Compound, resin, resist composition, and method for producing resist pattern

Abstract

To provide a compound, a resin, and a resist composition capable of producing a resist pattern having good line edge roughness (LER).SOLUTION: The compound is represented by formula (IA) or formula (IB), and the resin and the resist composition contain a structural unit derived from the compound. (Formula IA): CH=C(-R)-X-L(-OR)(-OR)(-0R). (Formula IB): CH=C(-R)-X-L(-X-C(-R)=CH)(-OR)(-0R). [Rand Reach represent H or a methyl group; Xand Xeach represent -C(=O)O- or the like; Lrepresents a substituted / unsubstituted C1-48 hydrocarbon group; and R, Rand Reach represent a C2-4 cyclic hydrocarbon group containing one O, which may have a saturated hydrocarbon group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, a resin, a resist composition, and a method for producing a resist pattern using the resist composition. [Background technology]

[0002] Patent Document 1 describes the following compound. TIFF0007763575000001.tif3340 Patent Document 2 describes a resist composition containing a resin having a structural unit derived from the following compound. TIFF0007763575000002.tif2244 Patent Document 3 describes the following compound. TIFF0007763575000003.tif3035 Patent Document 4 describes a resist composition containing a resin having a structural unit derived from the following compound. TIFF0007763575000004.tif4341 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 55-060941 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-155851 [Patent Document 3] Japanese Patent Application Publication No. 09-258441 [Patent Document 4] Japanese Patent Application Laid-Open No. 2017-095444 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a compound that enables the production of a resist pattern with better CD uniformity (CDU) than a resist pattern formed from a resist composition containing a resin having a structural unit derived from the above compound. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A compound represented by formula (IA) or formula (IB): TIFF0007763575000005.tif10282 [In formula (IA) and formula (IB), R 1 and R 2 each independently represents a hydrogen atom or a methyl group. X 1 and X 2 are each independently a group of the formula (X 1 -1)~Formula(X 1 -7). TIFF0007763575000006.tif45140(formula(X 1 -1)~Formula(X 1 -7) Medium, *, ** represent binding sites, ** represents L 1 ) L 1 represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. R 3 represents a hydrocarbon group having 1 to 36 carbon atoms and having a group represented by formula (IC) (the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by formula (IC) (the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). TIFF0007763575000007.tif2651[In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents an integer of 0 to 2, and when u1 is 2, a plurality of R A are either the same or different. s1 represents 1 or 2. t1 represents 0 or 1, provided that the sum of s1 and t1 is 1 or 2. * denotes a binding site.] [2]L 1 But the formula (L 1 A group represented by the formula (L 1 B) is a group represented by the formula (1), TIFF0007763575000008.tif31103[Formula(L 1 A) and formula (L 1 B) Medium; L 4 and L 4' each independently represents a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. L 2 and L 3 each independently represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3' represents an alkanetriyl group having 1 to 4 carbon atoms. *a is X 1 *b represents the binding site with -OR 5 Oxygen atom or X in 2 *c represents the binding site with -OR 3 represents the bond site with the oxygen atom in 4 represents the bonding site with the oxygen atom in [3]L 4 and L 4’ are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms, or a group in which an alkanediyl group having 1 to 6 carbon atoms is combined with an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), and L2 is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and L 3 is an alkanediyl group having 1 to 4 carbon atoms, and L 3' is an alkanetriyl group having 1 to 4 carbon atoms. [4]X 1 But the formula (X 1 -1), formula (X 1 -3) or formula (X 1 The compound according to any one of [1] to [3], wherein the group is represented by any one of [1] to [3]. [5] A resin containing a structural unit derived from the compound according to any one of [1] to [4]. [6] The resin according to [5], further comprising a structural unit having an acid labile group. [7] The resin according to [6], wherein the structural unit having an acid labile group comprises at least one of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2): TIFF0007763575000009.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding site with —CO—. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group 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. [8] A resist composition comprising the resin according to any one of [5] to [7] and an acid generator. [9] The resist composition according to [8], wherein the acid generator comprises a salt represented by formula (B1): TIFF0007763575000010.tif2859[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and wherein a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S(O)2- or -CO-. Z + represents an organic cation.

[10] The resist composition according to [8] or [9], further comprising a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator.

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

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

[0006] By using a resist composition containing a resin having structural units derived from the compound of the present invention, it is possible to produce resist patterns with good CD uniformity (CDU). DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, unless otherwise specified, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate." The terms "(meth)acrylic acid" and "(meth)acryloyl" have the same meaning. When a structural unit having "CH2=C(CH3)-CO-" or "CH2=CH-CO-" is exemplified, it is understood that a structural unit having both groups is also exemplified. The term "combined group" refers to a group in which two or more of the exemplified groups are bonded, and the valence of these groups may be changed appropriately depending on the bonding form. Furthermore, when stereoisomers exist, all stereoisomers are included. In this specification, the term "solid content of the resist composition" refers to the sum of all components in the resist composition excluding the solvent (E), which will be described later.

[0008] [Compounds represented by formula (IA) and formula (IB)] The compound of the present invention relates to a compound represented by formula (IA) (hereinafter sometimes referred to as "compound (IA)") and a compound represented by formula (IB) (hereinafter sometimes referred to as "compound (IB)"). In formula (IA) and formula (IB), X 1 and X 2 is the formula (X 1 -1)~Formula(X 1 -7). Among them, X 1 is the formula (X 1 -1), formula (X 1 -3) or formula (X 1 -4), and 1 -1) or formula (X 1 It is more preferable that the group is a group represented by any one of the following formulae:-4). L 1Examples of the hydrocarbon group having 1 to 48 carbon atoms include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanetetrayl groups, alkenetetrayl groups, and alkinetetrayl groups, and monocyclic or polycyclic alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and the like, and may be tetravalent hydrocarbon groups combining two or more of these groups (for example, a tetravalent hydrocarbon group combining a tetravalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group, a tetravalent hydrocarbon group combining a tetravalent alicyclic hydrocarbon group or an aromatic hydrocarbon group and one or more divalent aliphatic hydrocarbon groups, a tetravalent hydrocarbon group combining a trivalent or tetravalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group and an alkanediyl group, etc.).

[0009] Examples of the alkanetetrayl group include linear or branched alkanetetrayl groups such as a methanetetrayl group, an ethanetetrayl group, a propanetetrayl group, a butanetetrayl group, a pentanetetrayl group, a hexanetetrayl group, a heptanetetrayl group, an octanetetrayl group, a nonanetetrayl group, a decanetetrayl group, an undecanetetrayl group, and a dodecanetetrayl group. Examples of the alkenetetrayl group include an ethenetetrayl group, a propenetetrayl group, an isopropenetetrayl group, a butenetetrayl group, an isobutenetetrayl group, a tert-butenetetrayl group, a pentenetetrayl group, a hexenetetrayl group, a heptenetetrayl group, an octynetetrayl group, an isooctinetetrayl group, and a nonenetetrayl group. Examples of the alkynetetrayl group include a propynetetrayl group, an isopropynetetrayl group, a butynetetrayl group, an isobutynetetrayl group, a tert-butynetetrayl group, a pentynetetrayl group, a hexynetetrayl group, an octynetetrayl group, and a nonynetetrayl group. Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkanetetrayl groups such as a cyclobutanetetrayl group, a cyclopentanetetrayl group, a cyclohexanetetrayl group, a cyclohexenetetrayl group, and a cyclooctanetetrayl group. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkanetetrayl groups such as a norbornanetetrayl group, a norbornanetetrayl group, a 5-norbornenetetrayl group, an adamantanetetrayl group, and an adamantanetetrayl group. Examples of the aromatic hydrocarbon group include a benzenetetrayl group, a naphthalenetetrayl group, and an anthracenetetrayl group. Examples of hydrocarbon groups that combine two or more types include groups that combine a chain hydrocarbon group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group. Specific examples include groups that combine an alkanetetrayl group with a monovalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, groups in which a methylene group in an alkanetetrayl group is replaced with a divalent alicyclic hydrocarbon group and / or a divalent aromatic hydrocarbon group, and groups that combine a trivalent or tetravalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group with an alkanediyl group.

[0010] L 1 Examples of the substituent that the hydrocarbon group may have include a halogen atom and a cyano group. Hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), carboxy group (a group in which -CH2-CH2- in an ethyl group is replaced with -O-CO-), alkoxy group having 1 to 12 carbon atoms (a group in which -CH2- in an alkyl group having 2 to 13 carbon atoms is replaced with -O-), alkoxycarbonyl group having 2 to 13 carbon atoms (a group in which -CH2-CH2- in an alkyl group having 4 to 15 carbon atoms is replaced with -O-), is replaced with -O-CO-), an alkylcarbonyl group having 2 to 13 carbon atoms (a group in which -CH2- in an alkyl group having 3 to 14 carbon atoms is replaced with -CO-), and an alkylcarbonyloxy group having 2 to 13 carbon atoms (a group in which -CH2-CH2- in an alkyl group having 4 to 15 carbon atoms is replaced with -CO-O-) are groups in which -CH2- in a hydrocarbon group is replaced with -O- or -CO-. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group. L 1 The tetravalent hydrocarbon group having 1 to 48 carbon atoms represented by the following formula may have one or more substituents.

[0011] L 1 -CH2- contained in the hydrocarbon group having 1 to 48 carbon atoms may be replaced by -O-, -S-, -CO- or -SO2-. L 1 When the hydrocarbon group having 1 to 48 carbon atoms has a substituent, or when a -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2-, the number of carbon atoms before replacement is regarded as the number of carbon atoms of the hydrocarbon group.

[0012] L 1 is the formula (L 1 A) or formula (L 1 B) is preferred. TIFF0007763575000011.tif31103 [In formula (IIA) and formula (IIB), L 4 and L 4'each independently represents a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. L 2 and L 3 each independently represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3' represents an alkanetriyl group having 1 to 4 carbon atoms. *a is X 1 *b represents the bonding site with an oxygen atom or X 2 *c represents the binding site with -OR 3 represents the bond site with the oxygen atom in 4 represents the bonding site with the oxygen atom in

[0013] L 4 and L 4' Examples of the hydrocarbon group having 1 to 24 carbon atoms include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, and alkynediyl groups, and monocyclic or polycyclic divalent alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and the like, and may be divalent hydrocarbon groups formed by combining two or more of these groups.

[0014] Examples of the alkanediyl group include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group; Examples of branched alkanediyl groups include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, an isopropenediyl group, a butenediyl group, an isobutenediyl group, a tert-butenediyl group, a pentenediyl group, a hexenediyl group, a heptenediyl group, an octynediyl group, an isooctenediyl group, and a nonenediyl group. Examples of the alkynediyl group include an ethynediyl group, a propynediyl group, an isopropynediyl group, a butynediyl group, an isobutynediyl group, a tert-butynediyl group, a pentynediyl group, a hexynediyl group, an octynediyl group, and a nonynediyl group. Examples of the monocyclic divalent alicyclic hydrocarbon group include monocyclic cycloalkanediyl groups such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene-3,6-diyl group, and a cyclooctane-1,5-diyl group. Examples of the polycyclic divalent alicyclic hydrocarbon group include polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group. Examples of hydrocarbon groups that combine two or more types include groups that combine a chain hydrocarbon group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, and specific examples include groups that combine an alkanediyl group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, such as -cycloalkanediyl group-alkanediyl group-, -alkanediyl group-cycloalkanediyl group-, -alkanediyl group-cycloalkanediyl group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, and -aromatic hydrocarbon group-alkanediyl group-.

[0015] L 4 and L 4' The substituents that the hydrocarbon group may have include 1The substituents of the hydrocarbon group of L are the same as those of the hydrocarbon group of L. In addition, groups encompassed by replacing -CH2- in the hydrocarbon group are also included in L. 1 The hydrocarbon group is the same as that of the above. L 4 and L 4' The divalent hydrocarbon group having 1 to 24 carbon atoms represented by the following formula may have one or more substituents.

[0016] L 4 and L 4' -CH2- contained in the hydrocarbon group having 1 to 24 carbon atoms may be replaced by -O-, -S-, -CO- or -SO2-. L 4 and L 4' When the hydrocarbon group having 1 to 24 carbon atoms has a substituent, or when -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the hydrocarbon group.

[0017] L 4 and L 4' are preferably each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms, or a group formed by combining an alkanediyl group having 1 to 6 carbon atoms with an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH2- contained in the alkanediyl group may be replaced with -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), It is more preferably a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-alicyclic hydrocarbon group having 3 to 18 carbon atoms-alkanediyl group having 1 to 6 carbon atoms (wherein —CH— contained in the alkanediyl group may be replaced by —O— or —CO—), A single bond, an alkanediyl group having 1 to 4 carbon atoms, or *-adamantanediyl group-alkanediyl group having 1 to 4 carbon atoms (-CH2- contained in the alkanediyl group may be replaced by -O- or -CO-)- is more preferred (* represents X 1 or X 2 It represents the binding site with L. 4and LL 4' may be different groups, but are preferably the same group.

[0018] L 2 and L 3 Examples of the alkanediyl group include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group; Examples of branched alkanediyl groups include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. L 3' Examples of the alkanetriyl group include a methine group, an ethyne group, a propanetriyl group, and a butanetriyl group. L 2 and L 3 are each independently preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms, and more preferably a single bond or a methylene group. 2 and L 3 may be different groups, but are preferably the same group. L 3' is preferably an alkanetriyl group having 1 to 4 carbon atoms, more preferably a methine group or an ethyne group.

[0019] R 3 , R 4 and R 5 The hydrocarbon group having a group represented by formula (IC) in the above means a hydrocarbon group substituted with one or more groups represented by formula (IC) as substituents. The hydrocarbon group here may have -CH2- contained in the hydrocarbon group replaced with -O-, -S-, -CO- or -SO2-, or may have one or more substituents other than the group represented by formula (IC). R 3 , R 4 and R 5Examples of the hydrocarbon group in include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, and more preferably 1 to 4. Examples of the alkenyl group include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, and a nonynyl group. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl, and polycyclic cycloalkyl groups such as norbornyl and adamantyl. R 3 , R 4 and R 5 The alicyclic hydrocarbon group represented by the formula (Y1) is preferably a group represented by any one of formulas (Y1) to (Y41) (where * represents a bonding site), more preferably a group represented by any one of formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), and (Y39) to (Y41), and even more preferably a group represented by formula (Y3), (Y4), (Y9), (Y11), (Y14), (Y15), (Y16), (Y20), or (Y30). The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably 3 to 16. TIFF0007763575000012.tif77148 Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and binaphthyl. The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, as in the combined groups described below. Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups having a chain hydrocarbon group (such as tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group (such as p-cyclohexylphenyl and p-adamantylphenyl). The combined groups are: a group combining an alicyclic hydrocarbon group with a chain hydrocarbon group (an alkyl group, an alkenyl group, and / or an alkynyl group) (-CH2- contained in the chain hydrocarbon group (an alkyl group, an alkenyl group, an alkynyl group) and the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-); a group combining a chain hydrocarbon group (an alkyl group, an alkenyl group, and / or an alkynyl group) with an aromatic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group (an alkyl group, an alkenyl group, and / or an alkynyl group) may be replaced with -O-, -S-, -CO-, or -SO2-), and It represents a group formed by combining an alicyclic hydrocarbon group with an aromatic hydrocarbon group (wherein -CH2- in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-). Note that in the combination, two or more types of alicyclic hydrocarbon groups, chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups), and aromatic hydrocarbon groups may be combined. Specifically, the combined groups include: an alicyclic hydrocarbon group such as an adamantylmethyl group or a cyclohexylmethyl group - a chain hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group or the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); a chain hydrocarbon group such as a methyladamantyl group - an alicyclic hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group or the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); a chain hydrocarbon group such as a tolyl group or a xylyl group - an aromatic hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); an alicyclic hydrocarbon group such as a cyclohexylphenyl group-aromatic hydrocarbon group-* (wherein —CH— contained in the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO—); a chain hydrocarbon group such as a methylcyclohexylmethyl group-alicyclic hydrocarbon group-chain hydrocarbon group-* (wherein —CH— contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO—); an aromatic hydrocarbon group such as a benzyl group - a chain hydrocarbon group -* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-); A chain hydrocarbon group such as a tolylmethyl group-aromatic hydrocarbon group-chain hydrocarbon group-* (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) Here, * indicates the bonding site with the oxygen atom.

[0020] R 3 is preferably an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (wherein -CH- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO-, and at least one hydrogen atom contained in the aliphatic hydrocarbon group is substituted with a group represented by formula (IC)), More preferably, it is an alkyl group (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC)), or a group comprising a combination of an alicyclic hydrocarbon group and an alkyl group (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC)), More preferred is a *-alkyl group (-CH2- contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents the bonding site to an oxygen atom) or a *-alkyl group-alicyclic hydrocarbon group-alkyl group (-CH2- contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents the bonding site to an oxygen atom).

[0021] R 4 and R 5 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (however, -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and at least one of the hydrogen atoms contained in the aliphatic hydrocarbon group may be substituted by a group represented by formula (IC)), More preferably, it is a hydrogen atom, an alkyl group (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC)), or a group in which an alicyclic hydrocarbon group and an alkyl group are combined (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group may be substituted with a group represented by formula (IC)), More preferably, it is a hydrogen atom, a *-alkyl group (wherein —CH— contained in the alkyl group may be replaced by —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents a bonding site to an oxygen atom), or a *-alkyl group-alicyclic hydrocarbon group-alkyl group (wherein —CH— contained in the alkyl group may be replaced by —O— or —CO—, and at least one hydrogen atom contained in the alkyl group may be substituted with a group represented by formula (IC). * represents a bonding site to an oxygen atom), Even more preferably, it is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (wherein -CH- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO-, and at least one hydrogen atom contained in the aliphatic hydrocarbon group is substituted with a group represented by formula (IC)), Even more preferably, it is a hydrogen atom, an alkyl group (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC)), or a group in combination of an alicyclic hydrocarbon group and an alkyl group (wherein —CH— contained in the alkyl group may be replaced with —O— or —CO—, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC)), Particularly preferred is a hydrogen atom, *-alkyl group (-CH2- contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents the bonding site to an oxygen atom), or *-alkyl group-alicyclic hydrocarbon group-alkyl group (-CH2- contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents the bonding site to an oxygen atom).

[0022] The group represented by formula (IC) is as follows: TIFF0007763575000013.tif2651[In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents an integer of 0 to 2, and when u1 is 2, a plurality of R A are either the same or different. s1 represents 1 or 2. t1 represents 0 or 1, provided that the sum of s1 and t1 is 1 or 2. * denotes a binding site.]

[0023] s1 is preferably 1, t1 is preferably 1, the sum of s1 and t1 is preferably 1 or 2, and the sum of s1 and t1 is more preferably 2. The group represented by formula (IC) is preferably a group represented by the following formula: TIFF0007763575000014.tif2389

[0024] In the group represented by formula (IC), when u1 is 1, groups represented by the following formulas are also included in formula (IC). TIFF0007763575000015.tif2834R A The saturated hydrocarbon group includes an alkyl group, an alicyclic hydrocarbon group, and a combination thereof. R A Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, and more preferably 1 to 4. The alicyclic hydrocarbon group may be any of a monocyclic, polycyclic, and spirocyclic group, and examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group, and polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group.

[0025] R 3 , R 4 and R 5 Examples of the substituent other than the group represented by formula (IC) in the hydrocarbon group represented by formula (IC) include a halogen atom and a cyano group. The halogen atoms include L 1 Examples include the same as those exemplified above. Furthermore, groups encompassed by the replacement of -CH2- in a hydrocarbon group, that is, 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, and an alkylcarbonyloxy group having 2 to 13 carbon atoms, are also included in L. 1 is the same as: R 3 , R 4 and R 5 In the case where -CH2- in the hydrocarbon group represented by the formula (I) is replaced with -O-, -S-, -CO- or -SO2-, the number of carbon atoms before the replacement is the total number of carbon atoms in the hydrocarbon group. 3 , R 4 and R 5 When a substituent such as that of formula (IC) is bonded to a hydrocarbon group represented by the following formula, the number of carbon atoms before substitution is taken as the total number of carbon atoms in the hydrocarbon group.

[0026] Examples of compound (IA) include the following compounds: TIFF0007763575000016.tif232166

[0027] TIFF0007763575000017.tif213153

[0028] TIFF0007763575000018.tif229148

[0029] In the compounds represented by formulae (IA-1) to (IA-10), (IA-12), (IA-14), and (IA-16) to (IA-32), R in formula (IA) 1In the compounds represented by formula (IA-11), formula (IA-13), and formula (IA-15), in which the methyl group corresponding to R 1 Specific examples of compound (IA) include compounds in which the hydrogen atom corresponding to the formula (IA) is replaced by a methyl group. Among these, the compounds represented by formulas (IA-1) to (IA-12), (IA-17) to (IA-18), and (IA-23) to (IA-26) are preferred.

[0030] Examples of compound (IB) include the following compounds: TIFF0007763575000019.tif226144

[0031] TIFF0007763575000020.tif222156

[0032] TIFF0007763575000021.tif61140

[0033] In the compounds represented by formulas (IB-1) to (IB-10), (IB-12), (IB-14), and (IB-16) to (IB-26), R in formula (IB) 1 and R 2 In the compounds represented by formula (IB-11), formula (IB-13), and formula (IB-15), R 1 and R 2 Specific examples of compound (IB) include compounds in which the hydrogen atom corresponding to formula (IB) is replaced by a methyl group. Among these, the compounds represented by formulas (IB-1) to (IB-12), (IB-17) to (IB-18), and (IB-23) to (IB-26) are preferred.

[0034] <Method for producing compound (IA) or compound (IB)> In compound (IA), R 3 , R 4 and R 5are each independently a group represented by formula (ICI) (a compound represented by formula (IA1)), R 5 is a hydrogen atom, and R 3 and R 4 are each independently a group represented by formula (ICI) (a compound represented by formula (IA2)), R 4 and R 5 is a hydrogen atom, and R 3 The compound represented by formula (IA3) (compound represented by formula (IA3)) in which the group represented by formula (ICI) is a group represented by formula (ICI) can be produced, for example, by reacting a compound represented by formula (Ib) with carbonyldiimidazole in a solvent, and then further reacting the resulting compound with a salt represented by formula (IA-a). In compound (IB), R 3 and R 4 are each independently a group represented by formula (ICI) (a compound represented by formula (IB1)), R 4 is a hydrogen atom, and R 3 The compound in which the group represented by formula (ICI) is a group represented by formula (ICI) (the compound represented by formula (IB2)) can be produced, for example, by reacting a compound represented by formula (Ib) with carbonyldiimidazole in a solvent, and then further reacting the resulting compound with a salt represented by formula (IB-a). TIFF0007763575000022.tif2283 (In formula (ICI), s1, t1, u1 and R A have the same meanings as above. 2I represents a hydrocarbon group having 1 to 34 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. nn represents 0 or 1. * represents a bonding site with an oxygen atom. TIFF0007763575000023.tif122167

[0035] JPEG0007763575000024.jpg92159 (wherein all symbols have the same meanings as defined above.) Examples of solvents used in this reaction include chloroform and acetonitrile. When 2.6 moles or more (preferably 3.0 moles or more) of a compound represented by formula (Ib) is reacted with 1 mole of a compound represented by formula (IA-a), a compound represented by formula (IA1) is obtained as a main product. When 1.6 to 2.4 moles (preferably 1.8 to 2.2 moles) of a compound represented by formula (Ib) is reacted with 1 mole of a compound represented by formula (IA-a), a compound represented by formula (IA2) is obtained as a main product. When 0.6 to 1.4 moles (preferably 0.8 to 1.1 moles) of a compound represented by formula (Ib) is reacted with 1 mole of a compound represented by formula (IA-a), a compound represented by formula (IA3) is obtained as a main product. When 1 mole of a compound represented by formula (IB-a) is reacted with 1.6 moles or more (preferably 2.0 moles or more) of a compound represented by formula (Ib), a compound represented by formula (IB1) is obtained as a main product. When 1 mole of a compound represented by formula (IB-a) is reacted with 0.6 mole to 1.4 moles (preferably 0.8 to 1.1 moles) of a compound represented by formula (Ib), a compound represented by formula (IB2) is obtained as a main product. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 to 24 hours. Examples of the compound represented by formula (Ib) include compounds represented by the following formula, which are readily available on the market. TIFF0007763575000025.tif18125

[0036] In the compound represented by formula (IA-a), X 1 But the formula (X 1 -1), formula (X 1 -3) or formula (X 1 The compound represented by formula (I1A-a) (compound represented by formula (I1A-a)) can be produced by reacting a compound represented by formula (I1-c1) with carbonyldiimidazole in a solvent, and then reacting the resulting mixture with a compound represented by formula (Id), followed by treatment with an acid. In the compound represented by formula (IB-a), X1 and X 2 are each independently expressed by the formula (X 1 -1), formula (X 1 -3) or formula (X 1 The compound represented by formula (I1B-a) (compound represented by formula (I1B-b)) can be produced by reacting a compound represented by formula (I1-c1), a compound represented by formula (I1-c2), and carbonyldiimidazole in a solvent, and then reacting the resulting mixture with a compound represented by formula (Id), followed by treatment with an acid. TIFF0007763575000026.tif92160 (in the formula, R 1 , L 1 , and R 2 Each of the symbols has the same meaning as above. X 1A and X 2A is a single bond, a 1,4-phenylene group, or -CO-O-Ar 1 -* represents Ar 1 represents a 1,4-phenylene group. * represents the bonding site of the carbonyl group to the carbon atom. Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. Examples of the acid include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours. Compounds represented by formula (I1-c1) and formula (I1-c2) include compounds represented by the following formulas, which are readily available on the market. TIFF0007763575000027.tif40107 Examples of the compound represented by formula (Id) include compounds represented by the following formula, which are readily available on the market and can also be easily produced by known synthesis methods. TIFF0007763575000028.tif2171

[0037] In the compound represented by formula (IA-a), X 1 But the formula (X 1 -2) or formula (X 1The compound represented by formula (I2A-a) which is a group represented by formula (I2A-c1)-5) can be produced by reacting a compound represented by formula (I2-c1) with a compound represented by formula (Id) in a solvent in the presence of a base, followed by treatment with an acid. In the compound represented by formula (IB-a), X 1 and X 2 are each independently expressed by the formula (X 1 -2) or formula (X 1 The compound represented by formula (I2B-a) which is a group represented by formula (I2-c1), formula (I2-c2), and formula (Id) can be produced by reacting the compound represented by formula (I2-c1), formula (I2-c2), and formula (Id) in a solvent in the presence of a base, followed by treatment with an acid. TIFF0007763575000029.tif90158 (in the formula, R 1 , L 1 and R 2 Each of the symbols has the same meaning as above. X 1B and X 2B -Ar 1 -* or -CO-O-Ar 1 -*. Ar represents a 1,4-phenylene group. * represents the bonding site with the oxygen atom.) Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. The base includes potassium hydroxide and the like. Examples of the acid include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours. Compounds represented by formula (I2-c1) and formula (I2-c2) include compounds represented by the following formulas, which are readily available on the market. TIFF0007763575000030.tif3446

[0038] X 1 But the formula (X 1 -6) or formula (X 1The compound represented by formula (I3A-a), which is a group represented by formula (I3A-7), can be produced by reacting a compound represented by formula (I2-c1) with carbonyldiimidazole in a solvent, and then reacting the resulting mixture with a compound represented by formula (Id), followed by treatment with an acid. X 1 and X 2 are each independently expressed by the formula (X 1 -6) or formula (X 1 The compound represented by formula (I3B-a), which is a group represented by formula (I2-c1), formula (I2-c2), and carbonyldiimidazole in a solvent, can be produced by further reacting the resulting compound with a compound represented by formula (Id), followed by treatment with an acid. TIFF0007763575000031.tif112157 (wherein all symbols have the same meanings as defined above.) Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. Examples of the acid include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0039] 〔resin〕 The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") containing a structural unit derived from compound (IA) or compound (IB) (hereinafter sometimes referred to as "structural unit (I)"). Resin (A) may be a homopolymer of structural unit (I), a copolymer consisting of structural unit (I) alone, or a polymer containing one or more structural units other than structural unit (I). Examples of structural units other than the structural unit (I) include a structural unit having an acid labile group (hereinafter sometimes referred to as "structural unit (a1)"), a structural unit other than a structural unit having an acid labile group and having a halogen atom (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)"), etc. Here, the acid labile group refers to a group that has a leaving group and that is eliminated by contact with an acid to form a hydrophilic group (e.g., a hydroxy group or a carboxy group).

[0040] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid labile group contained in the resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter also referred to as group (2)). TIFF0007763575000032.tif2298[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form, together with the carbon atoms to which they are bonded, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF0007763575000033.tif2378[In formula (2), R a1' and R a2' each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2' and R a3'are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic ring may be replaced with -O- or -S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0041] R a1 , R a2 and R a3 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, and norbornyl groups, as well as the following groups (* indicates a bonding site): a1 , R a2 and R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms. TIFF0007763575000034.tif11159 Examples of groups combining an alkyl group with an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornylethyl group. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 ) includes the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding site with -O-. TIFF0007763575000035.tif30135

[0042] R a1' , R a2' and R a3' Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 Examples of the groups include the same as those listed in the above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), aralkyl groups such as a benzyl group, aromatic hydrocarbon groups having an alkyl group (e.g., a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (e.g., a p-cyclohexylphenyl group, a p-adamantylphenyl group), and aryl-cycloalkyl groups (e.g., a phenylcyclohexyl group). R a2' and R a3' are bonded to each other to form a heterocycle together with the carbon atoms to which they are attached and X, -C(R a1' )(R a3' )-XR a2' Examples of the groups include the following: * represents a binding site. TIFF0007763575000036.tif21142R a1' and R a2' At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0043] Examples of the group (1) include the following groups. In formula (1), Ra1 , R a2 and R a3 is an alkyl group, ma=0, and na=1. The group is preferably a tert-butoxycarbonyl group. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, and R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group, and R a3 is an adamantyl group, ma=0, and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF0007763575000037.tif73158

[0044] Specific examples of group (2) include the following groups: * represents a binding site. TIFF0007763575000038.tif66153

[0045] 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.

[0046] Of the (meth)acrylic monomers having an acid labile group, preferred are those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. When a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in a resist composition, the resolution of the resist pattern can be improved.

[0047] The structural unit derived from a (meth)acrylic monomer having group (1) is preferably a structural unit represented by formula (a1-0) (hereinafter, sometimes referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter, sometimes referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter, sometimes referred to as structural unit (a1-2)). These may be used alone or in combination of two or more. TIFF0007763575000039.tif39127 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or * -O-(CH2) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding site with —CO—. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group 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.

[0048] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2)k01 It is —CO—O— (wherein k01 is preferably an integer of any one of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alicyclic hydrocarbon group and combination thereof in the formula (1) include R a1 , R a2 and R a3 Examples of the groups include the same groups as those listed in the above. R a02 , R a03 , and R a04 The alkyl group in the formula (I) preferably has 1 to 6 carbon atoms, is more preferably a methyl group or an ethyl group, and is even more preferably a methyl group. R a6 and R a7 The alkyl group in the formula (I) preferably has 1 to 6 carbon atoms, is more preferably a methyl group, an ethyl group, or an isopropyl group, and is even more preferably an ethyl group or an isopropyl group. R a02 , R a03 and R a04 The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms. In the group in which an alkyl group and an alicyclic hydrocarbon group are combined, the total number of carbon atoms in the combination of the alkyl group and the alicyclic hydrocarbon group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and even more preferably an ethyl group or an isopropyl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0049] Examples of the structural unit (a1-0) include structural units represented by any one of formulas (a1-0-1) to (a1-0-12) and R a01 Examples of structural units include those in which a methyl group corresponding to the formula (a1-0-1) is replaced with a hydrogen atom, and structural units represented by any of formulas (a1-0-1) to (a1-0-10) are preferred. TIFF0007763575000040.tif67163

[0050] Examples of the structural unit (a1-1) include structural units derived from monomers described in JP-A-2010-204646. Among these, structural units represented by any one of formulas (a1-1-1) to (a1-1-4) and R in the structural unit (a1-1) are preferred. a4 A structural unit in which a methyl group corresponding to the formula (a1-1-1) is replaced with a hydrogen atom is preferred, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferred. TIFF0007763575000041.tif41113

[0051] The structural unit (a1-2) includes a structural unit represented by any one of formulas (a1-2-1) to (a1-2-6) and R a5 and structural units in which a methyl group corresponding to the formula (a1-2-2), (a1-2-5) and (a1-2-6) are preferred. TIFF0007763575000042.tif33145

[0052] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 1 to 50 mol %, preferably 3 to 40 mol %, and more preferably 5 to 30 mol %, based on all structural units in the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content of these structural units relative to all structural units of the resin (A) is: It is usually 10 to 95 mol %, preferably 15 to 80 mol %, more preferably 15 to 75 mol %, even more preferably 20 to 70 mol %, and even more preferably 20 to 65 mol %.

[0053] An example of the structural unit (a1) having the group (2) is a structural unit represented by formula (a1-4) (hereinafter, sometimes referred to as "structural unit (a1-4)"). TIFF0007763575000043.tif3867[In formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 may be the same or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form, together with the -CO- to which they are bonded, a divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group and the -CH2- contained in the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0054] R a32 and R a33 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a32 and R a33 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. Alkylcarbonyl groups include acetyl, propionyl and butyryl groups. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. R a34 , R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group consisting of a combination of these. Examples of the alkyl group and the alicyclic hydrocarbon group include R a02 , R a03 , R a04 , R a6 and R a7Examples of the alkyl group and alicyclic hydrocarbon group are the same as those in the above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon 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 (phenylcyclohexyl group, etc.), etc. In particular, R a36 Examples of the group include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these.

[0055] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 As the alkyl group, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group and an ethoxy group are more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group in R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. a36The alkyl group and alicyclic hydrocarbon group in R are preferably unsubstituted. a36 The aromatic hydrocarbon group in is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-OR a36 is eliminated on contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group.

[0056] Examples of the structural unit (a1-4) include structural units derived from monomers described in JP-A-2010-204646. Preferred are structural units represented by formulas (a1-4-1) to (a1-4-12) and R in the structural unit (a1-4). a32 and more preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-5) and formula (a1-4-10), respectively. TIFF0007763575000044.tif72168

[0057] When the resin (A) has the structural unit (a1-4), the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on the total of all structural units in the resin (A).

[0058] Examples of the structural unit derived from a (meth)acrylic monomer having the group (2) include a structural unit represented by formula (a1-5) (hereinafter, sometimes referred to as "structural unit (a1-5)"). TIFF0007763575000045.tif4354 formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 represents an integer of 1 to 4, * represents L51 represents the binding site with L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0059] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group, and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0060] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among these, the structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and the structural unit represented by formula (a1-5-1) or (a1-5-2) is more preferred. TIFF0007763575000046.tif30124

[0061] When the resin (A) has the structural unit (a1-5), the content thereof is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, even more preferably 5 to 40 mol %, and even more preferably 5 to 30 mol %, based on the total structural units of the resin (A).

[0062] Examples of the structural unit (a1) include a structural unit represented by the formula (a1-0X) (hereinafter, sometimes referred to as the structural unit (a1-0X)). TIFF0007763575000047.tif3961[In formula (a1-0X), R X1 represents a hydrogen atom or a methyl group. R x2 and R x3 each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar X1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.]

[0063] R x2 and R x3 The saturated hydrocarbon group includes alkyl groups, alicyclic hydrocarbon groups, and groups formed by combining these groups. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Ar X1 Examples of the aromatic hydrocarbon group include aryl groups having 6 to 36 carbon atoms, such as a phenyl group, a naphthyl group, and an anthryl group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably has 6 to 18 carbon atoms, and is even more preferably a phenyl group. Ar X1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. R X1 , R x2 and R x3 are each independently preferably a methyl group or an ethyl group, more preferably a methyl group.

[0064] The structural unit (a1-0X) includes the following structural units and R in the structural unit (a1-0X): X1 In this case, the structural unit (a1-0X) is preferably a structural unit (a1-0X-1) to a structural unit (a1-0X-3). TIFF0007763575000048.tif34156

[0065] When the resin (A) has the structural unit (a1-0X), the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on all monomers in the resin (A). The resin (A) may contain two or more types of structural units (a1-0X).

[0066] Further, examples of the structural unit (a1) include the following structural units. TIFF0007763575000049.tif30161

[0067] When the resin (A) contains the above structural unit, the content thereof is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %, based on the total structural units of the resin (A).

[0068] <Structural unit(s)> As the monomer from which the structural unit (s) is derived, a monomer having no acid labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using a resin having a structural unit that has a hydroxy group but no acid labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit that has a lactone ring but no acid labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and adhesion to the substrate can be improved.

[0069] <Structural unit (a2)> The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, if a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) is used as an exposure light source, it is preferable to use a structural unit (a2) having a phenolic hydroxy group as the structural unit (a2). Furthermore, if an ArF excimer laser (193 nm) or the like is used, it is preferable to use a structural unit (a2) having an alcoholic hydroxy group as the structural unit (a2), and it is more preferable to use the structural unit (a2-1) described below. The structural unit (a2) may contain one type alone or two or more types.

[0070] In the structural unit (a2), the structural unit having a phenolic hydroxy group includes a structural unit represented by formula (a2-A) (hereinafter, sometimes referred to as "structural unit (a2-A)"). TIFF0007763575000050.tif3946[In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. Aa50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - represents -R a50 represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different from each other.]

[0071] R a50 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in the formula (I) include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. R a51Examples of the alkoxy group in include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. R a51 Examples of the alkylcarbonyl group in the formula include an acetyl group, a propionyl group, and a butyryl group. R a51 The alkylcarbonyloxy group in the formula (I) includes an acetyloxy group, a propionyloxy group, and a butyryloxy group. R a51 is preferably a methyl group.

[0072] * -X a51 -(A a52 -X a52 ) nb -As * -O-, * -CO-O-, * -O-CO-, * -CO-OA a52 -CO-O-, * -O-CO-A a52 -O-, * -OA a52 -CO-O-, * -CO-OA a52 -O-CO-, * -O-CO-A a52 -O-CO-. Among them, * -CO-O-, * -CO-OA a52 -CO-O- or * -OA a52 -CO-O- is preferred.

[0073] 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.

[0074] A a50 is a single bond, * -CO-O- or * -CO-OA a52 -CO-O- is preferably a single bond, * -CO-O- or * -CO-O-CH2-CO-O- is more preferred, and is a single bond or * More preferably, it is —CO—O—.

[0075] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the o- or p-position of the benzene ring, more preferably to the p-position.

[0076] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A Nos. 2010-204634 and 2012-12577.

[0077] The structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-6) and R in the structural unit (a2-A) in the structural units represented by formulas (a2-2-1) to (a2-2-6). a50The structural unit (a2-A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula (a2-2-6), in which R in the structural unit (a2-A) is substituted with a hydrogen atom. a50 It is preferable that the structural unit is a structural unit in which a methyl group corresponding to the following formula is substituted with a hydrogen atom: TIFF0007763575000051.tif42166

[0078] When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, even more preferably 15 to 65 mol %, and still more preferably 20 to 65 mol %, based on all structural units. The structural unit (a2-A) can be incorporated into the resin (A) by treating a resin containing the structural unit (a1-4) with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into the resin (A) by polymerizing the resin using acetoxystyrene or the like and then treating the resulting resin with an alkali such as tetramethylammonium hydroxide.

[0079] An example of the structural unit (a2) having an alcoholic hydroxy group is a structural unit represented by formula (a2-1) (hereinafter, sometimes referred to as "structural unit (a2-1)"). TIFF0007763575000052.tif3956 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding site with —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0080] In equation (a2-1), L a3 is preferably -O-, -O-(CH2) f1 It is —CO—O— (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0081] 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. TIFF0007763575000053.tif49138

[0082] 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 1 to 20 mol %, and still more preferably 1 to 10 mol %, based on all structural units of the resin (A).

[0083] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring with another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

[0084] The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). One of these may be contained alone, or two or more may be contained. TIFF0007763575000054.tif46147 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or * -O-(CH2) k3 It represents a group represented by —CO—O— (k3 represents an integer of 1 to 7). L a7 is -O-, * -OL a8 -O-, * -OL a8 -CO-O-, * -OL a8 -CO-OL a9 -CO-O- or * -OL a8 -O-CO-L a9 Represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 may be the same as or different from each other.

[0085] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group. R a24 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, and preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. R a24Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

[0086] L a8 and L a9 Examples of the alkanediyl group in the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.

[0087] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or -O-(CH2) k3 In -CO-O-, k3 is a group in which k3 is any integer of 1 to 4, more preferably -O- and *-O-CH2-CO-O-, and even more preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group, or a methyl group. p1, q1 and r1 each independently represent an integer of preferably 0 to 2, and more preferably 0 or 1.

[0088] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Ra25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably —O— or * -OL a8 It is —CO—O—, and more preferably —O—, —O—CH 2 —CO—O— or —O—C 2 H 4 —CO—O—. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007763575000055.tif5330 (in the formula, R a24 , L a7 has the same meaning as above.)

[0089] Examples of the structural unit (a3) ​​include structural units derived from monomers described in JP 2010-204646 A, JP 2000-122294 A, and JP 2012-41274 A. Examples of the structural unit (a3) ​​include structural units represented by any of formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and (a3-4-1) to (a3-4-12), and in the structural units, R in formulas (a3-1) to (a3-4) a18 , R a19 , R a20 and R a24 A structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom is preferred. TIFF0007763575000056.tif115158

[0090] When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol %, preferably 10 to 65 mol %, and more preferably 10 to 60 mol %, based on all structural units in the resin (A). Furthermore, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), or the structural unit (a3-4) is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 50 mol %, based on the total structural units of the resin (A).

[0091] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007763575000057.tif2453[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO.] R 42 Examples of the saturated hydrocarbon group represented by the formula (I) include chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these groups.

[0092] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* indicates a bonding site): TIFF0007763575000058.tif11158 Examples of groups formed by combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0093] The structural unit (a4) includes at least one structural unit selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4). TIFF0007763575000059.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.

[0094] L 4a Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group.

[0095] L 3aExamples of the perfluoroalkanediyl group in the formula (I) include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3 ,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, and perfluorooctane-4,4-diyl group. L 3a Examples of the perfluorocycloalkanediyl group in the formula (I) include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

[0096] L 4a is preferably a single bond, a methylene group, or an ethylene group, and more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0097] The structural unit (a4-0) includes the structural units shown below and R in the structural unit (a4-0) in the structural units shown below. 5a The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007763575000060.tif92161

[0098] JPEG0007763575000061.jpg3654 [In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1), a41 and R a42 At least one of the groups has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007763575000062.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represents -O-, -CO-, -CO-O- or -O-CO-. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates the binding site, and the * on the right is -O-CO-R a42 represents the binding site with

[0099] R a42 Examples of the saturated hydrocarbon group in include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and groups formed by combining these groups.

[0100] Examples of the chain saturated hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; decahydronaphthyl, adamantyl, and norbornyl groups; and polycyclic alicyclic saturated hydrocarbon groups such as the following groups (* indicates a bonding site): TIFF0007763575000063.tif11158 Examples of groups formed by this combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0101] R a42 The substituent that may be possessed by may be at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3): Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF0007763575000064.tif752[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O- (* represents R a42 represents the binding site with ). A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes a binding site.] However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0102] A a45 Examples of the aliphatic hydrocarbon group in include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups; monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site): TIFF0007763575000065.tif11158 Examples of groups formed by combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0103] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably a saturated hydrocarbon group having an alkyl group having a halogen atom and / or a group represented by formula (a-g3). R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of perfluorocycloalkyl groups include a perfluorocyclohexyl group. R a42is a saturated hydrocarbon group having a group represented by formula (a-g3), the number of carbon atoms contained in the group represented by formula (a-g3) is a42 The total number of carbon atoms is preferably 15 or less, more preferably 12 or less. When the group represented by formula (a-g3) is contained as a substituent, the number thereof is preferably 1.

[0104] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 is more preferably a group represented by formula (a-g2). TIFF0007763575000066.tif874[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents *-O-CO- or *-CO-O- (* represents A a46 represents the binding site with ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 At least one of the groups has at least one halogen atom. * indicates the bonding site with the carbonyl group.]

[0105] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0106] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates the bonding site with the carbonyl group): TIFF0007763575000067.tif13163

[0107] A a41 Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and branched alkanediyl groups such as propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. A a41 Examples of the substituent in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0108] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and a group formed by combining an alkanediyl group with a divalent alicyclic hydrocarbon group. Specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. Preferably, s is 0.

[0109] In the group represented by formula (a-g1), X a42In the following examples, * and ** each represent a bonding site, and ** represents -O-CO-R a42 represents the binding site with TIFF0007763575000068.tif49154

[0110] The structural unit represented by formula (a4-1) includes the structural units shown below and R in the structural unit represented by formula (a4-1) in the structural units shown below. a41 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007763575000069.tif99142

[0111] TIFF0007763575000070.tif122140

[0112] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). TIFF0007763575000071.tif3045[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The maximum total carbon number is 21.]

[0113] L 44 The alkanediyl group of L 4a Examples of the groups include the same groups as those exemplified in R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in L 44The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.

[0114] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11). f5 The structural unit represented by formula (a4-2) also includes a structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom:

[0115] TIFF0007763575000072.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may contain a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 represents the binding site with ). A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom, 5 , A f13 and A f14 The total number of carbon atoms in a molecule is limited to 20.

[0116] L 5 The alkanediyl group in 4a Examples of the alkanediyl group include the same groups as those exemplified as the alkanediyl group.

[0117] A f13The divalent saturated hydrocarbon group optionally having a fluorine atom in the formula (I) is preferably a divalent chain saturated hydrocarbon group optionally having a fluorine atom and a divalent alicyclic saturated hydrocarbon group optionally having a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group; and perfluoroalkanediyl groups such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group. The divalent alicyclic hydrocarbon group optionally having a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

[0118] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42Among these, a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, Preferred are fluorinated alkyl groups such as a hexyl group, a perfluorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group, and a perfluorooctyl group, a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, and a perfluoroadamantylmethyl group.

[0119] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is preferably a group containing a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group containing a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group.

[0120] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a4-1'-11).f7 The structural unit represented by formula (a4-3) also includes a structural unit in which a methyl group corresponding to the following is replaced with a hydrogen atom:

[0121] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF0007763575000073.tif3858[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 -CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0122] R f22 The saturated hydrocarbon group of R a42 Examples of saturated hydrocarbon groups include the same as those represented by R f22 is preferably an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom.

[0123] In formula (a4-4), A f21 As -(CH2) j1 - is preferred, an ethylene group or a methylene group is more preferred, and a methylene group is even more preferred.

[0124] Examples of the structural unit represented by formula (a4-4) include the following structural units and structural units represented by the following formulas: f21 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007763575000074.tif88138

[0125] When the resin (A) has the structural unit (a4), the content thereof is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and even more preferably 3 to 10 mol %, based on all structural units in the resin (A).

[0126] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a group containing a linear, branched, or cyclic hydrocarbon group, and among these, the structural unit (a5) is preferably a group containing an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by formula (a5-1). TIFF0007763575000075.tif3971[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.]

[0127] R 52 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0128] L 55 The divalent saturated hydrocarbon group in the formula (I) includes a divalent saturated chain hydrocarbon group and a divalent saturated alicyclic hydrocarbon group, and is preferably a divalent saturated chain hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and an alkanediyl group such as a propanediyl group, a butanediyl group, and a pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantanediyl and norbornanediyl.

[0129] L 55 Examples of the divalent saturated hydrocarbon group represented by formula (L1-1) in which one -CH2- is replaced with -O- or -CO- include groups represented by formula (L1-1) to formula (L1-4). In the following formulae, * and ** each represent a bonding site, and * represents a bonding site to an oxygen atom. TIFF0007763575000076.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 represents the binding site with ). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0130] 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 x5is 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.

[0131] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007763575000077.tif53136

[0132] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007763575000078.tif23130

[0133] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007763575000079.tif15145

[0134] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007763575000080.tif26114

[0135] L 55is preferably a single bond or a group represented by formula (L1-1).

[0136] The structural unit (a5-1) includes the structural units shown below and R in the structural unit (a5-1) in the structural units shown below. 51 The structural unit in which a methyl group corresponding to the above is replaced with a hydrogen atom is an example. TIFF0007763575000081.tif75150

[0137] When the resin (A) has the structural unit (a5), the content thereof is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and even more preferably 3 to 15 mol %, based on all structural units in the resin (A).

[0138] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter, this may be referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and the structural unit (II) is preferably a structural unit having a sulfonate group or carboxylate group and an organic cation in the side chain, or a structural unit having a sulfonio group and an organic anion in the side chain.

[0139] The structural unit having a sulfonate group or carboxylate group and an organic cation on the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007763575000083.tif3497 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, wherein one -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group. A x1represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0140] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: a8 Examples of the alkyl group include the same alkyl groups having 1 to 6 carbon atoms which may have a halogen atom and which are represented by the following formula: A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. X III3Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination thereof. Specific examples thereof include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; butane-1,3-diyl, 2-methylpropane-1,3-diyl, and 2-methylpropane-1,3-diyl; Examples include branched alkanediyl groups such as pentane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; and divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl. Examples of saturated hydrocarbon groups in which -CH2- is replaced with -O-, -S-, or -CO- include divalent groups represented by formulae (X1) to (X53). However, the number of carbon atoms before the -CH2- in the saturated hydrocarbon group is replaced with -O-, -S-, or -CO- is 17 or less. In the following formulae, * and ** represent bonding sites, and * represents A X1 represents the binding site with TIFF0007763575000084.tif145161

[0141] 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 6represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0142] ZA + Examples of the organic cation represented by the formula (I) include organic onium cations, such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, organic benzothiazolium cations, and organic phosphonium cations. Of these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. ZA in formula (II-2-A') + represents the organic cation Z in the acid generator (B1) described below. + The same can be mentioned.

[0143] The structural unit represented by formula (II-2-A') is preferably a structural unit represented by formula (II-2-A). TIFF0007763575000085.tif38108 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms; when z is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.] R III2 , R III4 , Q a and Q bAs the perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula (I), the following Q b1 Examples include the same perfluoroalkyl groups having 1 to 6 carbon atoms as those represented by the following formula:

[0144] The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1). TIFF0007763575000086.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and ZA + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-, and wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom or a hydroxy group. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. X I2 As the divalent saturated hydrocarbon group represented by X III3 Examples of the divalent saturated hydrocarbon group include those similar to those represented by the following formula:

[0145] As the structural unit represented by formula (II-2-A-1), a structural unit represented by formula (II-2-A-2) is more preferred. TIFF0007763575000087.tif5287 [In formula (II-2-A-2), R III3 , R III5and ZA + has the same meaning as above. m and n each independently represent 1 or 2.

[0146] Examples of the structural unit represented by formula (II-2-A') include the following structural units and structural units described in WO 2012 / 050015: ZA + represents an organic cation. TIFF0007763575000088.tif79163

[0147] TIFF0007763575000089.tif82153

[0148] The structural unit having a cation having a sulfonio group in the side chain and an organic anion is preferably a structural unit represented by formula (II-1-1). TIFF0007763575000090.tif3485 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula include a phenylene group and a naphthylene group. R II2 and R II3Examples of the hydrocarbon group represented by R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. a1’ , R a2’ and R a3’ The hydrocarbon groups are the same as those in the above. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: a8 Examples of the alkyl group include the same alkyl groups having 1 to 6 carbon atoms which may have a halogen atom and which are represented by the following formula: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. III3 Examples include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms as those represented by the following formula:

[0149] The structural unit containing a cation in formula (II-1-1) includes the structural unit represented by the following formula and R II4 and structural units in which a group corresponding to the methyl group in the above formula (I) is replaced with a hydrogen atom, a fluorine atom, trifluoromethyl, or the like. TIFF0007763575000091.tif85130

[0150] A - Examples of the organic anion represented by the formula (A) include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. - The organic anion represented by the formula (B1) is preferably a sulfonate anion, and the sulfonate anion is more preferably an anion contained in a salt represented by the formula (B1) described below.

[0151] A -Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007763575000092.tif43135

[0152] Examples of sulfonylmethide anions include the following: TIFF0007763575000093.tif29123

[0153] Examples of carboxylate anions include the following: TIFF0007763575000094.tif51153

[0154] Examples of the structural unit represented by formula (II-1-1) include structural units represented by the following formulas. TIFF0007763575000095.tif161141

[0155] When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and even more preferably 3 to 10 mol %, based on the total structural units of the resin (A).

[0156] The resin (A) may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well known in the art.

[0157] The resin (A) is preferably a resin comprising the structural unit (I) and an acid labile group, further a resin comprising the structural unit (I) and the structural unit (a1), a resin comprising the structural unit (I) and the structural unit (s), a resin comprising the structural unit (I), the structural unit (a1) and the structural unit (s), a resin comprising the structural unit (I), the structural unit (a1), the structural unit (s), the structural unit (a4) and / or the structural unit (a5), a resin comprising only the structural unit (I), or It is a resin consisting only of the structural unit (I) and the structural unit (a4), and more preferably a resin consisting of the structural unit (I), the structural unit (a1), and the structural unit (s), a resin consisting of the structural unit (I) and the structural unit (s), a resin consisting of the structural unit (I), the structural unit (a4), and the structural unit (a5), a resin consisting of the structural unit (I), the structural unit (a4), or a resin consisting of the structural unit (I), the structural unit (a4), and the structural unit (a1). The content of the structural unit (I) is usually 1 to 20 mol %, preferably 2 to 10 mol %, and more preferably 2 to 6 mol %, based on all monomers in the resin (A). When the resin (A) contains structural units represented by formula (a4) and / or (a5) (hereinafter sometimes referred to as "resin (AX)"), the content of the structural unit (I) in the resin (AX) of the present invention is preferably 2 to 10 mol %, more preferably 2 to 6 mol %, based on the total of all structural units in the resin (AX) of the present invention.

[0158] The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-0X), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), and more preferably at least two selected from the group consisting of the structural unit (a1-0), the structural unit (a1-0X), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group). 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). 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).

[0159] The structural units constituting the resin (A) may be used singly or in combination of two or more, and can be produced by a known polymerization method (e.g., radical polymerization) using monomers that lead to these structural units. The content of each structural unit in the resin (A) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, even more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, even more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography, which can be measured under the analytical conditions described in the Examples.

[0160] [Resist Composition] The resist composition of the present invention preferably contains a resin (A) and an acid generator known in the resist field (hereinafter sometimes referred to as "acid generator (B)"). The resist composition of the present invention preferably further contains a resin other than the resin (A). The resist composition of the present invention preferably contains a quencher such as a salt that generates an acid with a weaker acidity than the acid generated from the acid generator (hereinafter may be referred to as "quencher (C)"), and preferably contains a solvent (hereinafter may be referred to as "solvent (E)").

[0161] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than resin (A). A resin other than resin (A) is a resin that does not contain structural unit (I). Examples of such a resin include a resin that has a structural unit having an acid labile group but does not contain structural unit (I) (hereinafter may be referred to as "resin (A2)"), a resin consisting only of structural unit (a4), and a resin consisting of structural unit (a4) and structural unit (a5) (hereinafter, a resin consisting only of structural unit (a4) and a resin consisting of structural unit (a4) and structural unit (a5) may be collectively referred to as resin (X)).

[0162] In the resin (X), the content of the structural unit (a4) is preferably 30 mol % or more, more preferably 40 mol % or more, and even more preferably 45 mol % or more, based on the total of all structural units in the resin (X).

[0163] The structural units constituting the resin (X) may be used singly or in combination of two or more, and can be produced by a known polymerization method (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in the resin (X) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weights of resin (A2) and resin (X) are each independently 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 weights of resin (A2) and resin (X) are the same as those for resin (A). When the resist composition of the present invention contains resin (A2), the content thereof is typically 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) per 100 parts by mass of resin (A). Furthermore, when the resist composition contains resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and especially preferably 1 to 8 parts by mass, relative to 100 parts by mass of resin (A).

[0164] The content of resin (A) in the resist composition is preferably 80% to 99% by mass, and more preferably 90 to 99% by mass, based on the solid content of the resist composition. Furthermore, when resins other than resin (A) are contained, the total content of resin (A) and the resins other than resin (A) is preferably 80% to 99% by mass, and more preferably 90 to 99% by mass, based on the solid content of the resist composition. The solid content of the resist composition and the resin content relative to the solid content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0165] <Acid generator (B)> The acid generator (B) may be either nonionic or ionic. Nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Anions of onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0166] The acid generator (B) may be a compound that generates an acid when exposed to radiation, as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent No. 3,914,407, or European Patent No. 126,712. Compounds produced by known methods may also be used. Two or more types of acid generator (B) may be used in combination.

[0167] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007763575000096.tif2650[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and wherein a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S(O)2- or -CO-. Z + represents an organic cation.

[0168] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by the formula (I) include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Q b1 and Q b2 and are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0169] L b1 Examples of the divalent saturated hydrocarbon group in include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and may also be a group formed by combining two or more of these groups. Specific examples include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; branched alkanediyl groups such as ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; monocyclic divalent alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0170] L b1 Examples of the divalent saturated hydrocarbon group represented by the formula (b1-1) in which one -CH2- is replaced with -O- or -CO- include groups represented by any of formulas (b1-1) to (b1-3). In the groups represented by formulas (b1-1) to (b1-3) and specific examples thereof, groups represented by formulas (b1-4) to (b1-11), * and ** represent bonding sites, and * represents the bonding site to -Y.

[0171] TIFF0007763575000097.tif26117[In formula (b1-1), L b2represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0172] In the groups represented by formulae (b1-1) to (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group. L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-. L 1 As the divalent saturated hydrocarbon group represented by the formula (b1-1) or (b1-3), in which one --CH.sub.2-- contained in the group is replaced by --O-- or --CO--, a group represented by the formula (b1-1) or (b1-3) is preferred.

[0173] Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8). TIFF0007763575000098.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b17represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L 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, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0174] Examples of the group represented by formula (b1-3) include groups represented by formulas (b1-9) to (b1-11). TIFF0007763575000099.tif23139 formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0175] In addition, in the groups represented by formulae (b1-9) to (b1-11), when a hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0176] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

[0177] Examples of the group represented by formula (b1-4) include the following. TIFF0007763575000100.tif15138

[0178] Examples of the group represented by formula (b1-5) include the following. TIFF0007763575000101.tif59138

[0179] Examples of the group represented by formula (b1-6) include the following. TIFF0007763575000102.tif28163

[0180] Examples of the group represented by formula (b1-7) include the following. TIFF0007763575000103.tif56140

[0181] Examples of the group represented by formula (b1-8) include the following. TIFF0007763575000104.tif21133

[0182] Examples of the group represented by formula (b1-2) include the following. JPEG0007763575000105.jpg29140

[0183] Examples of the group represented by formula (b1-9) include the following. TIFF0007763575000106.tif38125

[0184] Examples of the group represented by formula (b1-10) include the following. TIFF0007763575000107.tif86155

[0185] Examples of the group represented by formula (b1-11) include the following. TIFF0007763575000108.tif77150

[0186] Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulae (Y1) to (Y11) and (Y36) to (Y38). When one -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S(O)2- or -CO-, the number may be 1 or 2 or more. Examples of such groups include groups represented by formulae (Y12) to (Y35) and formulae (Y39) to (Y41).

[0187] The alicyclic hydrocarbon group represented by TIFF0007763575000109.tif77148Y is preferably a group represented by any one of formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y41), more preferably a group represented by formula (Y11), (Y15), (Y16), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) or (Y40), and even more preferably a group represented by formula (Y11), (Y15), (Y20), (Y30), (Y39) or (Y40). When the alicyclic hydrocarbon group represented by Y is a spiro ring such as those of formulae (Y28) to (Y35) and formulae (Y39) to (Y40), the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, it is preferred that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

[0188] The substituent of the methyl group represented by Y is a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents an integer of 0 to 4. -CH2- contained in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms may be replaced by -O-, -S(O)2-, or -CO-. Substituents of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents an integer of 0 to 4. -CH2- contained in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms may be replaced by -O-, -S(O)2-, or -CO-.

[0189] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain hydrocarbon group (such as tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group (such as p-cyclohexylphenyl and p-adamantylphenyl). 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, and a dodecyl group. 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 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 aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0190] Examples of Y include the following: TIFF0007763575000110.tif106163

[0191] TIFF0007763575000111.tif33149

[0192] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent, and -CH2- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S(O)2- or -CO-. Y is even more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the following formula: TIFF0007763575000112.tif86140

[0193] The anion in the salt represented by formula (B1) is preferably an anion represented by formula (B1-A-1) to formula (B1-A-55) (hereinafter, sometimes referred to as "anion (B1-A-1)" depending on the formula number).), and more preferably an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), and formula (B1-A-47) to formula (B1-A-55). TIFF0007763575000113.tif143153

[0194] TIFF0007763575000114.tif71161

[0195] TIFF0007763575000115.tif102157

[0196] TIFF0007763575000116.tif65156

[0197] TIFF0007763575000117.tif109144

[0198] TIFF0007763575000118.tif124164 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. i8 is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 has the same meaning as above. Specific examples of the sulfonate anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

[0199] Preferred anions in the salt represented by formula (B1) include the anions represented by formulas (B1a-1) to (B1a-34). TIFF0007763575000119.tif194159

[0200] TIFF0007763575000120.tif186164

[0201] Among these, anions represented by any one of formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-34) are preferred.

[0202] Z + Examples of the organic cation include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specific examples include cations represented by any of formulas (b2-1) to (b2-4) (hereinafter, sometimes referred to as "cation (b2-1)" depending on the formula number).

[0203] TIFF0007763575000121.tif75115In equations (b2-1) to (b2-4), R b4 ~R b6each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, a hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached, and -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. R b7 and R b8 each independently represents a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5; When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, multiple R b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached, and -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12represents 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 may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 and may be bonded to each other to form a ring including the -CH-CO- to which they are bonded, and -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, and when r2 is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 are the same or different, and when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. In particular, R b9 ~R b12The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, and norbornyl groups, as well as the following groups: TIFF0007763575000122.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, and more preferably has 4 to 12 carbon atoms.

[0204] Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornyl group, an isobornyl group, etc. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

[0205] Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenylyl, naphthyl, and phenanthryl. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and aromatic hydrocarbon groups having a chain hydrocarbon group of 1 to 18 carbon atoms (such as tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group of 3 to 18 carbon atoms (such as p-adamantylphenyl and p-cyclohexylphenyl) are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl.

[0206] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

[0207] R b4 and R b5 and bond to each other together with the sulfur atom to which they are bonded to form a ring which may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring, for example, the following rings. * represents a bonding site. TIFF0007763575000123.tif23144

[0208] R b9 and R b10The ring formed by these together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples thereof include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. R b11 and R b12 The ring formed by combining these may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of this ring include a 3- to 12-membered ring, and preferably a 3- to 7-membered ring. Examples include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

[0209] Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferred. Examples of the cation (b2-1) include the following cations. TIFF0007763575000124.tif104148

[0210] TIFF0007763575000125.tif31119

[0211] Examples of the cation (b2-2) include the following cations. TIFF0007763575000126.tif16130

[0212] Examples of the cation (b2-3) include the following cations. TIFF0007763575000127.tif26122

[0213] Examples of the cation (b2-4) include the following cations. TIFF0007763575000128.tif107153

[0214] Acid generator (B) is a combination of the above-mentioned sulfonate anion and the above-mentioned organic cation, and these can be combined arbitrarily. Preferred examples of acid generator (B) include a combination of an anion represented by any of formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-34) with cation (b2-1) or cation (b2-3).

[0215] The acid generator (B) is preferably one represented by formulas (B1-1) to (B1-48), of which those containing an arylsulfonium cation are preferred, and those represented by formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), and (B1-31) to (B1-48) are particularly preferred. TIFF0007763575000129.tif53128

[0216] TIFF0007763575000130.tif63141

[0217] JPEG0007763575000131.jpg74142

[0218] JPEG0007763575000132.jpg60142

[0219] TIFF0007763575000133.tif163153

[0220] TIFF0007763575000134.tif159148

[0221] In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, and still more preferably 10 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 may contain a plurality of kinds.

[0222] The acidity of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is represented by the acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid having 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 having a lower acidity than the acid generated from the acid generator (B) is preferably the weak acid inner salt (D). TIFF0007763575000135.tif112135

[0223] Examples of the weak acid inner salt (D) include the following salts. TIFF0007763575000136.tif85136

[0224] The content of the salt that generates an acid having a lower acidity than the acid generated from the acid generator contained in the resist composition is usually 0.01 to 5% by mass, preferably 0.01 to 3% by mass, in the solid content of the resist composition.

[0225] <Solvent (E)> The content of the solvent (E) in the resist composition is usually from 90 to 99.9% by mass, preferably from 92 to 99% by mass, and more preferably from 94 to 99% by mass. The content of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; etc. One type of solvent (E) may be used alone, or two or more types may be used.

[0226] <Quencher (C)> Examples of the quencher (C) include the aforementioned salts that generate an acid weaker in acidity than the acid generated from the acid generator (B), as well as basic nitrogen-containing organic compounds. The content of the quencher (C) is preferably about 0.01 to 5 mass % based on the solid content of the resist composition. The basic nitrogen-containing organic compound includes amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary amines, secondary amines, and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, Amine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine amine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane Examples of the amines include 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Preferred are aromatic amines such as diisopropylaniline, and more preferred is 2,6-diisopropylaniline. Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

[0227] <Other ingredients> The resist composition of the present invention may optionally contain components other than those described above (hereinafter, these may be referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes, can be used.

[0228] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing the resin (A) of the present invention, the acid generator (B), a salt that generates an acid weaker in acidity than the acid generated by the acid generator, and, if necessary, the resin (A2), the resin (X), the quencher (C), the solvent (E), and other components (F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing can be selected from 10 to 40°C, depending on the type of resin, the solubility of the resin in the solvent (E), and other factors. The mixing time can be selected from 0.5 to 24 hours, depending on the mixing temperature. The mixing method is also not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm.

[0229] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating is included. The resist composition can be applied to a substrate using a commonly used device such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. The composition after coating is dried to remove the solvent and form a composition layer. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. The pressure during vacuum drying is preferably 1 to 1.0 x 10 5 It is preferable that the pressure is about Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Various exposure light sources can be used, including those that emit ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm); those that convert the wavelength of laser light from a solid-state laser source (such as a YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range; and those that irradiate with electron beams or extreme ultraviolet light (EUV). In this specification, irradiation with these types of radiation may be collectively referred to as "exposure." During exposure, exposure is typically performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called post-exposure bake) to promote the deprotection reaction of the acid labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C. The heated composition layer is usually developed using a developer in a developing device. Development methods include dipping, puddling, spraying, and dynamic dispensing. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 300 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant. After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed. When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among these, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant and a small amount of water. During development, development may be stopped by replacing the organic developer with a different type of solvent. The developed resist pattern is preferably washed with a rinse solution. There are no particular limitations on the rinse solution as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0230] <Application> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and is more suitable as 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 useful for semiconductor microfabrication. [Example]

[0231] The present invention will be explained in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are by mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Device: HLC-8120GPC model (Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guard column (Tosoh) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100, MASS: Agilent LC / MSD). In the following examples, the value of this molecular ion peak is indicated by "MASS."

[0232] Example 1: Synthesis of compound represented by formula (IB-1) 20 parts of the compound represented by formula (I-1-a), 140 parts of the compound represented by formula (I-1-b), and 0.74 parts of sulfuric acid were mixed and stirred at 70°C for 10 hours, then cooled to 23°C. 300 parts of chloroform and 130 parts of a 5% aqueous sodium bicarbonate solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated to obtain the organic layer. 100 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated and the organic layer was obtained. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated residue was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., eluent: ethyl acetate) to obtain 10.22 parts of the compound represented by formula (I-1-c). TIFF0007763575000138.tif38131 0.65 parts of a compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C, and stirred at 50 ° C for 2 hours. 0.66 parts of a compound represented by formula (I-1-c) was added to the resulting mixture and stirred at 50 ° C for 2 hours. The resulting mixture was cooled to 23 ° C, and then 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C for 30 minutes, followed by separation and isolation of the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer and stirred at 23 ° C for 30 minutes, followed by separation and isolation of the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 0.52 parts of the compound represented by formula (IB-1-f). 0.52 parts of the resulting compound represented by formula (IB-1-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.41 parts of the compound represented by formula (IB-1-g). TIFF0007763575000139.tif44123 0.29 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.39 parts of a compound represented by formula (I-1-e) was added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.33 parts of a compound represented by formula (IB-1-g) was added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, after which it was cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.35 parts of the compound represented by formula (IB-1). MASS:557.3[M+H] +

[0233] Example 2: Synthesis of compound represented by formula (IA-1) TIFF0007763575000140.tif38134 0.65 parts of a compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C, and stirred at 50 ° C for 2 hours. 1.32 parts of a compound represented by formula (I-1-c) was added to the resulting mixture and stirred at 50 ° C for 2 hours. The resulting mixture was cooled to 23 ° C, and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C for 30 minutes, and then separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23 ° C for 30 minutes, and then separated to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 2) to obtain 0.68 parts of the compound represented by formula (IA-1-f). 0.68 parts of the resulting compound represented by formula (IA-1-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.52 parts of the compound represented by formula (IA-1-g). 0.44 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.59 parts of a compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.25 parts of a compound represented by formula (IA-1-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.42 parts of the compound represented by formula (IA-1). MASS:631.3[M+H] +

[0234] Example 3: Synthesis of compound represented by formula (IB-6) TIFF0007763575000142.tif86156 1.79 parts of a compound represented by formula (I-6-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C., and stirred at 50 ° C. for 2 hours. 1.24 parts of a compound represented by formula (I-1-c) was added to the resulting mixture and stirred at 50 ° C. for 2 hours. The resulting mixture was cooled to 23 ° C., and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C. for 30 minutes, and then separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 1.09 parts of the compound represented by formula (IB-6-f). 1.05 parts of the resulting compound represented by formula (IB-6-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.92 parts of the compound represented by formula (IB-6-g). 0.29 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.39 parts of a compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.80 parts of a compound represented by formula (IB-6-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.65 parts of the compound represented by formula (IB-6). MASS:945.4[M+H] +

[0235] Example 4: Synthesis of compound represented by formula (IA-6) TIFF0007763575000144.tif79149 1.79 parts of a compound represented by formula (I-6-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C., and stirred at 50 ° C. for 2 hours. 2.48 parts of a compound represented by formula (I-1-c) was added to the resulting mixture and stirred at 50 ° C. for 2 hours. The resulting mixture was cooled to 23 ° C., and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C. for 30 minutes, and then separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 2) to obtain 2.21 parts of the compound represented by formula (IA-6-f). 1.50 parts of the resulting compound represented by formula (IA-6-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23° C. for 6 hours. The resulting mixture was concentrated to obtain 1.22 parts of the compound represented by formula (IA-6-g). TIFF0007763575000145.tif62147 0.44 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.59 parts of a compound represented by formula (I-1-e) was added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.49 parts of a compound represented by formula (IA-6-g) was added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.62 parts of the compound represented by formula (IA-6). MASS:825.4[M+H] +

[0236] Example 5: Synthesis of compound represented by formula (IB-12) TIFF0007763575000146.tif47163 1.56 parts of a compound represented by formula (I-12-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C, and stirred at 50 ° C for 2 hours. 0.35 parts of a compound represented by formula (I-1-c) was added to the resulting mixture and stirred at 50 ° C for 2 hours. The resulting mixture was cooled to 23 ° C, and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C for 30 minutes, followed by separation and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23 ° C for 30 minutes, followed by separation and the organic layer was isolated. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 0.28 parts of the compound represented by formula (IB-12-f). 0.27 parts of the resulting compound represented by formula (IB-12-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.24 parts of the compound represented by formula (IB-12-g). 0.10 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.13 parts of a compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.21 parts of a compound represented by formula (IB-12-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, after which it was cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.24 parts of the compound represented by formula (IB-12). MASS:797.3[M+H] +

[0237] Example 6: Synthesis of compound represented by formula (IA-12) 1.56 parts of the compound represented by formula (I-12-d) and 20 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. Then, 1.34 parts of the compound represented by formula (I-1-e) were added, and the mixture was heated to 50°C and stirred at 50°C for 2 hours. 0.70 parts of the compound represented by formula (I-1-c) were added to the resulting mixture and stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C, and 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23°C for 30 minutes, and then separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 2) to obtain 0.39 parts of the compound represented by formula (IA-12-f). 0.27 parts of the resulting compound represented by formula (IA-12-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23° C. for 6 hours. The resulting mixture was concentrated to obtain 0.28 parts of the compound represented by formula (IA-12-g). 0.22 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.30 parts of a compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.20 parts of a compound represented by formula (IA-12-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.22 parts of the compound represented by formula (IA-12). MASS:751.3[M+H] +

[0238] Example 7: Synthesis of compound represented by formula (IB-17) 0.65 parts of a compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) were added, the mixture was heated to 50°C, and stirred at 50°C for 2 hours. 0.61 parts of a compound represented by formula (I-17-c) were added to the resulting mixture and stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C, and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 0.48 parts of the compound represented by formula (IB-17-f). 0.48 parts of the resulting compound represented by formula (IB-17-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.39 parts of the compound represented by formula (IB-17-g). 0.29 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.39 parts of the compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.31 parts of the compound represented by formula (IB-17-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.29 parts of the compound represented by formula (IB-17). MASS:543.2[M+H] +

[0239] Example 8: Synthesis of compound represented by formula (IA-17) TIFF0007763575000152.tif33129 0.65 parts of a compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 30 minutes, after which 1.34 parts of a compound represented by formula (I-1-e) was added, the mixture was heated to 50 ° C, and stirred at 50 ° C for 2 hours. 1.22 parts of a compound represented by formula (I-17-c) was added to the resulting mixture and stirred at 50 ° C for 2 hours. The resulting mixture was cooled to 23 ° C, and then 50 parts of chloroform and 20 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C for 30 minutes, followed by separation and the organic layer was isolated. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23 ° C for 30 minutes, followed by separation and the organic layer was isolated. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 2) to obtain 0.57 parts of the compound represented by formula (IA-17-f). 0.57 parts of the resulting compound represented by formula (IA-17-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. The resulting mixture was concentrated to obtain 0.46 parts of the compound represented by formula (IA-17-g). 0.44 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.59 parts of a compound represented by formula (I-1-e) were added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.23 parts of a compound represented by formula (IA-17-g) were added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, after which it was cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.34 parts of the compound represented by formula (IA-17). MASS:617.3[M+H] +

[0240] Example 9: Synthesis of compound represented by formula (IA-2) TIFF0007763575000154.tif47123 0.29 parts of a compound represented by formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes. 0.59 parts of a compound represented by formula (I-1-e) was added to the resulting mixture, and the mixture was further stirred at 50°C for 2 hours. 0.25 parts of a compound represented by formula (IA-1-g) was added to the resulting reaction mixture, and the mixture was further stirred at 50°C for 4 hours, and then cooled to 23°C. 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution were added to the resulting reaction mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. 30 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to isolate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 0.21 parts of the compound represented by formula (IA-2). MASS: 489.2 [M+H] +

[0241] Resin synthesis The compounds (monomers) used in the synthesis of the resin are shown below. TIFF0007763575000155.tif113156

[0242] TIFF0007763575000156.tif157155Hereinafter, these monomers will be referred to as "monomer (a1-1-3)" etc. according to their formula numbers.

[0243] Example 10 [Synthesis of Resin A1] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IB-1) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IB-1)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.7 × 10 3 Resin A1 was obtained in a yield of 60%. This resin A1 has the following structural units. TIFF0007763575000157.tif45164

[0244] Example 11 [Synthesis of Resin A2] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IA-1) were mixed in a molar ratio of 45:14:4:3:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IA-1)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.9 × 10 3 Resin A2 was obtained in a yield of 58%. This resin A2 has the following structural units. TIFF0007763575000158.tif43163

[0245] Example 12 [Synthesis of Resin A3] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IB-6) were mixed in a molar ratio of 45:14:4:3:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IB-6)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 8.0 × 10 3 Resin A3 was obtained in a yield of 62%. This resin A3 has the following structural units. TIFF0007763575000159.tif54161

[0246] Example 13 [Synthesis of Resin A4] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IA-6) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IA-6)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.9 × 10 3 Resin A4 was obtained in a yield of 62%. This resin A4 has the following structural units. TIFF0007763575000160.tif53162

[0247] Example 14 [Synthesis of Resin A5] Monomers (a1-1-1), (a1-0-1), (a3-2-1), and (IB-1) were used and mixed in a molar ratio of 46:11:34:9 (monomer (a1-1-1):monomer (a1-0-1):monomer (a3-2-1):monomer (IB-1)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.8 × 10 3 Resin A5 was obtained in a yield of 85%. This resin A5 has the following structural units. TIFF0007763575000161.tif46161

[0248] Example 15 [Synthesis of Resin A9] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IB-17) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IB-17)). A 1.5-fold increase in the total monomer mass of propylene glycol monomethyl ether acetate was added to form a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.4 × 10 3 Resin A9 was obtained in a yield of 62%. This resin A9 has the following structural units. TIFF0007763575000162.tif45164

[0249] Example 16 [Synthesis of Resin A10] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IA-17) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IA-17)). A 1.5-fold increase in the total monomer mass of propylene glycol monomethyl ether acetate was added to form a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.7 × 10 3 Resin A10 was obtained in a yield of 61%. This resin A10 has the following structural units. TIFF0007763575000163.tif41163

[0250] Example 17 [Synthesis of Resin A11] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IA-2) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IA-2)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.8 × 10 3 Resin A11 was obtained in a yield of 60%. This resin A11 has the following structural units. TIFF0007763575000164.tif43162

[0251] Synthesis Example 1 [Synthesis of Resin AX1] Monomers (a1-1-1), (a1-0-1), (a3-2-1), and (IX-1) were mixed in a molar ratio of 46:11:34:9 (monomer (a1-1-1):monomer (a1-0-1):monomer (a3-2-1):monomer (IX-1)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.8 × 10 3 Resin AX1 was obtained in a yield of 85%. This resin AX1 has the following structural units. TIFF0007763575000165.tif33163

[0252] Synthesis Example 2 [Synthesis of Resin AX2] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IX-1) were mixed in a molar ratio of 45:14:4:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IX-1)) of 45:14:4:3. A solution was then prepared by adding 1.5 times the total weight of the monomers of propylene glycol monomethyl ether acetate. To this solution were added initiators, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile), at 1.5 mol% and 4.5 mol%, respectively, based on the total monomer weight. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.9 × 10 3 Resin AX2 was obtained in a yield of 60%. This resin AX2 has the following structural units. TIFF0007763575000166.tif41170

[0253] Synthesis Example 3 [Synthesis of Resin AX3] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IX-2) were mixed in a molar ratio of 45:14:4:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IX-2)) of 45:14:4:3. A solution was then prepared by adding 1.5 times the total weight of the monomers of propylene glycol monomethyl ether acetate. To this solution were added initiators, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile), at 1.5 mol% and 4.5 mol%, respectively, based on the total monomer weight. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.8 × 10 3 Resin AX3 was obtained in a yield of 64%. This resin AX3 has the following structural units. TIFF0007763575000167.tif42170

[0254] Synthesis Example 4 [Synthesis of Resin AX4] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IX-3) were mixed in a molar ratio of 45:14:4:3:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IX-3)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 8.0 × 10 3 Resin AX4 was obtained in a yield of 60%. This resin AX4 has the following structural units. TIFF0007763575000168.tif39163

[0255] Synthesis Example 5 [Synthesis of Resin AX5] Monomers (a1-1-3), (a1-2-5), (a2-1-1), (a3-4-2), and (IX-4) were mixed in a molar ratio of 45:14:4:34:3 (monomer (a1-1-3):monomer (a1-2-5):monomer (a2-1-3):monomer (a3-4-2):monomer (IX-4)). A solution was then prepared by adding propylene glycol monomethyl ether acetate in an amount 1.5 times the total monomer mass. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, relative to the total monomer mass. The mixture was heated at 73°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin. This resin was then filtered. This reprecipitation procedure was repeated twice to obtain a polymer with a weight-average molecular weight of 7.6 × 10 3 Resin AX5 was obtained in a yield of 55%. This resin AX5 has the following structural units. TIFF0007763575000169.tif53161

[0256] Example 18 [Synthesis of Resin A6] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IB-12) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IB-12)]. This monomer mixture was then mixed with methyl isobutyl ketone in an amount 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 12 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, which was stirred for 6 hours and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.6 x 10. 3 Resin A6 having the following structural units was obtained in a yield of 55%. TIFF0007763575000170.tif61164

[0257] Example 19 [Synthesis of Resin A7] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IA-12) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-12)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.9 x 10. 3 Resin A7 having the following structural units was obtained in a yield of 59%. TIFF0007763575000171.tif64161

[0258] Example 20 [Synthesis of Resin A8] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IB-1) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IB-1)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 12 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.9 x 10. 3 Resin A8 having the following structural units was obtained in a yield of 48%. TIFF0007763575000172.tif42159

[0259] Example 21 [Synthesis of Resin A12] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IA-1) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-1)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers, and the mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, which was stirred for 6 hours and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.6 x 10. 3 Resin A12 having the following structural units was obtained in a yield of 64%. TIFF0007763575000173.tif42162

[0260] Example 22 [Synthesis of Resin A13] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IB-17) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IB-17)]. This monomer mixture was then mixed with methyl isobutyl ketone in an amount of 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 12 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.5 x 10. 3 Resin A13 having the following structural units was obtained in a yield of 54%. TIFF0007763575000174.tif44163

[0261] Example 23 [Synthesis of Resin A14] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IA-17) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-17)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.4 x 10. 3 Resin A14 having the following structural units was obtained in a yield of 62%. TIFF0007763575000175.tif39161

[0262] Example 24 [Synthesis of Resin A15] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IA-2) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-2)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers, and the mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, which was stirred for 6 hours and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.5 x 10. 3 Resin A15 having the following structural units was obtained in a yield of 65%. TIFF0007763575000176.tif41154

[0263] Synthesis Example 6 [Synthesis of Resin AX6] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IX-1) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-1)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 12 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, which was stirred for 6 hours and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.7 x 10. 3 Resin AX6 having the following structural units was obtained in a yield of 50%. TIFF0007763575000177.tif27152

[0264] Synthesis Example 7 [Synthesis of Resin AX7] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IX-2) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-2)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 12 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.8 x 10. 3 Resin AX7 having the following structural units was obtained in a yield of 53%. TIFF0007763575000178.tif37155

[0265] Synthesis Example 8 [Synthesis of Resin AX8] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IX-3) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-3)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.7 x 10. 3 Resin AX8 having the following structural units was obtained in a yield of 50%. TIFF0007763575000179.tif34153

[0266] Synthesis Example 9 [Synthesis of Resin AX9] Monomers (a1-4-2), (a1-1-3), (a1-2-6), and (IX-4) were used and mixed in a molar ratio of 38:29:30:3 [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-4)]. This monomer mixture was then mixed with 1.5 times the total mass of all monomers of methyl isobutyl ketone. Azobisisobutyronitrile was added as an initiator to the resulting mixture in an amount of 7 mol% based on the total moles of all monomers. The mixture was heated at 85°C for approximately 5 hours to polymerize. A p-toluenesulfonic acid solution was then added to the polymerization reaction mixture, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate a resin. The resin was then filtered and recovered, yielding a polymer with a weight-average molecular weight of approximately 5.9 x 10. 3 Resin AX9 having the following structural units was obtained in a yield of 55%. TIFF0007763575000180.tif56153

[0267] Synthesis Example 10: Synthesis of Resin X1 Monomer (a5-1-1) and monomer (a4-0-12) were used as monomers, and they were mixed in a molar ratio of 50:50 [monomer (a5-1-1):monomer (a4-0-12)]. Methyl isobutyl ketone was added in an amount 1.2 times the total amount of monomers by mass to form a solution. Azobis(2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol% relative to the total amount of monomers to this solution, and the mixture was heated at 70°C for approximately 5 hours. The resulting reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin. The resin was filtered and measured to obtain a resin having a weight-average molecular weight of 1.0 x 10 4 Resin X1 was obtained in a yield of 91%. This resin X1 has the following structural units. TIFF0007763575000181.tif3584

[0268] <Preparation of Resist Composition> The components shown in Table 1 were mixed and dissolved to obtain a mixture, which was then filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

[0269] [Table 1] TIFF0007763575000183.tif190169

[0270] <Resin> A1 to A15, AX1 to AX9, X1: Resin A1 to Resin A15, Resin AX1 to Resin AX9, Resin X1 <Acid generator (B)> B1-21: Salt represented by formula (B1-21) (synthesized according to the examples in JP 2012-224611 A) B1-22: Salt represented by formula (B1-22) (synthesized according to the examples in JP 2012-224611 A) TIFF0007763575000184.tif33108B1-43: Salt represented by formula (B1-43) (synthesized according to the examples in JP 2016-47815 A) TIFF0007763575000185.tif4284<Quencher (C)> (Salts that generate acids that are weaker in acidity than the acid generated by acid generators) D1: Synthesized by the method described in JP-A 2011-39502 TIFF0007763575000186.tif3646D2: (Tokyo Chemical Industry Co., Ltd.) TIFF0007763575000187.tif1931<Solvent: Compositions 1-5, 9-11, Comparative Compositions 1-5> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts <Solvent: Compositions 6 to 8, 12 to 15, Comparative Compositions 6 to 9> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

[0271] (ArF exposure evaluation of resist composition) An organic antireflective film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205 °C for 60 seconds to form an organic antireflective film with a thickness of 78 nm on the wafer. Next, the above resist composition was applied (spin-coated) onto this organic antireflective film so that the film thickness after drying would be 85 nm. After application, the silicon wafer was prebaked for 60 seconds at the temperature described in the "PB" column of Table 1 on a direct hot plate to form a composition layer. The silicon wafer on which the composition layer was formed was exposed using an ArF excimer stepper for immersion lithography (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3 / 4 Annular X-Y polarization) with a mask for forming a contact hole pattern (hole pitch 90 nm / hole diameter 55 nm), and the exposure dose was changed stepwise for exposure. Note that ultrapure water was used as the immersion medium. After exposure, post-exposure baking was performed for 60 seconds at the temperature described in the "PEB" column of Table 1 on a hot plate. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer at 23 °C for 20 seconds by the dynamic dispense method to produce a negative resist pattern. In the resist pattern obtained after development, the exposure dose at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

[0272] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained using as the population the measurement of the average hole diameter of the patterns formed with a mask having a hole diameter of 55 nm at 400 locations within the same wafer. The results are shown in Table 2. The numerical values in parentheses indicate the standard deviation (nm).

[0273]

Table 2

[0274] (Electron Beam Exposure Evaluation of Resist Composition) A 6-inch silicon wafer was treated with hexamethyldisilazane at 90 °C for 60 seconds on a direct hot plate. The resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 1 on a direct hot plate to form a composition layer. A contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer using an electron beam lithography machine ["ELS-F125 125 keV" manufactured by Elionix Co., Ltd.] while changing the exposure dose step by step. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 1 on a hot plate, and further paddle development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. In the resist pattern obtained after development, the exposure dose at which the hole diameter formed using the mask was 17 nm was defined as the effective sensitivity.

[0275] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a mask having a hole diameter of 17 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was determined using, as the population, the average hole diameters of the patterns formed with a mask having a hole diameter of 55 nm measured at 400 locations within the same wafer. The results are shown in Table 3. The numerical values in parentheses indicate the standard deviation (nm).

[0276]

Table 3

[0277] The resist composition of the present invention is capable of producing a resist pattern with excellent CD uniformity (CDU), and is therefore suitable for semiconductor microfabrication and extremely useful industrially.

Claims

1. A compound represented by formula (IA) or formula (IB): [In formula (IA) and formula (IB), R 1 and R 2 each independently represents a hydrogen atom or a methyl group. X 1 and X 2 are each independently a group represented by the formula (X 1 -1). (Formula (X)) 1 -1) Middle * and ** represent binding sites, and ** represents L 1 represents the binding site with L 1 is the formula (L 1 A) is a group represented by the formula (I). (Formula (L) 1 A) China L 4 *a-C1-C6 alkanediyl group-, *a-C3-C18 alicyclic hydrocarbon group -O-CO-O-CH 2 -, *a-C1-C3 alkanediyl group -CO-O-CH 2 -, *a-Alicyclic hydrocarbon group having 3 to 18 carbon atoms -CO-O-CH 2 Represents -. L 4' *b-C1-C6 alkanediyl group-, *b-C3-C18 alicyclic hydrocarbon group -O-CO-O-CH 2 -, *b-C1-C3 alkanediyl group -CO-O-CH 2 -, *b-Alicyclic hydrocarbon group having 3 to 18 carbon atoms -CO-O-CH 2 Represents -. L 2 and L 3 represents a methylene group. *a is X 1 *b represents a binding site with -OR 5 Oxygen atom or X in 2 *c represents a binding site with -OR 3 represents the bonding site with the oxygen atom in 4 represents the bonding site with the oxygen atom in R 3 is *-CO-O-CH 2 - a group represented by formula (IC), *-CO-adamantanediyl group -O-CO-O-CH 2 - a group represented by formula (IC), or *-CO-O-adamantanediyl group -O-CO-O-CH 2 - represents a group represented by formula (IC) (* represents the bonding site to the oxygen atom). R 4 and R 5 are each independently a hydrogen atom, *—CO—O—CH 2 - a group represented by formula (IC), *-CO-adamantanediyl group -O-CO-O-CH 2 - a group represented by formula (IC), or *-CO-O-adamantanediyl group -O-CO-O-CH 2 - represents a group represented by formula (IC) (* represents the bonding site to the oxygen atom). [In formula (IC), R A represents a saturated hydrocarbon group having 1 to 12 carbon atoms. u1 represents an integer of 0 to 2, and when u1 is 2, a plurality of R A are either the same or different. s1 represents 1 or 2. t1 represents 0 or 1, provided that the sum of s1 and t1 is 2. * indicates a binding site.]

2. A resin containing a structural unit in which the polymerizable C═C bond in the compound according to claim 1 is a single bond.

3. The resin according to claim 2, further comprising a structural unit having an acid labile group.

4. 4. The resin according to claim 3, wherein the structural unit having an acid labile group comprises at least one 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 are each independently —O— or *—O—(CH 2 ) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding site with —CO—. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1′ represents an integer of 0 to 3.

5. A resist composition comprising the resin according to any one of claims 2 to 4 and an acid generator.

6. 6. The resist composition according to claim 5, wherein the acid generator comprises a salt represented by formula (B1). [In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH 2 The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH 2 - is -O-, -S(O) 2 It may be replaced by - or -CO-. Z + represents an organic cation.

7. 7. The resist composition according to claim 5, further comprising a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator.

8. (1) a step of applying the resist composition according to any one of claims 5 to 7 onto a substrate; (2) a step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) a step of heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising:

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