFF0007691872000064.tif83166 Examples of the alicyclic hydrocarbon group represented by Y are preferably groups represented by any of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), more preferably groups 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 groups represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42), formula (Y43), etc., 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, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

[0101] 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, -(CH 2 ) ja -CO-O-R b1 group or -(CH 2 ) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. ja represents any integer from 0 to 4. -CH 2 - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -S(O) 2 -, or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted with a hydroxy group (wherein -CH 2 - 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, -(CH 2 ) ja -CO-O-R b1 group or -(CH 2 ) ja -O-CO-R b1 group (wherein R b1represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. ja represents any integer from 0 to 4. -CH contained in the alkyl group and the alicyclic hydrocarbon group 2 - may be replaced by -O-, -SO 2 -, or -CO-, and the hydrogen atoms 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. ) etc. are mentioned.

[0102] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom etc. 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 etc. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group, a dimethylcyclohexyl group etc. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples include an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-methylphenyl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group having 3 to 18 carbon atoms (a p-cyclohexylphenyl group, a p-adamantylphenyl group etc.). The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and the like. The number of carbon atoms in 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 a hydroxymethyl group and a hydroxyethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. -CH 2 - in the alkyl group replaced with -O-, -SO 2 - or -CO- and the like include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a group combining these. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, 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 obtained by combining an alkoxy group and an alkyl group, a group obtained by combining an alkoxy group and an alkoxy group, a group obtained by combining an alkoxy group and an alkylcarbonyl group, a group obtained by combining an alkoxy group and an alkylcarbonyloxy group, and the like. Examples of the group obtained 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 obtained 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 obtained 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 a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. -CH contained in the alicyclic hydrocarbon group 2 - is replaced by -O-, -SO 2 - or -CO- and the like include groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43), and the like.

[0103] Examples of Y include the following. TIFF0007691872000065.tif103165

[0104] TIFF0007691872000066.tif66163

[0105] 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, even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group substituted with a hydroxy group, and even more preferably an adamantyl group which may have a substituent. -CH 2 - is -CO-, -SO 2 - or -CO- may be replaced. 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), and particularly preferably a hydroxyadamantyl group, an oxoadamantyl group, a group containing these, or a group represented by formula (Y42), formula (Y100) to formula (Y114).

[0106] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and an anion represented by any one of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), and formula (B1-A-47) to formula (B1-A-59) is more preferable.

[0107] JPEG0007691872000067.jpg75158

[0108] JPEG0007691872000068.jpg115162

[0109] TIFF0007691872000069.tif125157

[0110] TIFF0007691872000070.tif129140

[0111] TIFF0007691872000071.tif111158

[0112] TIFF0007691872000072.tif67139

[0113] Here, R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as described above. Examples of the anion represented by formula (B1-A) include specifically the anions described in JP-A-2010-204646.

[0114] Examples of the anion in the preferably salt represented by formula (B1) include the anions represented by formula (B1a-1) to formula (B1a-38), respectively. TIFF0007691872000073.tif89152

[0115] TIFF0007691872000074.tif94139

[0116] TIFF0007691872000075.tif142156

[0117] TIFF0007691872000076.tif63150

[0118] Among them, an anion represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-19), and formula (B1a-22) to formula (B1a-38) is preferable.

[0119] Z1 + Examples of the organic cation of include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations, etc. 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) are included. TIFF0007691872000077.tif48169In formula (b2-1) to formula (b2-4), R b4 ~R b6Each independently represents an aliphatic 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 atoms contained in the aliphatic 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. The hydrogen atoms 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. The hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH 2 - in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent 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 an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH 2 - in the ring may be replaced with -O-, -S-, or -CO-. R b11represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a hydrogen atom contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 and may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH 2 - may be replaced with -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, a plurality of R b13 are the same or different, when p2 is 2 or more, a plurality of R b14 are the same or different, when q2 is 2 or more, a plurality of R b15 are the same or different, when r2 is 2 or more, a plurality of R b16 are the same or different, when s2 is 2 or more, a plurality of R b17 are the same or different, when t2 is 2 or more, a 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, R b9 ~R b12 The chain hydrocarbon group is preferably a C1-C12 group. 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. TIFF0007691872000078.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group is preferably a C3-C18 group, more preferably a C4-C12 group. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorbornyl group, and isobornyl group. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, and perfluorobutyl. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include an aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-cyclohexylphenyl group, p-adamantylphenyl group, etc.). When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group with 1 to 18 carbon atoms and an alicyclic hydrocarbon group with 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group, etc. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group, etc. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, etc. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group, etc. R b4 and R b5The ring formed by the combination of them together with the sulfur atom to which they are attached may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings, and examples thereof include the following rings. * represents the bonding position. TIFF0007691872000079.tif23144R b9 and R b10 The ring formed by the combination of them together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Examples thereof include thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring and the like. R b11 and R b12 The ring formed by the combination of them together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Examples thereof include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring and the like.

[0120] Among the cations (b2-1) to (b2-4), preferably, it is the cation (b2-1). Examples of the cation (b2-1) include the following cations. TIFF0007691872000080.tif79158

[0121] TIFF0007691872000081.tif109165

[0122] Examples of the cation (b2-2) include the following cations and the like. TIFF0007691872000082.tif18150

[0123] Examples of the cation (b2-3) include the following cations and the like. TIFF0007691872000083.tif25122

[0124] Examples of the cation (b2-4) include the following cations and the like. TIFF0007691872000084.tif127166

[0125] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, 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), the cation (b2-3) or the cation (b2-4) is mentioned.

[0126] As the acid generator (B), preferably, those represented by the formulas (B1-1) to (B1-56) are mentioned. Among them, those containing an arylsulfonium cation are preferable, 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 preferable. TIFF0007691872000085.tif98162

[0127] TIFF0007691872000086.tif152164

[0128] TIFF0007691872000087.tif92158

[0129] TIFF0007691872000088.tif131161

[0130] TIFF0007691872000089.tif98130

[0131] TIFF0007691872000090.tif92158

[0132] In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and still more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds.

[0133] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)")), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0134] 〈Structural unit (a1)〉 The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid-labile group contained in the resin (A) is preferably a group represented by the formula (1) (hereinafter also referred to as "group (1)") and / or a group represented by the formula (2) (hereinafter also referred to as "group (2)"). TIFF0007691872000091.tif2397[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding position.] TIFF0007691872000092.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 group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.]

[0135] R a1 、R a2 and R a3 Examples of the alkyl group in R 、R a1 、R a2 and R a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. R a1 、R a2 and R a3The 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 groups (* represents a bond). R a1 , R a2 and R a3 The carbon number of the alicyclic hydrocarbon group of and is preferably 3 to 16. TIFF0007691872000093.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group in and include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined groups include groups combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. Preferably, ma is 0 and na is 1. R a1 and R a2 When and are bonded to each other to form an alicyclic hydrocarbon group, examples of -C(R a1 )(R a2 )(R a3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding position with -O-. TIFF0007691872000094.tif31135

[0136] R a1’ , R a2’ and Ra3’ Examples of the hydrocarbon group in a3’ include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 and are the same as the groups exemplified by a1 , a2 , and a3 . Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group (such as a benzyl group), an aromatic hydrocarbon group having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.), an alicyclic hydrocarbon group having an aromatic hydrocarbon group (a phenylcyclohexyl group, etc.). R a2’ and R a3’ When R a1’ and R a2’ are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X, examples of -C(R a1’ )(R a2’ )-X-R a3’ include the following groups. * represents the bonding position. TIFF0007691872000095.tif21142R a1’ and R a2’ Among them, at least one of R and R is preferably a hydrogen atom. na’ is preferably 0.

[0137] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3A group in which it is an alkyl group, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, and R a3 is an alkyl group, ma = 0, and na = 1. In formula (1), R a1 and R a2 are each independently an alkyl group, R a3 is an adamantyl group, ma = 0, and na = 1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007691872000096.tif154163

[0138] Specific examples of the group (2) include the following groups. * represents a bonding position. TIFF0007691872000097.tif55153

[0139] 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.

[0140] Among the (meth)acrylic monomers having an acid-labile group, preferably those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are 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.

[0141] As the structural unit derived from the (meth)acrylic monomer having a group (1), there are 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)). 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. TIFF0007691872000098.tif41139[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-(CH 2 ) k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1’ represents an integer of 0 to 3.]

[0142] Ra01 , R a4 and R a5 are preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 , L a1 and L a2 are preferably an oxygen atom or *-O-(CH 2 ) 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 and R a04 Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 ~R a3 are the same groups as those exemplified for the groups in formula (1). R a6 and R a7 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 , R a2 and R a3 are the same groups as those exemplified for the groups in formula (1). R a02 , R a03 , and R a04 The alkyl group in R , R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. , R a6 and R a7 The alkyl group in R , R a02 , R a03 and R a04The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12, more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, more preferably 6 to 10. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and alicyclic hydrocarbon group combined is 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and aromatic hydrocarbon group combined is 18 or less. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 are preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, and still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.

[0143] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-18) and R in the structural unit (a1-0)a01 Examples of the structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13), and formula (a1-0-14), and the structural units are preferred. TIFF0007691872000099.tif99159

[0144] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, the structural units represented by any of formula (a1-1-1) to formula (a1-1-7) and R in the structural unit (a1-1) a4 The structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom is preferred, and the structural units represented by any of formula (a1-1-1) to formula (a1-1-4) are more preferred. TIFF0007691872000100.tif39167

[0145] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-14) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) a5 is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and the structural units represented by any of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6), and formula (a1-2-10) to formula (a1-2-14) are preferred. TIFF0007691872000101.tif67163

[0146] When the resin (A) contains the structural unit (a1-0), the content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, and even more preferably 20 to 75 mol% based on all the structural units of the resin (A).

[0147] Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007691872000102.tif3954[In the formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a30 represents a single bond or * -X a31 -(A a32 -X a32 ) nc - and * represents the bonding site with the carbon atom to which -R a32 is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer of 2 or more, a plurality of R a33 may be the same as or different from each other. R a34 and R a35Each 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 -CH 2 - contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0148] R a32 and R a33 Examples of the halogen atom in include fluorine atom, chlorine atom, bromine atom and the like. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in 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 a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group. R a33 Examples of the alkoxy group in include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably methoxy group or ethoxy group, and even more preferably methoxy group. R a33 Examples of the alkoxyalkyl group in R include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy group in R include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in R include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in R include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 R is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0149] *-X a31 -(A a32 -X a32 ) nc- include, among others, *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32 -O-CO- is included. Among these, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0150] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0151] A a30 is preferably a single bond, *-CO-O- or *-CO-O-A a32 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH 2 -CO-O-, and even more preferably a single bond or *-CO-O-.

[0152] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 、R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these. 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 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 groups (* represents the bonding site). Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. In particular, R a36 Examples of R 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.

[0153] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group formed by combining these, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. R a36The alkyl group and alicyclic hydrocarbon group in [it] are preferably unsubstituted. R a36 The aromatic hydrocarbon group in [it] preferably has an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0154] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0155] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-18) and the hydrogen atom corresponding to R a32 in the structural unit (a1-4) are replaced with a halogen atom, a haloalkyl group or an alkyl group, and more preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), formula (a1-4-14) are mentioned. When the resin (A) has the structural unit (a1-4), its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol% based on the total of all the structural units of the resin (A).

[0156] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007691872000105.tif4354In formula (a1-5), R a8represents 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 *-(CH 2 ) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding position with L 51 . L 51 , L 52 , L 53 and L 54 each independently represent -O- or -S-. s1 represents an integer of any one of 1 to 3. s1’ represents an integer of any one of 0 to 3.

[0157] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably an integer of any one of 0 to 2. Z a1 is preferably a single bond or *-CH 2 -CO-O-.

[0158] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by 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 even more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0159] Examples of the structural unit (a1) also include the following structural units. When the resin (A) contains the above structural unit, its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 40 mol% based on all the structural units of the resin (A).

[0160] <Structural unit (s)> The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using 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)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0161] <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 preferable, and it is more preferable to use the structural unit (a2-A) described later. Further, when using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be contained alone as one kind, or may contain two or more kinds.

[0162] 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)"). TIFF0007691872000108.tif4348[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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, and * represents the bonding position with the carbon atom to which -R a50 is bonded. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

[0163] R a50 and R a51 Examples of the halogen atom in R and R include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51Examples of the alkoxyalkyl group in [context] include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in [context] include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in [context] include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group in [context] include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0164] *-X a51 -(A a52 -X a52 ) nb- includes, among others, *-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- is included. Among these, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A a52 -CO-O- is preferred. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group. A a50 is preferably a single bond, *-CO-O- or *-CO-O-A a52 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH 2 -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.

[0165] 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 (a2-2-16) and the R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-16). a50Examples of the structural unit include those in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The structural unit (a2-A) is the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural unit (a2-A), R a50 is preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-3) or the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural unit (a2-A), R a50 is more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, and in the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2-8), and in the structural unit (a2-A), R a50 is even more preferably a structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom. When the resin (A) contains the structural unit (a2-A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all the structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide, the structural unit (a2-A) can be incorporated into the resin (A).

[0166] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). TIFF0007691872000110.tif4260In the formula (a2-1), L a3 represents -O- or * -O-(CH 2 ) k2 -CO-O-, k2 represents any integer from 1 to 7. * represents the bonding position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group, or a hydroxy group. o1 represents any integer from 0 to 10.

[0167] In the formula (a2-1), L a3 is preferably -O-, -O-(CH 2 ) 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, and more preferably 0 or 1.

[0168] Examples of the structural unit (a2-1) include structural units derived from monomers described in JP 2010-204646 A. A structural unit represented by any one of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. TIFF0007691872000111.tif53151 When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, even more preferably 2 to 20 mol %, and still more preferably 2 to 10 mol %, based on all structural units of the resin (A).

[0169] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), (a3-2), (a3-3) or (a3-4). One of these may be contained alone, or two or more of them may be contained. TIFF0007691872000112.tif51162 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH 2 ) k3 It represents a group represented by -CO-O- (k3 represents an integer of any of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OLa8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O- represents. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding site with the carbonyl group. R a18 , R a19 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 is -CH 2 - 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.

[0170] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in R R a24Examples of the halogen atom in [context] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in [context] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, etc. Preferably, an alkyl group having 1 to 4 carbon atoms is mentioned, and more preferably, a methyl group or an ethyl group is mentioned. R a24 Examples of the alkyl group having a halogen atom in [context] include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc.

[0171] L a8 and L a9 Examples of the alkanediyl group in [context] and [context] include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group, etc.

[0172] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently, preferably -O- or, *-O-(CH 2 ) k3 -CO-O- in which k3 is an integer of any one of 1 to 4, more preferably -O- and, *-O-CH 2 -CO-O-, even more preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. R a22 and R a23is, independently of each other, preferably a carboxy group, a cyano group or a methyl group. p1, q1 and r1 are, independently of each other, preferably any integer from 0 to 2, more preferably 0 or 1.

[0173] 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, still 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-CH 2 -CO-O- or -O-C 2 H 4 -CO-O-. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007691872000113.tif4151 (wherein R a24 , L a7 represent the same meaning as described above.)

[0174] 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, R a18 , R a19 , R a20 and R a24A structural unit in which a methyl group corresponding thereto is replaced by a hydrogen atom is preferred. TIFF0007691872000114.tif115165 When 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). In addition, 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).

[0175] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007691872000115.tif3165 [In the formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a fluorine atom and having 1 to 24 carbon atoms, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. ]] R 42 Examples of the saturated hydrocarbon group represented by include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

[0176] 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). As the group formed by the combination of 11160 combinations of TIFF0007691872000116.tif, groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups can be mentioned, such as -alkanediyl group - alicyclic hydrocarbon group, -alicyclic hydrocarbon group - alkyl group, -alkanediyl group - alicyclic hydrocarbon group - alkyl group, and the like.

[0177] As the structural unit (a4), structural units 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) can be mentioned. TIFF0007691872000117.tif3953[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 6a represents a hydrogen atom or a fluorine atom.]

[0178] L 4a Examples of the alkanediyl group in include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0179] L 3aExamples of the perfluoroalkanediyl group in [reference] include difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a Examples of the perfluorocycloalkanediyl group in [reference] include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, perfluoroadamantanediyl group, and the like.

[0180] 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.

[0181] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R 5a in (a4-0) is replaced by a hydrogen atom. TIFF0007691872000118.tif95165

[0182] TIFF0007691872000119.tif4764[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 -CH 2 - included 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. TIFF0007691872000120.tif1383[In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-. However, the total number of carbon atoms of A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less. ] * represents a bonding position, and the * on the right side is the bonding position with -O-CO-R a42 . ]

[0183] R a42 Examples of the saturated hydrocarbon group in R include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0184] Examples of the chain saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding position). Examples of the group formed by the combination of TIFF0007691872000121.tif11160 include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0185] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, and preferably a fluorine atom. TIFF0007691872000122.tif752[In the 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 which has at least one halogen atom. ​

[0186] A a45 Examples of the aliphatic hydrocarbon group in 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, and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding position). TIFF0007691872000123.tif11160

[0187] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, and perfluorooctyl group. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl group. R a42 When 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), the total number of carbon atoms of R a42 is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0188] Ra42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF0007691872000124.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.]

[0189] A a46 The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms of the aliphatic hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0190] A preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007691872000125.tif13161

[0191] A a41Examples 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, 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 butane-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. A a41 Examples of the substituent in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and further preferably an ethylene group.

[0192] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, and groups formed by combining alkanediyl groups and divalent alicyclic hydrocarbon groups, etc. Specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, etc. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula (1) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0193] In the group represented by formula (a-g1), X a42 Examples of the group in which is -O-, -CO-, -CO-O-, or -O-CO- include the following groups. In the following examples, * and ** each represent a bond position, and ** represents -O-CO-Ra42 is a bonding site with TIFF0007691872000126.tif48153

[0194] Examples of the structural unit represented by formula (a4-1) include the following structural units and the structural units represented by formula (a4-1) in the following structural units, where the methyl group corresponding to R a41 is replaced by a hydrogen atom. TIFF0007691872000127.tif100142

[0195] TIFF0007691872000128.tif123141

[0196] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. TIFF0007691872000129.tif3251[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having a fluorine atom and 1 to 20 carbon atoms. However, the upper limit of the total carbon number of L 44 and R f6 is 21.]

[0197] The alkanediyl group of L 44 includes the same groups as those exemplified by A a41 The saturated hydrocarbon group of R R f6 includes the same groups as those exemplified by R a42 As the alkanediyl group in L L 44 an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0198] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11), respectively. In the structural unit (a4-2), R f5 The structural unit in which the methyl group corresponding to is replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-2).

[0199] TIFF0007691872000130.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 to A f13 .). A f14 represents 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.]

[0200] Examples of the alkanediyl group in L 5 include the same groups as those exemplified for the alkanediyl group of A a41 . A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in preferably includes a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkane diyl groups such as methylene group, ethylene group, propane diyl group, butane diyl group and pentane diyl group; perfluoroalkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluorobutane diyl group and perfluoropentane diyl group, etc. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexane diyl group and perfluorocyclohexane diyl group, etc. Examples of the polycyclic group include adamantane diyl group, norbornane diyl group, perfluoroadamantane diyl group, etc.

[0201] A f14 Examples of the saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of a42 are the same groups as those exemplified by R. Among them, fluorinated alkyl groups such as trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group; cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group, etc. are preferred.

[0202] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group preferably includes 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 preferably includes 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 including 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 including 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.

[0203] Examples of the structural unit represented by formula (a4-3) include structural units respectively represented by formulas (a4-1'-1) to (a4-1'-11). The methyl group corresponding to R f7 in the structural unit (a4-3) replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-3).

[0204] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-4). TIFF0007691872000131.tif4264 [In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH 2 ) j1 -, -(CH 2 ) j2 -O-(CH 2 ) j3 - or -(CH 2 ) j4 -CO-O-(CH 2 ) j5 -. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.

[0205] R f22 The saturated hydrocarbon group of R a42 is the same as the saturated hydrocarbon group represented by R f22 is preferably an alkyl group having 1 to 10 carbon atoms with a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms with a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms with a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms with a fluorine atom. In formula (a4-4), A f21 is preferably -(CH 2 ) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0206] Examples of the structural unit represented by formula (a4-4) include the following structural units and the structural units represented by the following formulas, in which the methyl group corresponding to R f21 in the structural unit (a4-4) is replaced by a hydrogen atom. When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0207] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group of 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 the structural unit represented by formula (a5-1). TIFF0007691872000133.tif3972[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group 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 -CH 2 - in the saturated hydrocarbon group may be replaced by -O- or -CO-.]

[0208] R 52 As the alicyclic hydrocarbon group in, it 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, etc. 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, etc. R 52 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.

[0209] L 55 Examples of the divalent saturated hydrocarbon group in include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and 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 propanediyl group, a butanediyl group, and a pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include 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, etc.

[0210] L55 The -CH contained in the divalent saturated hydrocarbon group represented by 2 Examples of the group in which - is replaced by -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents the bonding position with L x1 .). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, the total number of carbon atoms of L x1 and L x2 is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, the total number of carbon atoms of 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 of 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 x1represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 have a total carbon number of 15 or less.

[0211] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0212] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007691872000135.tif54134

[0213] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007691872000136.tif24131

[0214] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007691872000137.tif15145

[0215] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007691872000138.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0216] Examples of the structural unit (a5-1) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. 51 and structural units in which the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. TIFF0007691872000139.tif110150When the resin (A) has the 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% based on all the structural units of the resin (A).

[0217] 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO 2 - group, and preferably has a -SO 2 - group in the side chain. -SO 2 The structural unit having a - group may have a linear structure having a -SO 2 - group, or may have a branched structure having a -SO 2 - group, or -SO 2It may have a cyclic structure (monocyclic and polycyclic structures) having a - group. Preferably, -SO 2 It is a structural unit having a cyclic structure having a - group, and more preferably, -SO 2 It is a structural unit having a cyclic structure (sultone ring) containing -O-.

[0218] Examples of the sultone ring include the rings represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO 2 -O- as an atomic group constituting the ring, and examples include the rings represented by formula (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a heteroatom in addition to -SO 1 -O- as an atomic group constituting the ring, like the ring represented by formula (T 2 Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, and preferably an oxygen atom. TIFF0007691872000140.tif3187

[0219] The sultone ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms, etc.

[0220] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group, and preferably a trifluoromethyl group. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a hydroxyalkyl group such as a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or less carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0221] From the viewpoint of easy production of the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferred. As the sultone ring, a ring represented by the following formula (T1’) is preferable. TIFF0007691872000141.tif3172[In formula (T1’), X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. R 41 is exemplified by the same ones as the substituents of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

[0222] As the sultone ring, a ring represented by formula (T1) is more preferable. TIFF0007691872000142.tif3149[In formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.]

[0223] R 8 is the same as R 41 and the like can be mentioned. ma in formula (T1') and m in formula (T1) are preferably 0 or 1, more preferably 0.

[0224] Examples of the ring represented by formula (T1') and the ring represented by formula (T1) include the following rings. The bonding site can be at any position. TIFF0007691872000143.tif53161

[0225] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007691872000144.tif50161

[0226] -SO 2 The structural unit having a - group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0227] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007691872000145.tif4956[In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH contained in the saturated hydrocarbon group 2- may be replaced by -O-, -CO- or -N(R d )-. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0228] R x Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. x Examples of the alkyl group of R include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, etc., preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. x Examples of the alkyl group having a halogen atom of R include, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, etc. x R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.

[0229] A x Examples of the divalent saturated hydrocarbon group of A include linear alkanediyl groups, branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of 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, 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, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups that are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group, etc.

[0230] R 41 、X 11 and ma are the same as those in formula (T1’). Examples of the sultone ring include those described above, and among them, those with a specific bonding position are preferred.

[0231] Examples of the structural unit (a6) include the following structural units. TIFF0007691872000146.tif100158

[0232] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferred, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferred. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and still more preferably 3 to 30 mol% based on all the structural units of the resin (A).

[0233] <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 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 is preferable.

[0234] The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007691872000147.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH 2 - in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the 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 the hydrogen atom contained in the alkanediyl group may be substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0235] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted on A 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, etc. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations 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. -CH contained in the saturated hydrocarbon group 2 Examples of those in which - is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formula, * represents a bond with A 2 -O-, -S- or -CO-. x1 represents a bond. TIFF0007691872000148.tif145161

[0236] 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. X8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0237] ZA in formula (II-2-A’) + is the same as the cation Z1 in the acid generator (B1). + Examples thereof include the same ones as above.

[0238] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007691872000149.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

[0239] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007691872000150.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Qa , Q b and ZA + have 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, and -CH 2 - 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 groups as the divalent saturated hydrocarbon group represented by X III3 represented by.

[0240] 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. TIFF0007691872000151.tif5288 [In the formula (II-2-A-2), R III3 , R III5 and ZA + have the same meaning as described above. mA and nA each independently represent 1 or 2.

[0241] Examples of the structural unit represented by the formula (II-2-A') include, for example, the following structural unit, R III3A structural unit in which a group corresponding to the methyl group is replaced with 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), and a structural unit described in International Publication No. 2012 / 050015 are exemplified. ZA + represents an organic cation. TIFF0007691872000152.tif87163

[0242] 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). TIFF0007691872000153.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 represents 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. II2 R II3 Examples of the hydrocarbon group represented by and R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. II4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. II4Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by a8 . A II1 Examples of the divalent linking group represented by II1 include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and -CH 2 - contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, X III3 are the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 .

[0243] Examples of the structural unit containing the cation in formula (II-1-1) include the structural unit represented by the following and the structural unit in which the group corresponding to the methyl group of R II4 is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group or the like. TIFF0007691872000154.tif85130

[0244] A - Examples of the organic anion represented by - include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions and the like. A - Among the organic anions represented by - , sulfonate anions are preferred, and among the sulfonate anions, those which are the anions contained in the salts represented by the aforementioned formula (B1) are more preferred.

[0245] A - Examples of the sulfonylimide anions represented by - include the following. TIFF0007691872000155.tif35134 Examples of the sulfonylmethide anions include the following. TIFF0007691872000156.tif29123 Examples of the carboxylic acid anions include the following. TIFF0007691872000157.tif41155

[0246] Examples of the structural unit represented by formula (II-1-1) include the structural units represented below. TIFF0007691872000158.tif98165 When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0247] The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well-known in the art.

[0248] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two kinds, and still more preferably the structural unit (a1-1) and / or the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-A) or a structural unit represented by formula (a2-1). The structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by formula (a3-1), the structural unit represented by formula (a3-2), and the structural unit represented by formula (a3-4).

[0249] Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that leads to these structural units. The content of each structural unit of the resin (A) can be adjusted by the amount of the monomer used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the examples.

[0250] <Resins 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, as the resin (X), a resin containing the structural unit (a4) is preferable. In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, 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 structural units derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using 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 means for measuring 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, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin (A).

[0251] 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, based on 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, based on 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 analytical means such as liquid chromatography or gas chromatography.

[0252] <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 analytical means such as liquid chromatography or gas chromatography. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0253] <Quencher (C)> The quencher (C) includes salts that generate an acid with a lower acidity than the acid generated from the basic nitrogen-containing organic compound or the acid generator (B) (excluding carboxylates 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% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass, based on the solid content of the resist composition. Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of the amine include aliphatic amines and aromatic amines. Examples of the aliphatic amine 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.

[0254] The acidity of a salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). A salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably the weak acid inner salt (D). TIFF0007691872000159.tif89166

[0255] Examples of the weak acid inner salt (D) include the following salts. TIFF0007691872000160.tif72165

[0256] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0257] 〈Preparation of Resist Composition〉 The resist composition of the present invention can be prepared by mixing a carboxylate (I), a resin (A), an acid generator (B), and, if necessary, a resin other than the resin (A), a solvent (E), a 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.

[0258] 〈Method for Manufacturing Resist Pattern〉 The method for manufacturing a resist pattern of the present invention (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer. To apply the resist composition onto a substrate, it can be performed by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers and organic substrates such as already formed resist films. Before applying the resist composition, the substrate may be washed, or an antireflection film, etc. may be formed on the substrate. By drying the composition after coating, 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-baking), 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 F 2 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 composition layer after exposure 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. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Also, before development, the steps of coating, drying, exposing, and heating the resist composition may be repeated on the composition layer after exposure. The composition layer after heating 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 small amount of water. During development, the 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.

[0259] <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, and is particularly suitable as a resist composition for ArF excimer laser exposure and is useful for semiconductor microfabrication.

Examples

[0260] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing content or usage amount 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 model 1100, MASS is Agilent LC / MSD model). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0261] Example 1: Synthesis of the salt represented by formula (I-1) 20 parts of the compound represented by formula (I-1-a), 2.28 parts of the compound represented by formula (I-1-c), 100 parts of ethyl acetate and 15 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 6.55 parts of the compound represented by formula (I-1-b) was added and stirred at 23 °C for 18 hours. To the resulting reaction mass, 20 parts of n-heptane and 70 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. This water washing operation was repeated 4 times. The resulting organic layer was concentrated, and the concentrated mass was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 7.48 parts of the compound represented by formula (I-1-d). 0.95 part of the compound represented by formula (I-1-d) and 10 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.14 part of sodium hydride was added. To the resulting mixture, 1.81 parts of the salt represented by formula (I-1-e) was added and stirred at 5 °C for 3 hours. To the resulting mixture, 6.30 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the resulting mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, and then separated to extract the organic layer. After concentrating the resulting organic layer, 1 part of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.52 parts of the salt represented by formula (I-1-f). 0.95 parts of the salt represented by TIFF0007691872000163.tif55115 formula (I-1-f) and 30 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes. Then, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 0.45 parts of the compound represented by formula (I-1-g) was added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.13 parts of the salt represented by formula (I-1-h) was obtained. 0.71 parts of the salt represented by TIFF0007691872000164.tif70146 formula (I-1-h), 0.37 parts of the salt represented by formula (I-1-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.76 parts of the salt represented by formula (I-1) was obtained. MASS(ESI(+)Spectrum):M + 525.2 MASS(ESI(-)Spectrum):M - 195.1

[0262] Example 2: Synthesis of the salt represented by formula (I-2) 0.71 part of the salt represented by formula (I-1-h), 0.37 part of the salt represented by formula (I-2-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.78 part of the salt represented by formula (I-2) was obtained. MASS(ESI(+)Spectrum):M + 525.2 MASS(ESI(-)Spectrum):M - 193.1

[0263] Example 3: Synthesis of the salt represented by formula (I-4) 0.71 part of the salt represented by formula (I-1-h), 0.55 part of the salt represented by formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.99 part of the salt represented by formula (I-4) was obtained. MASS(ESI(+)Spectrum):M + 525.2 MASS(ESI(-)Spectrum):M - 337.1

[0264] Example 4: Synthesis of the salt represented by formula (I-2474) 2.10 parts of the compound represented by the formula (I-1-d) and 20 parts of tetrahydrofuran were mixed, stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.28 part of sodium hydride was added. To the resulting mixture, 1.91 parts of the salt represented by the formula (I-2474-e) was added, and the mixture was stirred at 5 °C for 3 hours. To the resulting mixture, 12.60 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C, and the mixture was stirred at 23 °C for 6 hours. To the resulting mixture, 50 parts of chloroform and 25 parts of ion-exchanged water were added, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. After concentrating the obtained organic layer, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, stirred at 23 °C for 30 minutes, then the supernatant was removed, and by concentrating, 2.42 parts of the salt represented by the formula (I-2474-f) was obtained. 1.20 parts of the salt represented by the formula (I-2474-f) and 30 parts of dimethylformamide were mixed, stirred at 23 °C for 30 minutes, then 0.32 part of potassium carbonate and 0.10 part of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 1.08 parts of the compound represented by the formula (I-1-g) was added, and the mixture was stirred at 75 °C for 5 hours, then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.49 parts of the salt represented by the formula (I-2474-h) was obtained. 1.03 parts of the salt represented by TIFF0007691872000169 (I-2474-h), 0.55 parts of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, and then liquid separation was carried out to take out the organic layer. To the obtained organic layer, 10 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 5 times. By concentrating the obtained organic layer, 1.38 parts of the salt represented by formula (I-2474) was obtained. MASS(ESI(+)Spectrum):M + 789.3 MASS(ESI(-)Spectrum):M - 337.1

[0265] Example 5: Synthesis of the salt represented by formula (I-2569) 3.15 parts of the compound represented by TIFF0007691872000170 (I-1-d) and 30 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.42 parts of sodium hydride was added. To the resulting mixture, 2.01 parts of the salt represented by formula (I-2569-e) was added and stirred at 5 °C for 3 hours. To the obtained mixture, 18.90 parts of 1N hydrochloric acid was added, then the temperature was raised to 23 °C and stirred at 23 °C for 6 hours. To the resulting mixture, 100 parts of chloroform and 50 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. After concentrating the obtained organic layer, to the concentrated residue, 5 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 3.11 parts of the salt represented by formula (I-2569-f). 1.45 parts of the salt represented by formula (I-2569-f) and 30 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes. Then, 0.48 part of potassium carbonate and 0.15 part of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 1.61 parts of the compound represented by formula (I-1-g) were added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 1.88 parts of the salt represented by formula (I-2569-h) were obtained. 1.36 parts of the salt represented by formula (I-2569-h), 0.55 part of the salt represented by formula (I-4-i), and 20 parts of chloroform were mixed and stirred at 23 °C for 12 hours. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 1.62 parts of the salt represented by formula (I-2569) were obtained. MASS(ESI(+)Spectrum):M + 1053.4 MASS(ESI(-)Spectrum):M - 337.1

[0266] Synthesis of Resin The compounds (monomers) used in 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. TIFF0007691872000173.tif39130

[0267] Synthesis Example 1: Synthesis of Resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-1) and monomer (a3-4-2) were used, and they were mixed so that the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-1): monomer (a3-4-2)] was 45:14:2.5:38.5. Propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer amount was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in amounts of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. This reprecipitation operation was performed twice, and resin A1 having a weight average molecular weight of 7.8×10 3 was obtained in a yield of 69%. This resin A1 has the following structural units. TIFF0007691872000174.tif36126

[0268] Synthesis Example 2: Synthesis of Resin X1 As a monomer, monomer (a4-1-4) was used, and dioxane in an amount 1.5 times the total monomer amount was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in amounts of 0.7 mol% and 2.1 mol%, respectively, based on the total monomer amount, and these were heated at 75 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. This reprecipitation operation was performed twice, and resin X1 having a weight average molecular weight of 1.8×10 4 was obtained in a yield of 77%. This resin X1 has the following structural units. TIFF0007691872000175.tif3658

[0269] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0270] <Resin> A1, X1: Resin A1, Resin X1 <Acid generator (B)> B1-21: Salt represented by formula (B1-21) B1-22: Salt represented by formula (B1-22) TIFF0007691872000177.tif30100<Carboxylate (I)> I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-2474: Salt represented by formula (I-2474) I-2569: Salt represented by formula (I-2569) <Quencher (C)> IX-1 IX-2 IX-3 IX-4 TIFF0007691872000178.tif75160<Solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-Heptanone 20 parts γ-Butyrolactone 3.5 parts

[0271] <Manufacture of resist pattern> An organic antireflective film composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205°C for 60 seconds to form an organic antireflective film with a thickness of 78 nm. Next, the above resist composition was spin-coated onto the organic antireflective film such that the film thickness after drying was 85 nm. The obtained silicon wafer was prebaked (PB) for 60 seconds at the temperature described in the "PB" column of Table 2 on a direct hot plate. Thus, a wafer with a resist composition film formed thereon was immersion-exposed to a line and space pattern (pitch 90 nm / line width 45 nm) by varying the exposure dose stepwise using an ArF excimer stepper for immersion exposure [XT: 1900Gi; manufactured by ASML, NA = 1.35, 3 / 4 Annular X-Y polarization]. Note that ultrapure water was used as the immersion medium. After exposure, post-exposure bake (PEB) was performed for 60 seconds at the temperature described in the "PEB" column of Table 2 on a hot plate, and further paddle development was carried out for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. In the obtained resist pattern, the exposure dose at which the line width and space width of the line and space pattern became 1:1 was defined as the effective sensitivity.

[0272] <Pattern collapse evaluation (PCM) evaluation> The line width of the line pattern becomes thinner as the exposure dose increases, and pattern disappearance is likely to occur. The numbers indicate the minimum line width (nm) of the resist pattern in which no pattern disappearance due to collapse or peeling is observed in the line pattern formed at an exposure dose equal to or higher than the effective sensitivity. The results are shown in Table 3.

Table 3

[0273] From the above results, it can be seen that the resist composition containing the carboxylate of the present invention can produce a resist pattern with a good pattern collapse evaluation (PCM).

Industrial applicability

[0274] The resist composition containing the salt of the present invention is suitable for semiconductor microfabrication and is extremely useful industrially because a resist pattern having good pattern collapse evaluation (PCM) can be obtained.

Claims

1. A carboxylate represented by formula (I). [In formula (I), R １ 、 R ２ and R ３ each independently represents -O-R １０ 、 -O-CO-R １０ 、 -O-CO-O-R １０ 、 -O-L １ -CO-O-R １０ respectively. R ４ , R ５ , R ６ , R ７ , R ８ and R ９ each independently represents a halogen atom, a hydroxy group, a C1-C12 perfluoroalkyl group or a C1-C18 hydrocarbon group, the hydrocarbon group may have a substituent, and the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R １０ represents a group represented by the formula (IC). X １ , X ２ and X ３ each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 0 to 5, and when m1 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m2 represents any integer from 0 to 4, and when m2 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m3 represents any integer from 0 to 4, and when m3 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. m5 represents any integer from 0 to 4, and when m5 is 2 or more, the plurality of Rs ５ may be the same as or different from each other. m6 represents any integer from 0 to 4, and when m6 is 2 or more, the plurality of Rs ６ may be the same as or different from each other. m7 represents any integer from 0 to 5, and when m7 is 2 or more, the plurality of Rs 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, the plurality of Rs ８ may be the same as or different from each other. m9 represents any integer from 0 to 4, and when m9 is 2 or more, the plurality of Rs ９ may be the same as or different from each other. However, 0 ≦ m1 + m7 ≦ 5, 0 ≦ m2 + m8 ≦ 4, 0 ≦ m3 + m9 ≦ 4, and at least one of m1, m2, and m3 represents an integer of 1 or more. X ４ represents a single bond, -CH 2 -, -O-, -S-, -CO-, -SO- or -SO ２ -. X ０ represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom or a hydroxy group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. [In formula (IC), R Ａ represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents any integer from 0 to 2. When u1 is 2, the plurality of Rs Ａ are either the same or different. s1 represents 1 or 2. t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2. L ２ represents a hydrocarbon group having 1 to 36 carbon atoms which may have a single bond or a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -. * represents a bonding site.]

2. X １ , X ２ and X ３ The carboxylate according to claim 1, wherein X, X, and X are oxygen atoms.

3. R １ 、 R ２ and R ３ is -O-CO-O-R １０ - or -O-L １ -CO-O-R １０ The carboxylate according to claim 1 or 2, wherein it is

4. L ２ The carboxylate according to any one of claims 1 to 3, wherein L is a methylene group.

5. A carboxylic acid generator containing the carboxylate according to any one of Claims 1 to 4.

6. A resist composition containing the carboxylic acid generator according to Claim 5, an acid generator other than the carboxylic acid generator, and a resin having an acid-labile group.

7. The resist composition according to Claim 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). [In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH ２ ) k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents a bond with -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents 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 Claim 6 or 7, further containing a resin containing a structural unit having a fluorine atom.

9. (1) A step of applying the resist composition according to any one of Claims 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, A method for manufacturing a resist pattern including these steps.

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