Salt, acid generator, resist composition and method for producing resist pattern

Abstract

[Problem] The objective is to provide a salt, an acid-generating agent, and a resist composition containing the same, which can produce a resist pattern having good CD uniformity (CDU). [Solution] A salt, acid-generating agent, and resist composition represented by Formula (I). [In the formula, R1, R2, and R3 represent a hydroxyl group, -O-R10, -O-CO-O-R10, and -O-L1-CO-O-R10, respectively. R4, R5, R6, R7, R8, and R9 represent a halogen atom, a hydroxyl group, etc., respectively. L1 represents an alkanedyl group. R10 represents an acid unstable group. X1, X2, and X3 represent an oxygen atom or a sulfur atom, respectively. m1 and m7 represent integers from 0 to 5, and m2 to m6 and m8, m9 represent integers from 0 to 4, provided that 0 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, and 0 ≤ m3 + m9 ≤ 4, and at least one of m1, m2, and m3 represents an integer greater than or equal to 1. X4 represents a single bond, -CH2-, -O-, -S-, etc. Al- represents an organic anion.]

Description

Technology Field

[0001] The present invention relates to a salt for an acid generator used in the microfabrication of semiconductors, an acid generator comprising said salt, a resist composition, and a method for manufacturing a resist pattern. Background Technology

[0002] Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generating agent. Patent Document 2 describes a salt represented by the following formula, and a resist composition containing said salt as an acid generating agent. Patent Document 3 describes a salt represented by the following formula. Prior art literature

[0003] 1. Japanese Patent Publication No. 2011-186248 2. Japanese Patent Publication No. 2020-015713 3. Japanese Patent Publication No. 2011-038091 The problem to be solved

[0004] The present invention provides a salt that forms a resist pattern having better CD uniformity (CDU; Critical Dimension uniformity) than a resist pattern formed by a resist composition containing the salt. means of solving the problem

[0005] The present invention includes the following inventions. [1] Salt represented by formula (I). [In the (I) formula, R 1 , R 2 and R 3 은, each independently, hydroxyl group, -OR 10 , -O-CO-OR 10 , -OL1 -CO-OR 10 It represents. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Each independently represents a halogen atom, a hydroxyl group, a carbon-1 to 12 fluoroalkyl group, or a carbon-1 to 18 hydrocarbon group, wherein the hydrocarbon group may have a substituent, and the -CH2- included in the hydrocarbon group may be substituted with -O-, -CO-, -S-, or -SO2-. L 1 It represents an alkandyl group having 1 to 6 carbon atoms. R 10 Silver indicates an acid instability phase. X 1 , X 2 and X 3 Each represents an oxygen atom or a sulfur atom, independently. m1 represents any integer from 0 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m2 represents any integer from 0 to 4, and when m2 is 2 or greater, the values ​​within the parentheses may be the same or different. m3 represents any integer from 0 to 4, and when m3 is 2 or greater, the values ​​within the parentheses may be the same or different. m4 represents any integer from 0 to 4, and when m4 is 2 or greater, multiple R 4 They may be the same or different. m5 represents any integer from 0 to 4, and when m5 is 2 or greater, multiple R 5 They may be the same or different. m6 represents any integer from 0 to 4, and when m6 is 2 or greater, multiple R6 They may be identical or different. m7 represents any integer from 0 to 5, and when m7 is 2 or greater, multiple R 7 They may be identical or different. m8 represents any integer from 0 to 4, and when m8 is 2 or greater, multiple R 8 They may be identical or different. m9 represents any integer from 0 to 4, and when m9 is 2 or greater, multiple R 9 They may be the same or different. Provided that 0≤m1+m7≤5, 0≤m2+m8≤4, 0≤m3+m9≤4, and at least one of m1, m2, and m3 represents an integer greater than or equal to 1. X 4 - represents a single bond, -CH2-, -O-, -S-, -CO-, -SO-, or -SO2-. AI - represents an organic anion. [2] X 1 , X 2 and X 3 The salt described in [1], which is an oxygen atom. [3] R 1 , R 2 and R 3 une, each independently, -OR 10 , -O-CO-OR 10 , -OL 1 -CO-OR 10 is, R 10 The acid unstable group is the group represented by formula (1a) or the salt described in [1] or [2] represented by formula (2a). [In Equation (1a), R aa1 , R aa2 and R aa3Each independently represents a C1- to C8 alkyl group that may have substituents, a C2- to C8 alkenyl group that may have substituents, a C3- to C20 alicyclic hydrocarbon group that may have substituents, or a C6- to C18 aromatic hydrocarbon group that may have substituents, or R aa1 and R aa2 They bond with each other to form a cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms they bond to. * indicates a joining hand.] [In Equation (2a), R aa1' and R aa2' Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R aa3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2' and R aa3' are combined with each other, and the -CX that they combine a - and together with - to form a heterocyclic group having 3 to 20 carbon atoms, and -CH2- included in the hydrocarbon group and the heterocyclic group may be substituted with -O- or -S-. X a represents an oxygen atom or a sulfur atom. * indicates a joining hand.] [4] R 1 , R 2 and R 3 The salt described in [1] or [2], which is a hydroxyl group. [5] A salt described in any one of [1] to [4], wherein m1 is 0, 1 or 2, m2 is 0 or 1, and m3 is 0 or 1. [6] AI - a. A salt described in any one of [1] to [5] which is a sulfonate anion, a sulfonylimide anion, a sulfonylmide anion, or a carboxylate anion. [7] AI -is a sulfonate anion, and the sulfonate anion is a salt described in any one of [1] to [6] which is an anion represented by the formula (IA). [In the case of (IA), Q 1 and Q 2 Each represents, independently, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L 1 The element represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- included in the saturated hydrocarbon group may be substituted with -O- or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. Y 1 ...represents a methyl group that may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms that may have a substituent, wherein the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -SO2-, or -CO-. [8] An acid-generating agent containing a salt described in any one of [1] to [7]. [9] A resist composition containing an acid-generating agent and a resin having an acid-unstable group as described in [8].

[10] A resist composition described in [9] comprising at least one selected from the group consisting of a resin having an acid instability group, a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [Among Equations (a1-1) and (a1-2), L a1 and L a2 is, each independently, -O- or *-O-(CH2) k1 It represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bond loss with -CO-. Ra4 and R a5 Each represents, independently, a hydrogen atom, a halogen atom, or a carbon-1 to 6 alkyl group that may have a halogen atom. R a6 and R a7 Each represents, independently, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3.

[11] A resin having an acid instability group, comprising a structural unit represented by formula (a2-A), a resist composition as described in [9] or

[10] . [Equation (a2-A), R a50 It represents a carbon 1 to 6 alkyl group that may have a hydrogen atom, a halogen atom, or a halogen atom. R a51 It represents silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 silver, single bond, or *-X a51 -(A a52 -X a52 ) nb It represents -, and * is -R a50 This represents the bond loss with the carbon atom it bonds with. A a52 represents an alkandyl group having 1 to 6 carbon atoms. X a51 and Xa52 Each represents -O-, -CO-O-, or -O-CO- independently. nb represents 0 or 1. mb represents any integer from 0 to 4. If mb is any integer greater than or equal to 2, multiple R a51 They may be identical or different.

[12] A resist composition described in any one of [9] to

[11] that contains a salt that generates an acid that is less acidic than the acid generated from the acid generator.

[13] (1) A process of applying a resist composition described in any one of [9] to

[12] onto a substrate, (2) A process of drying the composition after application to form a composition layer, (3) Process of exposing the composition layer to light, (4) A process for heating the composition layer after exposure, and (5) A method for manufacturing a resist pattern including a process of developing a composition layer after heating. Effects of the invention

[0006] By using a resist composition using the salt of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU). Specific details for implementing the invention

[0007] In this specification, "(meth)acrylic monomer" means "at least one of acrylic monomer and methacrylic monomer." Notations such as "(meth)acrylate" and "(meth)acrylic acid" also have the same meaning. Regarding groups described in this specification that can take both a straight-chain structure and a branched structure, either is acceptable. When -CH2- contained in hydrocarbon groups, etc. is substituted with -O-, -S-, -CO-, or -SO2-, the same example shall apply to each group. "Combined group" means a group formed by combining two or more of the exemplified groups, and the valence of these groups may be appropriately changed according to the bonding type. "Derived" or "induced" indicates that a polymerizable C=C bond contained in the molecule becomes a -CC- group through polymerization. When stereoisomers exist, it includes all stereoisomers.

[0008] [Salt represented by Formula (I)] The present invention relates to a salt represented by formula (I) (hereinafter referred to as “salt(I)”). Among the salts (I), the side with a negative charge is sometimes called the “anion (I)” and the side with a positive charge is called the “cation (I)”. [In the formula, all symbols have the same meaning as those above.]

[0009] In Equation (I), R 1 , R 2 and R 3 L included in 1 As the alkanedyl group in the above, linear alkanedyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group; and Examples of branched alkanedyl groups include ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. L 1 It is preferable that the silver be an alkanedial group having 1 to 3 carbon atoms, and more preferable that it be a methylene group.

[0010] R 1 , R 2 and R 3 R included in 10 The acid instability group refers to the fact that when it comes into contact with an acid (e.g., trifluoromethanesulfonic acid), R 10 It refers to a group that detaches from the group represented by to form a carboxyl group or a hydroxyl group. As for the acid instability group, the group represented by Equation (1a) (hereinafter referred to as "acid instability group (1a)" depending on the case) and the group represented by Equation (2a) (hereinafter referred to as "acid instability group (2a)" depending on the case) are preferred. [In Equation (1a), R aa1 , R aa2 and R aa3 Each independently represents a C1- to C8 alkyl group that may have substituents, a C2- to C8 alkenyl group that may have substituents, a C3- to C20 alicyclic hydrocarbon group that may have substituents, or a C6- to C18 aromatic hydrocarbon group that may have substituents, or R aa1 and R aa2 They bond with each other to form a cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms they bond to. * indicates a joining hand.] [In Equation (2a), R aa1' and R aa2'Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R aa3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2' and R aa3' are combined with each other, and the -CX that they combine a - and together with - to form a heterocyclic group having 3 to 20 carbon atoms, and -CH2- included in the hydrocarbon group and the heterocyclic group may be substituted with -O- or -S-. X a represents an oxygen atom or a sulfur atom. * indicates a joining hand.]

[0011] R aa1 , R aa2 and R aa3 Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. aa1 , R aa2 and R aa3 The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. R aa1 , R aa2 and R aa3 Examples of alkenyl groups include the ethene group, propene group, isopropene group, butene group, isobutene group, tert-butene group, pentene group, hexene group, heptene group, octene group, isooctenene group, and nonene group. R aa1 , R aa2 and R aa3 The alicyclic hydrocarbon group of may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for instance, decahydronaphthyl, adamantyl, norbornyl groups, and the following groups (* indicates a bond loss). R aa1 , R aa2and R aa3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16, and more preferably 3 to 12. R aa1 , R aa2 and R aa3 Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. aa1 , R aa2 and R aa3 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.

[0012] Examples of substituents for an alkyl group having 1 to 8 carbon atoms that may have substituents include an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of substituents for an alkenyl group having 2 to 8 carbon atoms that may have substituents include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of substituents for an alicyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of substituents for an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and a hydrocarbon group having 3 to 20 carbon atoms. More specifically, examples include a group combining the aforementioned alkyl group and an alicyclic hydrocarbon group (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methyl norbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesithyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and a phenylcyclohexyl group.

[0013] R aa1 and R aa2 -C(R in the case where they bond with each other to form a hydrocarbon group together with carbon atoms aa1 )(R aa2 )(R aa3 The following groups may be used as examples. The alicyclic hydrocarbon group is preferably 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. * indicates a bond loss with -O-.

[0014] As the group represented by formula (1a), the 1,1,1-trialkyl group (R in formula (1a) aa1 , R aa2 and R aa3 This alkyl group, preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yl group (in formula (1a), R aa1 , R aa2 and the carbon atoms to which they bond form an adamantyl group, and R aa3 This alkyl group) and 1-(adamantan-1-yl)-1,1-dialkyl group (in Formula (1a), R aa1 and R aa2 ga is an alkyl group, and R aa3 Examples include the Adamantine group.

[0015] R aa1' , R aa2' and R aa3' Examples of hydrocarbon groups include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. The alkyl group and the alicyclic hydrocarbon group are R aa1 , R aa2 and R aa3 One can cite the same thing as the example given. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, and phenanthryl groups. Examples of combined groups include a group combining the aforementioned alkyl group and an alicyclic hydrocarbon group (e.g., cycloalkylalkyl group or alkylcycloalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methyl norbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, etc. R aa2' and R aa3' They bond with each other, and the carbon atoms and X that bond to them a When forming a heterocyclic group with, -C(R aa1' )(R aa2' )-X a -(R aa3' The following examples can be cited as ). * indicates a combined hand. R aa1' and R aa2' It is desirable that at least one of them be a hydrogen atom.

[0016] Specific examples of acid instability (1a) include the following. * indicates a bond loss.

[0017] Specific examples of acid instability periods (2a) include the following periods. * indicates a bond loss. R 1 , R 2 and R 3 The bonding positions of are, respectively X 1 , X 2 and X 3 Regarding the bonding position of, it may be any of the o, m, or p positions. Among these, X1 , X 2 and X 3 Regarding the bonding position of, it is desirable to be bonded at the p position. R 1 , R 2 and R 3 은, each independently, hydroxyl group, -OR 10 or -OL 1 -CO-OR 10 It is desirable that it is.

[0018] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 The fluoroalkyl group having 1 to 12 carbon atoms represents an alkyl group having 1 to 12 carbon atoms having a fluorine atom, and examples include a perfluoroalkyl group having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), and 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms of the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of hydrocarbon groups having 1 to 18 carbon atoms include chain-type hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and Specifically, examples of alicyclic hydrocarbon groups include the groups shown below. The bonding site can be at any location. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, and norbornyl groups. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, biphenyl groups, anthryl groups, phenanthryl groups, non-naphthyl groups, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0019] As groups formed by combination, a group combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group-alkanedyl group-*, alkyl group-aromatic hydrocarbon group-*, wherein the -CH2- included in the alkandyl group and alkyl group may be substituted with -O-, -CO-, -S-, or -SO2-), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group-alkanedyl group-*, alkyl group-alicyclic hydrocarbon group-*, wherein the -CH2- included in the alkandyl group and alkyl group may be substituted with -O-, -CO-, -S-, or -SO2-), a group combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic Examples include hydrocarbon groups—aromatic hydrocarbon groups—*). * indicates the bonding site. Examples of aromatic hydrocarbon groups—alkanedyl groups—include aralkyl groups such as benzyl and phenethyl groups. Examples of alkyl groups—aromatic hydrocarbon groups—* include tolyl groups, xylyl groups, coumenyl groups, etc. Examples of alicyclic hydrocarbon groups—alkanedyl groups—* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, and 1-(adamantan-1-yl)-1-methylethyl group. Examples of alkyl groups-alpha-cyclohydrocarbon groups-* include cycloalkyl groups having alkyl groups such as methylcyclohexyl groups, dimethylcyclohexyl groups, and 2-alkyladamantan-2-yl groups. Examples of aromatic hydrocarbon groups—alicyclic hydrocarbon groups—* include phenylcyclohexyl groups. Examples of alicyclic hydrocarbon groups—aromatic hydrocarbon groups—* include cyclohexylphenyl groups. In addition, in the combination, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may each be combined. In addition, any group may be bonded to a benzene ring. As groups substituted with -CH2-, -O-, -CO-, -S-, or -SO2- included in the hydrocarbon group, the following are: a hydroxyl group (a group substituted with -CH2- or -O- included in the methyl group), a carboxyl group (a group substituted with -CH2- or -O- included in the ethyl group), a thiol group (a group substituted with -CH2- or -S- included in the methyl group), an alkoxy group (a group substituted with -CH2- or -O- at any position included in the alkyl group), an alkoxycarbonyl group (a group substituted with -CH2- or -O- at any position included in the alkyl group), an alkylthio group (a group substituted with -CH2- or -S- at any position included in the alkyl group), an alkylcarbonyl group (a group substituted with -CH2- or -CO- at any position included in the alkyl group), and an alkylcarbonyloxy group (a group at any position included in the alkyl group Examples include groups substituted with -CH2-CH2- or -CO-O-), alkylsulfonyl groups (groups substituted with -CH2- or -SO2- at any position within the alkyl group), cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, aromatic hydrocarbon groups-carbonyloxy groups, and groups formed by combining two or more of these groups.

[0020] Examples of alkoxy groups include alkoxy groups having 1 to 17 carbon atoms, such as methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, octyloxy groups, 2-ethylhexyloxy groups, nonyloxy groups, decyloxy groups, undecyloxy groups, phenyloxy groups, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkyl thio groups include alkyl thio groups having 1 to 17 carbon atoms, such as methyl thio groups, ethyl thio groups, propyl thio groups, butyl thio groups, etc. The number of carbon atoms of the alkyl thio group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group, and alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the aforementioned alkyl group or alkoxy group. As for the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 17 carbon atoms may be used, such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. As for the alkylcarbonyl group, an alkylcarbonyl group having 2 to 18 carbon atoms may be used, such as an acetyl group, a propionyl group, and a butyryl group, etc. As for the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 17 carbon atoms may be used, such as an acetyloxy group, a propionyloxy group, or a butyryloxy group, etc. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkyl carbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as cyclohexyloxy groups. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as cyclohexylmethoxy groups. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy groups. Examples of aromatic hydrocarbon-carbonyloxy groups include aromatic hydrocarbon-carbonyloxy groups having 7 to 17 carbon atoms, such as benzoyloxy groups. As for the alkylsulfonyl group, an alkylsulfonyl group having 1 to 17 carbon atoms may be used, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4.

[0021] In addition, the groups in which the -CH2- included in the alicyclic hydrocarbon group is substituted with -O- or -CO- may be the groups shown below. The bonding site may be at any position. The positions of -O- or -CO- of the groups shown below may be substituted with -S- or -SO2-, respectively. In cases where -CH2- included in a hydrocarbon group is substituted with -O-, -CO-, -S-, or -SO2-, the number of carbons before substitution is taken as the total number of carbons in the hydrocarbon group. In addition, the number may be one or two or more.

[0022] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of substituents that the hydrocarbon group may have include halogen atoms, cyano groups, and alkyl groups having 1 to 12 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-). As for halogen atoms, the same group as the one described above can be cited. Examples of alkyl groups having 1 to 12 carbon atoms include the same group as described above. As a substituent, when -CH2- included in the alkyl group is substituted with -O- or -CO-, the number of carbons before substitution is taken as the total number of carbons of the alkyl group. Examples of substituted groups include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, etc. Examples of alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups include groups identical to those described above. The hydrocarbon group may have one or more substituents. X 1 It is preferable that it be an oxygen atom. X 2 It is preferable that it be an oxygen atom. X 3 It is preferable that it be an oxygen atom. X 1 , X 2 and X 3 The bonding position of is, S + Regarding the bonding position of, it may be any of the o, m, or p positions. Among these, S + Regarding the bonding position, it is preferable to bond at the p position or the m position, and it is more preferable to bond at the p position. m1 is preferably 0, 1, or 2, more preferably 1 or 2, and even more preferably 1. It is preferable that m2 be 0 or 1. It is preferable that m3 be 0 or 1. m4 is preferably 0, 1, 2, or 4, and more preferably 0. m5 is preferably 0 or 1, and more preferably 0. m6 is preferably 0 or 1, and more preferably 0. m7 is preferably 0, 1, or 2, and more preferably 0. m8 is preferably 0 or 1, and more preferably 0. m9 is preferably 0 or 1, and more preferably 0. When m1 is 1, m2 and m3 may each be 0, either one may be 1, or both may be 1. Among these, when m1 is 1, it is preferable that both m2 and m3 are 0 or 1.

[0023] R 4 , R 5 and R 6It is preferable that each is independently a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-), more preferable that it is a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-), and even more preferable that it is an alkyl group having 1 to 4 carbon atoms. R 7 , R 8 and R 9 It is preferable that each is independently a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-), more preferable that it is a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-), even more preferable that it is a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the -CH2- included in the alkyl group may be substituted with -O- or -CO-), and even more preferable that it is a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxyl group, or a methoxy group.

[0024] Examples of cations (I) include the following cations.

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] AI - Examples of organic anions represented by Al include sulfonate anions, sulfonylimide anions, sulfonylmette anions, and carboxylate anions. - The organic anion represented by is preferably, independently, a sulfonic acid anion, and more preferably, independently is an anion represented by formula (IA). [In the case of (IA), Q 1 and Q 2 Each represents, independently, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L 1 The element represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- included in the saturated hydrocarbon group may be substituted with -O- or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. Y 1 ...represents a methyl group that may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms that may have a substituent, wherein the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -SO2-, or -CO-.

[0031] In the case of anion represented by formula (IA), if -CH2- included in a saturated hydrocarbon group is substituted with -O- or -CO-, the number of carbons before substitution is taken as the number of carbons in the saturated hydrocarbon group. Additionally, if -CH2- included in a licyclic hydrocarbon group is substituted with -O-, -SO2- or -CO-, the number of carbons before substitution is taken as the number of carbons in the licyclic hydrocarbon group.

[0032] Q 1 and Q 2Examples of perfluoroalkyl groups having 1 to 6 carbon atoms include trifluoromethyl groups, perfluoroethyl groups, perfluoropropyl groups, perfluoroisopropyl groups, perfluorobutyl groups, perfluorosec-butyl groups, perfluorotert-butyl groups, perfluoropentyl groups, and perfluorohexyl groups. Q 1 and Q 2 It is preferable that each be an independent fluorine atom or a trifluoromethyl group, and more preferable that all be fluorine atoms.

[0033] L 1 Examples of divalent saturated hydrocarbon groups in this case include straight-chain alkanedil groups, branched alkanedil groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and groups formed by combining two or more of these groups. Specifically, linear alkanedyl groups such as methylene groups, ethylene groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nonane-1,9-diyl groups, decane-1,10-diyl groups, undecane-1,11-diyl groups, dodecane-1,12-diyl groups, tridecane-1,13-diyl groups, tetradecane-1,14-diyl groups, pentadecane-1,15-diyl groups, hexadecane-1,16-diyl groups, and heptadecane-1,17-diyl groups; Branched alkanedyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; A monocyclic divalent alicyclic saturated hydrocarbon group that is a cycloalkanedyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as nobonan-1,4-diyl group, nobonan-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0034] L 1 As a group in which -CH2- included in the divalent saturated hydrocarbon group represented by is substituted with -O- or -CO-, for example, a group represented by any one of formulas (b1-1) to (b1-3). Furthermore, in the group represented by formulas (b1-1) to (b1-3) and the groups represented by formulas (b1-4) to (b1-11), which are specific examples thereof, * and ** represent bonding sites, and * represents -Y 1 It represents the bonding hand with.

[0035] [Equation (b1-1), L b2 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, wherein the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- included 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. Among the formulas (b1-2), L b4 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5...represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, wherein the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- included 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. Among the formulas (b1-3), L b6 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. L b7 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, wherein the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- included 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.

[0036] In the group represented by formulas (b1-1) to (b1-3), when -CH2- included in the saturated hydrocarbon group is substituted with -O- or -CO-, the number of carbons before substitution is taken as the number of carbons of the corresponding saturated hydrocarbon group. As a divalent saturated hydrocarbon group, L b1 Examples include the same as the divalent saturated hydrocarbon group. L b2 It is preferably a single bond. L b3 It is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4The is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms included in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. L b5 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms, preferably single bonds or divalent saturated hydrocarbon groups having 1 to 4 carbon atoms. L b7 The group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, wherein the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- included in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-. L 1 As a group in which -CH2- included in the divalent saturated hydrocarbon group represented by is substituted with -O- or -CO-, a group represented by formula (b1-1) or formula (b1-3) is preferred.

[0037] Examples of the apparatus represented by Equation (b1-1) include the apparatus represented by Equations (b1-4) to (b1-8), respectively. [Essence (b1-4), L b8 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. Among the formulas (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- included in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-. L b10It represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms included in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. Among the equations (b1-6), L b11 It represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms included in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12 The total number of carbon atoms is 21 or less. Among the formulas (b1-7), L b13 It 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 the -CH2- included in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-. L b15 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms included in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. Among the formulas (b1-8), L b16 It represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- included in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-. L b17It represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atoms included in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0038] L b8 It is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 It is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 The carbon 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 It is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 It is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 The 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 It is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 It is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18The 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.

[0039] Examples of the apparatus represented by Equation (b1-3) include the apparatus represented by Equations (b1-9) to (b1-11), respectively. [Essence (b1-9), L b19 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkyl carbonyloxy group. The -CH2- included in the alkyl carbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atoms included in the alkyl carbonyloxy group may be substituted with a hydroxyl group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. Among the equations (b1-10), L b21 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23It represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkyl carbonyloxy group. The -CH2- included in the alkyl carbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atoms included in the alkyl carbonyloxy group may be substituted with a hydroxyl group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. Among the equations (b1-11), L b24 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 It represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkyl carbonyloxy group. The -CH2- included in the alkyl carbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atoms included in the alkyl carbonyloxy group may be substituted with a hydroxyl group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0040] In addition, for the groups represented by formulas (b1-9) through (b1-11), if a hydrogen atom included in a saturated hydrocarbon group is substituted with an alkyl carbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the corresponding saturated hydrocarbon group.

[0041] Examples of alkyl carbonyloxy groups include acetyloxy groups, propionyloxy groups, butyryloxy groups, cyclohexylcarbonyloxy groups, and adamantylcarbonyloxy groups.

[0042] The following can be cited as the instrument represented by Equation (b1-4).

[0043] The following can be cited as the instrument represented by Equation (b1-5).

[0044] The following are examples of the apparatus represented by Equation (b1-6).

[0045] The following can be cited as the instrument represented by Equation (b1-7).

[0046] The following can be cited as the instrument represented by Equation (b1-8).

[0047] The following can be cited as the instrument represented by Equation (b1-2).

[0048] The following can be cited as the instrument represented by Equation (b1-9).

[0049] The following are examples of the apparatus represented by Equation (b1-10).

[0050] The following can be cited as the instrument represented by Equation (b1-11).

[0051] Y 1Examples of cyclic hydrocarbon groups represented by the formulas (Y1) to (Y11) and (Y36) to (Y38) can be cited. Y 1 When the -CH2- included in the alicyclic hydrocarbon group represented by is substituted with -O-, -S(O)2-, or -CO-, the number may be one or two or more. Examples of such groups include those represented by formulas (Y12) to (Y35) and (Y39) to (Y43). * represents L 1 It indicates the connection site with.

[0052] Y 1 The alicyclic hydrocarbon group represented by is preferably a group represented by any one of the formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y43), more preferably a group represented by the formulas (Y11), (Y15), (Y16), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42), or (Y43), and even more preferably a group represented by the formulas (Y11), (Y15), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42), or (Y43). Y 1 In the case where the alicyclic hydrocarbon group represented by is a spiro-ring such as formulas (Y28) to (Y35), (Y39), (Y40), (Y42), and (Y43), it is preferable that the alkandyl group between two oxygen atoms has one or more fluorine atoms. In addition, among the alkandyl groups included in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

[0053] Y 1 As substituents for the methyl group represented by, halogen atoms, hydroxyl groups, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -(CH2) ja -CO-OR b1 or -(CH2) ja -O-CO-R b1 Gi (among food, 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 any integer from 0 to 4. The -CH2- included in the alkyl group and the alicyclic hydrocarbon group may be substituted with -O-, -S(O)2-, or -CO-, and the hydrogen atoms included in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be substituted with a hydroxyl group or a fluorine atom.) etc. Y 1 As substituents for the alicyclic hydrocarbon group represented by, a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms that may be substituted with a hydroxyl group (the -CH2- included in the said alkyl group may be substituted with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-OR b1 or -(CH2) ja -O-CO-R b1 Gi (among food, 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 any integer from 0 to 4. The -CH2- included in the alkyl group and the alicyclic hydrocarbon group may be substituted with -O-, -S(O)2-, or -CO-, and the hydrogen atoms included in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be substituted with a hydroxyl group or a fluorine atom.) etc.

[0054] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, dimethylcyclohexyl groups, cycloheptyl groups, cyclooctyl groups, norbornyl groups, adamantyl groups, etc. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include methylcyclohexyl groups, dimethylcyclohexyl groups, etc. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, and phenanthryl groups. Aromatic hydrocarbon groups may have chain hydrocarbon groups or alicyclic hydrocarbon groups. Examples of aromatic hydrocarbon groups having chain hydrocarbon groups include tolyl groups, xylyl groups, coumenyl groups, mesithyl groups, p-ethylphenyl groups, p-tert-butylphenyl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Examples of aromatic hydrocarbon groups having alicyclic hydrocarbon groups include p-cyclohexylphenyl groups and p-adamantylphenyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10. Examples of alkyl groups include, for instance, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkyl groups substituted with hydroxyl groups include hydroxyalkyl groups such as hydroxymethyl and hydroxyethyl groups. Examples of aralkyl groups include benzyl groups, phenethyl groups, phenylpropyl groups, naphthylmethyl groups, and naphthylethyl groups. Examples of groups in which -CH2- included in the alkyl group is substituted with -O-, -SO2-, or -CO- include alkoxy groups, alkylsulfonyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, or a combination thereof. Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, heptyloxy groups, octyloxy groups, decyloxy groups, and dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkylsulfonyl groups include methylsulfonyl groups, ethylsulfonyl groups, propylsulfonyl groups, etc. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups, ethoxycarbonyl groups, butoxycarbonyl groups, etc. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkyl carbonyl groups include acetyl groups, propionyl groups, and butyryl groups. The number of carbon atoms in the alkyl carbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkyl carbonyloxy groups include acetyloxy groups, propionyloxy groups, butyryloxy groups, etc. The number of carbon atoms in the alkyl carbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include, for instance, a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkyl carbonyl group, and a group combining an alkoxy group and an alkyl carbonyloxy group. Examples of groups combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, and ethoxymethyl groups. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkoxy groups combined with alkoxy groups include alkoxyalkoxy groups such as methoxymethoxy groups, methoxymethoxy groups, ethoxymethoxy groups, and ethoxymethoxy groups. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkyl carbonyl group include alkoxyalkyl carbonyl groups such as methoxyacetyl groups, methoxypropionyl groups, ethoxyacetyl groups, and ethoxypropionyl groups. The number of carbon atoms in the alkoxyalkyl carbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of groups combining an alkoxy group and an alkyl carbonyloxy group include alkoxyalkyl carbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, and ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkyl carbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of groups in which -CH2- included in a cycloaliphatic hydrocarbon group is substituted with -O-, -SO2-, or -CO-, etc. include groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43).

[0055] Y 1 The following can be cited as examples.

[0056] Y 1 The alicyclic hydrocarbon group is preferably a carbon alicyclic hydrocarbon group having 3 to 24 carbon atoms that may have substituents, more preferably a carbon alicyclic hydrocarbon group having 3 to 20 carbon atoms that may have substituents, even more preferably a carbon alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have substituents, even more preferably a carbon alicyclic hydrocarbon group substituted with a hydroxyl group, and even more preferably an adamantyl group that may have substituents, wherein the -CH2- constituting the alicyclic hydrocarbon group or the adamantyl group may be substituted with -CO-, -SO2-, or -CO-. 1 The group is, specifically preferably, an adamantyl group, a hydroxyadamantyl group, an oxodamantyl group, or a group represented by formula (Y42), formula (Y100) to formula (Y114), and particularly preferably, a hydroxyadamantyl group, an oxodamantyl group, a group including these, or a group represented by formula (Y42), formula (Y100) to formula (Y114).

[0057] As for the anion represented by formula (IA), an anion represented by formulas (IA-1) to (IA-59) [hereinafter referred to as "anion (IA-1)" etc. according to the formula number] is preferred, and an anion represented by any one of formulas (IA-1) to (IA-4), formula (IA-9), formula (IA-10), formula (IA-24) to (IA-33), formula (IA-36) to (IA-40), formula (IA-47) to (IA-59) is more preferred.

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] Here, R i2 ~R i7 Each is independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. i8 The group is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a hydrocarbon group having 5 to 12 carbon atoms, or a group formed by a combination thereof, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 It is a single bond or an alkanedial group having 1 to 4 carbon atoms. Q 1 and Q 2 represents the same meaning as above. Specifically, anions represented by formula (IA) include the anions described in Japanese Patent Publication No. 2010-204646.

[0064] Preferably, as an anion represented by formula (IA), anions represented by formulas (Ia-1) to (Ia-38), respectively, may be used.

[0065]

[0066]

[0067] Among these, an anion represented by any one of formulas (Ia-1) to (Ia-3), formula (Ia-7) to (Ia-19), and formula (Ia-22) to (Ia-38) is preferred. AI - Examples of sulfonylimide anions represented as such include the following. AI - Examples of sulfonylmethane anions represented by the following can be cited. AI - Examples of carboxylate anions represented by the following include:

[0068] As a specific example of salt (I), a salt formed by arbitrarily combining the above-mentioned cation and anion can be cited. Specific examples of salt (I) are shown in Table 1 below. In Table 1 below, each symbol represents a symbol attached to a structure representing the anion and cation described above, and “∼” indicates that each of the salt (I) and the anion (I) corresponds. For example, salt (I-1) represents a salt composed of an anion represented by formula (Ia-1) and a cation represented by formula (Ic-1), salt (I-2) represents a salt composed of an anion represented by formula (Ia-2) and a cation represented by formula (Ic-1), and salt (I-39) represents a salt composed of an anion represented by formula (Ia-1) and a cation represented by formula (Ic-2). [Table 1]

[0069] Among these, salt (I) is preferably a salt formed by combining an anion represented by any one of formulas (Ia-1) to (Ia-4), (Ia-7) to (Ia-11), (Ia-14) to (Ia-30), and (Ia-35) to (Ia-38) with a cation represented by any one of formulas (Ic-1) to (Ic-70), and specifically, salt (I-1) to salt (I-4), salt (I-7) to salt (I-11), salt (I-14) to salt (I-30), salt (I-35) to salt (I-38), salt (I-39) to salt (I-42), salt (I-45) to salt (I-49), salt (I-52) to salt (I-68), salt (I-73) to salt (I-76), Salt (I-77)–Salt (I-80), Salt (I-83)–Salt (I-87), Salt (I-90)–Salt (I-106), Salt (I-111)–Salt (I-114), Salt (I-115)–Salt (I-118), Salt (I-121)–Salt (I-125), Salt (I-128)–Salt (I-144), Salt (I-149)–Salt (I-152), Salt (I-153)–Salt (I-156), Salt (I-159)–Salt (I-163), Salt (I-166)–Salt (I-182), Salt (I-187)–Salt (I-190), Salt (I-191)–Salt (I-194), Salt (I-197)–Salt (I-201), Salt (I-204)–Salt (I-220), Salt (I-225)–Salt (I-228), Salt (I-229)–Salt (I-232), Salt (I-235)–Salt (I-239), Salt (I-242)–Salt (I-258), Salt (I-263)–Salt (I-266), Salt (I-267)–Salt (I-270), Salt (I-273)–Salt (I-277), Salt (I-280)–Salt (I-296), Salt (I-301)–Salt (I-304), Salt (I-305)–Salt (I-308), Salt (I-311)–Salt (I-315), Salt (I-318)–Salt (I-334), Salt (I-339)–Salt (I-342), Salt (I-343) to Salt (I-346), Salt (I-349) to Salt (I-353), Salt (I-356) to Salt (I-372), Salt (I-377) to Salt (I-380), Salt (I-381) to Salt (I-384), Salt (I-387) to Salt (I-391), Salt (I-394) to Salt (I-410), Salt (I-415) to Salt (I-418),Salt (I-419)–Salt (I-422), Salt (I-425)–Salt (I-429), Salt (I-432)–Salt (I-448), Salt (I-453)–Salt (I-456), Salt (I-457)–Salt (I-460), Salt (I-463)–Salt (I-467), Salt (I-470)–Salt (I-486), Salt (I-491)–Salt (I-494), Salt (I-495)–Salt (I-498), Salt (I-501)–Salt (I-505), Salt (I-508)–Salt (I-524), Salt (I-529)–Salt (I-532), Salt (I-533)–Salt (I-536), Salt (I-539)–Salt (I-543), Salt (I-546)–Salt (I-562), Salt (I-567)–Salt (I-570), Salt (I-571)–Salt (I-574), Salt (I-577)–Salt (I-581), Salt (I-584)–Salt (I-600), Salt (I-605)–Salt (I-608), Salt (I-609)–Salt (I-612), Salt (I-615)–Salt (I-619), Salt (I-622)–Salt (I-638), Salt (I-643)–Salt (I-646), Salt (I-647)–Salt (I-650), Salt (I-653)–Salt (I-657), Salt (I-660)–Salt (I-676), Salt (I-681)–Salt (I-684), Salt (I-685)–Salt (I-688), Salt (I-691)–Salt (I-695), Salt (I-698)–Salt (I-714), Salt (I-719)–Salt (I-722), Salt (I-723)–Salt (I-726), Salt (I-729)–Salt (I-733), Salt (I-736)–Salt (I-752), Salt (I-757)–Salt (I-760), Salt (I-761)–Salt (I-764), Salt (I-767)–Salt (I-771), Salt (I-774)–Salt (I-790), Salt (I-795)–Salt (I-798), Salt (I-799)–Salt (I-802), Salt (I-805)–Salt (I-809), Salt (I-812)–Salt (I-828), Salt (I-833)–Salt (I-836), Salt (I-837)–Salt (I-840), Salt (I-843)–Salt (I-847), Salt (I-850)–Salt (I-866), Salt (I-871)–Salt (I-874), Salt (I-875)–Salt (I-878), Salt (I-881)–Salt (I-885), Salt (I-888)–Salt (I-904), Salt (I-909)–Salt (I-912),Salt (I-913)–Salt (I-916), Salt (I-919)–Salt (I-923), Salt (I-926)–Salt (I-942), Salt (I-947)–Salt (I-950), Salt (I-951)–Salt (I-954), Salt (I-957)–Salt (I-961), Salt (I-964)–Salt (I-980), Salt (I-985)–Salt (I-988), Salt (I-989)–Salt (I-992), Salt (I-995)–Salt (I-999), Salt (I-1002)–Salt (I-1018), Salt (I-1023)–Salt (I-1026), Salt (I-1027)–Salt (I-1030), Salt (I-1033)–Salt (I-1037), Salt (I-1040)–Salt (I-1056), Salt (I-1061)–Salt (I-1064), Salt (I-1065)–Salt (I-1068), Salt (I-1071)–Salt (I-1075), Salt (I-1078)–Salt (I-1094), Salt (I-1099)–Salt (I-1102), Salt (I-1103)–Salt (I-1106), Salt (I-1109)–Salt (I-1113), Salt (I-1116)–Salt (I-1132), Salt (I-1137)–Salt (I-1140), Salt (I-1141)–Salt (I-1144), Salt (I-1147)–Salt (I-1151), Salt (I-1154) ~ Salt (I-1170), Salt (I-1175) ~ Salt (I-1178), Salt (I-1179) ~ Salt (I-1182), Salt (I-1185) ~ Salt (I-1189), Salt (I-1192) ~ Salt (I-1208), Salt (I-1213) ~ Salt (I-1216), Salt (I-1217) ~ Salt (I-1220), Salt (I-1223) ~ Salt (I-1227), Salt (I-1230) ~ Salt (I-1246), Salt (I-1251) ~ Salt (I-1254), Salt (I-1255) ~ Salt (I-1258), Salt (I-1261) ~ Salt (I-1265), Salt (I-1268) ~ Salt (I-1284), Salt (I-1289) ~ Salt (I-1292), Salt (I-1293) ~ Salt (I-1296), Salt (I-1299) ~ Salt (I-1303), Salt (I-1306) ~ Salt (I-1322), Salt (I-1327) ~ Salt (I-1330), Salt (I-1331) ~ Salt (I-1334), Salt (I-1337) ~ Salt (I-1341), Salt (I-1344) ~ Salt (I-1360), Salt (I-1365) ~ Salt (I-1368),Salt (I-1369) ~ Salt (I-1372), Salt (I-1375) ~ Salt (I-1379), Salt (I-1382) ~ Salt (I-1398), Salt (I-1403) ~ Salt (I-1406), Salt (I-1407) ~ Salt (I-1410), Salt (I-1413) ~ Salt (I-1417), Salt (I-1420) ~ Salt (I-1436), Salt (I-1441) ~ Salt (I-1444), Salt (I-1445) ~ Salt (I-1448), Salt (I-1451) ~ Salt (I-1455), Salt (I-1458) ~ Salt (I-1474), Salt (I-1479) ~ Salt (I-1482), Salt (I-1483) ~ Salt (I-1486), Salt (I-1489) ~ Salt (I-1493), Salt (I-1496) ~ Salt (I-1512), Salt (I-1517) ~ Salt (I-1520), Salt (I-1521) ~ Salt (I-1524), Salt (I-1527) ~ Salt (I-1531), Salt (I-1534) ~ Salt (I-1550), Salt (I-1555) ~ Salt (I-1558), Salt (I-1559) ~ Salt (I-1562), Salt (I-1565) ~ Salt (I-1569), Salt (I-1572) ~ Salt (I-1588), Salt (I-1593) ~ Salt (I-1596), Salt (I-1597) ~ Salt (I-1600), Salt (I-1603) ~ Salt (I-1607), Salt (I-1610) ~ Salt (I-1626), Salt (I-1631) ~ Salt (I-1634), Salt (I-1635) ~ Salt (I-1638), Salt (I-1641) ~ Salt (I-1645), Salt (I-1648) ~ Salt (I-1664), Salt (I-1669) ~ Salt (I-1672), Salt (I-1673) ~ Salt (I-1676), Salt (I-1679) ~ Salt (I-1683), Salt (I-1686) ~ Salt (I-1702), Salt (I-1707) ~ Salt (I-1710), Salt (I-1711)–Salt (I-1714), Salt (I-1717)–Salt (I-1721), Salt (I-1724)–Salt (I-1740), Salt (I-1745)–Salt (I-1748), Salt (I-1749)–Salt (I-1752), Salt (I-1755)–Salt (I-1759), Salt (I-1762)–Salt (I-1778), Salt (I-1783)–Salt (I-1786), Salt (I-1787)–Salt (I-1790), Salt (I-1793)–Salt (I-1797), Salt (I-1800)–Salt (I-1816),Salt (I-1821)–Salt (I-1824), Salt (I-1825)–Salt (I-1828), Salt (I-1831)–Salt (I-1835), Salt (I-1838)–Salt (I-1852), Salt (I-1857)–Salt (I-1862), Salt (I-1863)–Salt (I-1866), Salt (I-1869)–Salt (I-1873), Salt (I-1876)–Salt (I-1892), Salt (I-1897)–Salt (I-1900), Salt (I-1901)–Salt (I-1904), Salt (I-1907)–Salt (I-1911), Salt (I-1914)–Salt (I-1930), Salt (I-1935)–Salt (I-1938), Salt (I-1939)–Salt (I-1942), Salt (I-1945)–Salt (I-1949), Salt (I-1952)–Salt (I-1968), Salt (I-1973)–Salt (I-1976), Salt (I-1977)–Salt (I-1980), Salt (I-1983)–Salt (I-1987), Salt (I-1990)–Salt (I-2006), Salt (I-2011)–Salt (I-2014), Salt (I-2015)–Salt (I-2018), Salt (I-2021)–Salt (I-2025), Salt (I-2028)–Salt (I-2044), Salt (I-2049)–Salt (I-2052), Salt (I-2053)–Salt (I-2056), Salt (I-2059)–Salt (I-2063), Salt (I-2066)–Salt (I-2082), Salt (I-2087)–Salt (I-2090), Salt (I-2091)–Salt (I-2094), Salt (I-2097)–Salt (I-2101), Salt (I-2104)–Salt (I-2120), Salt (I-2125)–Salt (I-2128), Salt (I-2129)–Salt (I-2132), Salt (I-2135)–Salt (I-2139), Salt (I-2142)–Salt (I-2158), Salt (I-2163)–Salt (I-2166), Salt (I-2167)–Salt (I-2170), Salt (I-2173)–Salt (I-2177), Salt (I-2180)–Salt (I-2196), Salt (I-2201)–Salt (I-2204), Salt (I-2205)–Salt (I-2208), Salt (I-2211)–Salt (I-2215), Salt (I-2218)–Salt (I-2234), Salt (I-2239)–Salt (I-2242), Salt (I-2243)–Salt (I-2246), Salt (I-2249)–Salt (I-2253),Salt (I-2256)–Salt (I-2272), Salt (I-2277)–Salt (I-2280), Salt (I-2281)–Salt (I-2284), Salt (I-2287)–Salt (I-2291), Salt (I-2294)–Salt (I-2310), Salt (I-2315)–Salt (I-2318), Salt (I-2319)–Salt (I-2322), Salt (I-2325)–Salt (I-2329), Salt (I-2332)–Salt (I-2348), Salt (I-2353)–Salt (I-2356), Salt (I-2357)–Salt (I-2360), Salt (I-2363)–Salt (I-2367), Salt (I-2370)–Salt (I-2386), Salt (I-2391)–Salt (I-2394), Salt (I-2395)–Salt (I-2398), Salt (I-2401)–Salt (I-2405), Salt (I-2408)–Salt (I-2424), Salt (I-2429)–Salt (I-2432), Salt (I-2433)–Salt (I-2436), Salt (I-2439)–Salt (I-2443), Salt (I-2446)–Salt (I-2462), Salt (I-2467)–Salt (I-2470), Salt (I-2471)–Salt (I-2474), Salt (I-2477)–Salt (I-2481), Salt (I-2484)–Salt (I-2500), Salt (I-2505)–Salt (I-2508), Salt (I-2509)–Salt (I-2512), Salt (I-2515)–Salt (I-2519), Salt (I-2522)–Salt (I-2538), Salt (I-2543)–Salt (I-2546), Salt (I-2547)–Salt (I-2550), Salt (I-2553)–Salt (I-2557), Salt (I-2560)–Salt (I-2576), Salt (I-2581)–Salt (I-2584), Salt (I-2585)–Salt (I-2588), Salt (I-2591)–Salt (I-2595), It is preferable that salt (I-2598) ~ salt (I-2614), salt (I-2619) ~ salt (I-2622), salt (I-2623) ~ salt (I-2626), salt (I-2629) ~ salt (I-2633), salt (I-2636) ~ salt (I-2652), salt (I-2657) ~ salt (I-2660).

[0070] <Method for manufacturing salt(I)> Salt (I) can be prepared by reacting the salt represented by formula (Ia) and the salt represented by formula (Ib) in a solvent. [In the formula, all symbols represent the same meaning as above. R A , R B and R C Each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or, R A , R B and R C It may become one to form an aromatic ring. R D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is typically 15°C to 80°C, and the reaction time is typically 0.5 to 24 hours.

[0071] Examples of salts represented by formula (Ib) include salts represented by the following formula. These salts can be easily manufactured by the same method as the method described in Japanese Patent Publication No. 2011-116747 and Japanese Patent Publication No. 2016-047815, or by a known manufacturing method.

[0072] In salt (Ia), R 1 , R 2 and R 3 This, -OL 1 -CO-OR 10 A phosphorus salt (a salt represented by formula (I-a1)) can be prepared by reacting a salt represented by formula (Ic) and a compound represented by formula (Id) in a solvent in the presence of a base catalyst. [In the formula, all symbols have the same meaning as those above.] Examples of bases include potassium carbonate, potassium iodide, pyridine, and triethylamine. Examples of solvents include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is typically 15°C to 80°C, and the reaction time is typically 0.5 to 24 hours.

[0073] Compounds represented by formula (Id) include, for example, compounds shown below, which are readily available from the market and can also be readily manufactured by known methods.

[0074] The salt represented by formula (Ic) can be prepared by reacting the salt represented by formula (Ie), the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) in a solvent in the presence of a catalyst. [In the formula, all symbols have the same meaning as those above.] Examples of catalysts include potassium carbonate and sodium hydride. Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is typically 15°C to 100°C, and the reaction time is typically 0.5 to 24 hours.

[0075] Examples of salts represented by formula (Ie) include salts represented by the following formula, which are readily available in the market.

[0076] Examples of compounds represented by formula (I-f1), compounds represented by formula (I-f2), and compounds represented by formula (I-f3) include the compounds shown below, which are readily available from the market.

[0077] The salt represented by formula (Ic) may also be prepared by reacting the salt represented by formula (Ie), the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) in a solvent in the presence of potassium carbonate, and then treating with acid. [In the formula, all symbols represent the same meaning as above. R ac indicates the acid instability phase.] Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is typically 15°C to 100°C, and the reaction time is typically 0.5 to 24 hours. Examples of acids include p-toluenesulfonic acid and hydrochloric acid.

[0078] Examples of compounds represented by formula (I-f4), compounds represented by formula (I-f5), and compounds represented by formula (I-f6) include the compounds shown below, which are readily available from the market.

[0079] In salt (Ia), R 1 , R 2 and R 3 This, -OR 10 A phosphorus salt (a salt represented by formula (I-a3)) can be prepared by reacting a salt represented by formula (Ic) and a compound represented by formula (I-d3) in a solvent in the presence of a base catalyst. [In the formula, all symbols have the same meaning as those above.] Examples of bases include sodium hydroxide and potassium hydroxide. Examples of solvents include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is typically 15°C to 80°C, and the reaction time is typically 0.5 to 24 hours.

[0080] Compounds represented by formula (I-d3) include, for example, compounds shown below, which are readily available from the market and can also be readily manufactured by known methods.

[0081] In salt (Ia), R 1 , R 2 and R 3 This, -O-CO-OR 10 The phosphorus salt (the salt represented by formula (I-a4)) can be prepared by reacting the salt represented by formula (Ic) and the compound represented by formula (I-d3) in a solvent in the presence of carbonyldiimidazole. [In the formula, all symbols have the same meaning as those above.] Examples of solvents include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is typically 15°C to 80°C, and the reaction time is typically 0.5 to 24 hours.

[0082] [Acid generator] The acid generating agent of the present invention contains salt (I). It may contain one type of salt (I) or two or more types of salt (I). The acid generating agent of the present invention may contain, in addition to the salt (I), an acid generating agent known in the field of resists (hereinafter referred to as “acid generating agent (B)”). The acid generating agent (B) may be used alone or in combination of two or more types.

[0083] The acid-generating agent (B) may be either nonionic or ionic. Examples of nonionic acid-generating agents include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oximesulfonate, N-sulfonylimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Examples of ionic acid-generating agents include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmethane anions.

[0084] As an acid generating agent (B), compounds that generate acid by radiation as described in Japanese Patent Publication No. S63-26653, Japanese Patent Publication No. S55-164824, Japanese Patent Publication No. S62-69263, Japanese Patent Publication No. S63-146038, Japanese Patent Publication No. S63-163452, Japanese Patent Publication No. S62-153853, Japanese Patent Publication No. S63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. may be used. In addition, compounds prepared by known methods may be used. Two or more types of acid generating agents (B) may be used in combination.

[0085] The acid generating agent (B) is preferably a fluorine-containing acid generating agent, and more preferably a salt represented by formula (B1) (hereinafter referred to as “acid generating agent (B1)”). [Equation (B1), Q b1 and Q b2 Each represents, independently, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 The element represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- included in the saturated hydrocarbon group may be substituted with -O- or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. Y represents a methyl group that may have a substituent or a carbon alicyclic hydrocarbon group having 3 to 24 carbon atoms that may have a substituent, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S(O)2- or -CO-. Z1 + represents an organic cation.

[0086] Q in Equation (B1) b1 , Q b2 , L b1 and Y are Q in the above-described equation (IA), respectively. 1 , Q 2 , L 1 and Y 1 One can cite the same thing as. As for the sulfonic acid anion in formula (B1), the same as the anion represented by formula (IA) can be cited.

[0087] Z1 ＋Examples of organic cations include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, examples include cations represented by any one of formulas (b2-1) to (b2-4) (hereinafter referred to as “cation (b2-1)”, etc., according to the formula number).

[0088] In equations (b2-1) to (b2-4), R b4 ~R b6 Each represents, independently, 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 included in the chain hydrocarbon group may be substituted with a hydroxyl 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 included in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group; and a hydrogen atom included in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, or a It may be substituted with an alkoxy group of 1 to 12. R b4 and R b5 They may combine with each other to form a ring with the sulfur atom to which they combine, and the -CH2- included in the ring may be substituted with -O-, -S- or -CO-. R b7 and R b8Each independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent any one integer from 0 to 5. When m2 is 2 or greater, multiple R b7 may be the same or different, and when n2 is 2 or greater, multiple R b8 It 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 a hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 The silver atoms may combine with each other to form a ring with the sulfur atoms they combine with, and the -CH2- included in the ring may be substituted with -O-, -S-, or -CO-. R b11 It represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, a hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 The group represents a chain hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein the hydrogen atoms included in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms included in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkyl carbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 They may combine with each other to form a ring including the -CH-CO- they combine with, and the -CH2- included in the ring may be substituted with -O-, -S- or -CO-. Rb13 ~R b18 Each independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. L b31 It represents silver, sulfur atoms, or oxygen atoms. o2, p2, s2, and t2 each independently represent any one integer from 0 to 5. q2 and r2 each independently represent any one integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or greater, multiple R b13 is identical or different, and when p2 is 2 or more, multiple R b14 is identical or different, and when q2 is 2 or greater, multiple R b15 is identical or different, and when r2 is 2 or more, multiple R b16 is identical or different, and when s2 is 2 or more, multiple R b17 is identical or different, and when t2 is 2 or greater, multiple R b18 It is the same or different.

[0089] Aliphatic hydrocarbon groups refer to chain hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and alkyl groups of 2-ethylhexyl. In particular, R b9 ~R b12 The chain hydrocarbon group is preferably 1 to 12 carbon atoms. As a monocyclic hydrocarbon group, it may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups. In particular, R b9 ~R b12 The alicyclic hydrocarbon group is preferably 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

[0090] Examples of alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl norbornyl group, 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 of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. A fluoroalkyl group refers to an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, or a perfluorobutyl group. The number of carbon atoms in the fluoroalkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4.

[0091] Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, biphenylyl groups, naphthyl groups, and phenanthyl groups. Aromatic hydrocarbon groups may have chain hydrocarbon groups or alicyclic hydrocarbon groups, and examples include aromatic hydrocarbon groups having chain hydrocarbon groups (tolyl groups, xylyl groups, coumenyl groups, mesithyl groups, p-ethylphenyl groups, p-tert-butylphenyl groups, 2,6-diethylphenyl groups, 2-methyl-6-ethylphenyl groups, etc.) and aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl groups, p-adamantylphenyl groups, etc.). In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl groups. Examples of chain hydrocarbon groups in which a hydrogen atom is substituted with an aromatic hydrocarbon group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, and aralkyl group.

[0092] Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, heptyloxy groups, octyloxy groups, decyloxy groups, and dodecyloxy groups. Examples of alkyl carbonyl groups include acetyl groups, propionyl groups, and butyryl groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkyl carbonyloxy groups include methyl carbonyloxy group, ethyl carbonyloxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butyl carbonyloxy group, sec-butyl carbonyloxy group, tert-butyl carbonyloxy group, pentyl carbonyloxy group, hexyl carbonyloxy group, octyl carbonyloxy group, and 2-ethylhexyl carbonyloxy group.

[0093] R b4 and Rb5 The ring formed by combining with each other to become one with the sulfur atom to which they combine may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated rings. Examples of this ring include a ring having 3 to 18 carbon atoms, and preferably a ring having 4 to 18 carbon atoms. In addition, the ring containing the sulfur atom may be a ternary to twelve-membered ring, and preferably a ternary to seven-membered ring, such as the rings below. * indicates a bonding site.

[0094] R b9 and R b10 The ring formed by this can be any ring among monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated. Examples of this ring include ternary to twelve-membered rings, and preferably ternary to seven-membered rings. Examples include thiolan-1-ium rings (tetrahydrothiophenium rings), thian-1-ium rings, 1,4-oxathian-4-ium rings, etc. R b11 and R b12 The ring formed by combining can be any of the following: monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated rings. Examples of this ring include ternary to twelve-membered rings, and preferably ternary to seven-membered rings. Examples include oxocycloheptane rings, oxocyclohexane rings, oxonorbonane rings, oxodamantan rings, etc.

[0095] Among the cations (b2-1) to cations (b2-4), preferably, it is the cation (b2-1). Examples of cations (b2-1) include the following cations.

[0096]

[0097] Examples of cations (b2-2) include the following cations.

[0098] Examples of cations (b2-3) include the following cations.

[0099] Examples of cations (b2-4) include the following cations.

[0100] The acid generating agent (B) is a combination of the aforementioned anion and the aforementioned organic cation, and these can be combined arbitrarily. Preferably, the acid generating agent (B) may be a combination of an anion represented by any one of formulas (Ia-1) to (Ia-3), formulas (Ia-7) to (Ia-16), formula (Ia-18), formula (Ia-19), formula (Ia-22) to (Ia-38), and a cation (b2-1), a cation (b2-3), or a cation (b2-4).

[0101] As for the acid generating agent (B), it is preferably represented by formulas (B1-1) to (B1-56). Among these, it is preferable to include an arylsulfonium cation, and it is particularly preferable to represent formulas (B1-1) to (B1-3), formulas (B1-5) to (B1-7), formulas (B1-11) to (B1-14), formulas (B1-20) to (B1-26), formula (B1-29), and formulas (B1-31) to (B1-56).

[0102]

[0103]

[0104]

[0105]

[0106] When salt (I) and acid generating agent (B) are contained as acid generating agents, the ratio of the content of salt (I) and acid generating agent (B) (mass ratio; salt (I): acid generating agent (B)) is typically 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, even more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85:15.

[0107] [Resist Composition] The resist composition of the present invention comprises an acid generating agent containing a salt (I) and a resin having an acid unstable group (hereinafter referred to as “resin (A)”). Herein, “acid unstable group” means a group having a leaving group, wherein the leaving group is removed upon contact with acid, and the constituent unit is converted into a constituent unit having a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). The resist composition of the present invention preferably contains a quencher (hereinafter referred to as “quencher (C”)) such as a salt that generates an acid that is less acidic than the acid generated from an acid generator, and preferably contains a solvent (hereinafter referred to as “solvent (E”)).

[0108] <Acid generator> In the resist composition of the present invention, the total content of the acid generating agent is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, even more preferably 3 parts by mass or more and 40 parts by mass or less, and even more preferably 3 parts by mass or more and 35 parts by mass or less, with respect to 100 parts by mass of the resin (A) described below.

[0109] <Suzy (A)> The resin (A) has a structural unit having an acid instability group (hereinafter referred to as "structural unit (a1)"). The resin (A) additionally preferably includes a structural unit other than the structural unit (a1). Examples of structural units other than the structural unit (a1) include a structural unit not having an acid instability group (hereinafter referred to as "structural unit(s)"), a structural unit other than the structural unit (a1) and structural unit(s) (e.g., a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4)"), a structural unit having a non-detached hydrocarbon group described later (hereinafter referred to as "structural unit (a5)"), and other structural units derived from monomers known in the relevant field.

[0110] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer having an acid instability group (hereinafter referred to as “monomer (a1)”). The acid instability group included in the resin (A) is preferably the group represented by Formula (1) (hereinafter also referred to as Group (1)) and / or the group represented by Formula (2) (hereinafter also referred to as Group (2)). [In Equation (1), R a1 , R a2 and R a3 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof, or R a1 and R a2 They bond with each other to form a cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms they bond to. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates a joining hand. [Equation (2), R a1' and R a2' Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2' and R a3' They bond together to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atoms and X to which they bond, and the -CH2- included in the hydrocarbon group and the heterocyclic group may be substituted with -O- or -S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * indicates a joining hand.]

[0111] R a1 , R a2 and R a3 Examples of alkyl groups in this include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. R a1 , R a2 and R a3 Examples of alkenyl groups in this include the ethene group, propene group, isopropene group, butene group, isobutene group, tert-butene group, pentene group, hexene group, heptene group, octene group, isooctenene group, and nonene group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in [the example] may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl groups, and the following groups (* indicates a bond loss). R a1 , R a2 and R a3The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16. R a1 , R a2 and R a3 Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, and phenanthryl groups. Examples of combined groups include a group combining the above-described alkyl group and an alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesithyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, etc. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R in the case where they combine to form alicyclic hydrocarbon groups a1 )(R a2 )(R a3 The following groups may be used as examples. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * indicates a bond loss with -O-.

[0112] R a1' , R a2' and R a3' Examples of hydrocarbon groups in this include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 One can cite the same thing as the example given. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, and phenanthryl groups. Examples of combined groups include a group combining the aforementioned alkyl group and an alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesithyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. R a2' and R a3' When they bond with each other to form a heterocyclic group with the carbon atom they bond to and X, -C(R a1' )(R a2' )-XR a3' As for, the following examples can be given. * indicates a combined hand. R a1' and R a2' It is desirable that at least one of them be a hydrogen atom. na' is preferably 0.

[0113] As for the device (1), the following devices can be cited. R in Equation (1) a1 , R a2 and R a3 This is an alkyl group, a group in which ma=0 and na=1. As the corresponding group, a tert-butoxycarbonyl group is preferred. In Equation (1), R a1 , R a2 a, they combine with the carbon atom to form an adamantyl group, and R a3 This is an alkyl group, where ma=0 and na=1. In Equation (1), R a1 and R a2Each is independently an alkyl group, and R a3 This is an adamantyl group, with ma=0 and na=1. Specifically, the following examples can be given as examples of the device (1). * indicates a joint.

[0114] Specific examples of the device (2) include the following devices. * indicates a joint.

[0115] The monomer (a1) is preferably a monomer having an acid unstable group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid unstable group.

[0116] Among the (meth)acrylic monomers having acid instability groups, preferably those having a cycloaliphatic hydrocarbon group having 5 to 20 carbon atoms can be used. If a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as a cycloaliphatic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0117] As a structural unit derived from a (meth)acrylic monomer having a group (1), preferably, a structural unit represented by formula (a1-0) (hereinafter referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter referred to as structural unit (a1-2)). More preferably, at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or two or more may be used in combination. [Among Equation (a1-0), Equation (a1-1) and Equation (a1-2), La01 , L a1 and L a2 is, each independently, -O- or *-O-(CH2) k1 It represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bond loss with -CO-. R a01 , R a4 and R a5 Each represents, independently, a hydrogen atom, a halogen atom, or a carbon-1 to 6 alkyl group that may have a halogen atom. R a02 , R a03 and R a04 Each represents, independently, an alkyl group having 1 to 8 carbon atoms, a hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. R a6 and R a7 Each represents, independently, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer between 0 and 3.

[0118] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. L a01 , L a1 and L a2 is, preferably, an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably an integer from 1 to 4, more preferably 1), and more preferably an oxygen atom. Ra02 , R a03 , R a04 , R a6 and R a7 In the case of alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these, R of Formula (1) a1 , R a2 and R a3 One can cite the same type of energy as exemplified by. R a02 , R a03 , and R a04 The alkyl group in the above is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7 The alkyl group in the above is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, isopropyl group, or t-butyl group, and even more preferably an ethyl group, isopropyl group, or t-butyl group. R a6 and R a7 The alkenyl group in the above is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, propenyl group, isopropenyl group, or butenyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, and more preferably 6 to 10. It is preferable that the total number of carbon atoms in the combination of the alkyl group and the alicyclic hydrocarbon group be 18 or less. It is preferable that the total number of carbon atoms in the combination of the alkyl group and the aromatic hydrocarbon group is 18 or less. R a02 and R a03 The group is preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group, or a naphthyl group. R a04 The group is preferably an alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. R a6 and R a7 The group is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms; more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group, or a naphthyl group; and even more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, or a phenyl group. m1 is preferably an integer from 0 to 3, and more preferably 0 or 1. n1 is preferably an integer from 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0119] As a structural unit (a1-0), for example, a structural unit represented by any one of equations (a1-0-1) to (a1-0-18), and R in the structural unit (a1-0). a01 Examples of structural units in which a methyl group corresponding to is substituted with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group may be used, and a structural unit represented by any one of formulas (a1-0-1) to (a1-0-10), formula (a1-0-13), and formula (a1-0-14) is preferred.

[0120] As for the structural unit (a1-1), for example, a structural unit derived from a monomer described in Japanese Patent Publication No. 2010-204646 may be cited. Among these, a structural unit represented by any one of formulas (a1-1-1) to (a1-1-7) and R in the structural unit (a1-1) a4 A structural unit in which a methyl group corresponding to is substituted with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is preferred, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferred.

[0121] As a structural unit (a1-2), a structural unit represented by any one of equations (a1-2-1) to (a1-2-14), and R in the structural unit (a1-2). a5 Examples of structural units in which a methyl group corresponding to is substituted with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group may be used, and a structural unit represented by any one of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-14) is preferred.

[0122] When the resin (A) contains a structural unit (a1-0), the content is typically 5 to 60 mol% with respect to the total structural unit of the resin (A), preferably 5 to 50 mol%, and more preferably 10 to 40 mol%. When the resin (A) includes structural units (a1-1) and / or structural units (a1-2), the total content of these is typically 10 to 95 mol% with respect to the total structural units of the resin (A), preferably 15 to 90 mol%, more preferably 20 to 85 mol%, even more preferably 25 to 75 mol%, and even more preferably 30 to 75 mol%.

[0123] As a structural unit having a (2) in a structural unit (a1), a structural unit represented by formula (a1-4) (hereinafter referred to as “structural unit (a1-4)”) can be cited. [Equation (a1-4), R a32 It represents a hydrogen atom, a halogen atom, or a carbon-1 to 6-alkyl group that may have a halogen atom. R a33 It represents silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a30 silver, single bond, or *-X a31 -(A a32 -X a32 ) nc It represents -, and * is -R a32 It represents the bonding site with the carbon atom to which it bonds. A a32 represents an alkandyl group having 1 to 6 carbon atoms. X a31 and X a32 Each represents -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents any integer from 0 to 4. If la is any integer greater than or equal to 2, multiple R a33 They may be identical or different. R a34 and R a35 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 Silver, representing a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36They bond with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they bond, and the -CH2- contained in the said hydrocarbon group and the said divalent hydrocarbon group may be substituted with -O- or -S-.

[0124] R a32 and R a33 Examples of halogen atoms in this include fluorine atoms, chlorine atoms, and bromine atoms. R a32 Examples of alkyl groups having 1 to 6 carbon atoms that may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, and perfluorohexyl group. R a32 A hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. R a33 Examples of alkyl groups in this include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. R a33 Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, sec-butoxy groups, tert-butoxy groups, pentyloxy groups, and hexyloxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a33Examples of the alkoxyalkyl groups include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy groups include methoxymethoxy groups, methoxymethoxy groups, ethoxymethoxy groups, ethoxymethoxy groups, propoxymethoxy groups, isopropoxymethoxy groups, butoxymethoxy groups, sec-butoxymethoxy groups, and tert-butoxymethoxy groups. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and a methoxyethyl group or an ethoxyethyl group is more preferable. R a33 Examples of alkyl carbonyl groups include acetyl groups, propionyl groups, and butyryl groups. An alkyl carbonyl group having 2 to 3 carbon atoms is preferred, and an acetyl group is more preferred. R a33 Examples of alkyl carbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. An alkyl carbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a33 Silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms are preferred, a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxymethoxy group, or an ethoxymethoxy group are more preferred, and a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxymethoxy group are even more preferred.

[0125] *-X a31 -(A a32 -X a32 ) nc As -, *-O-, *-CO-O-, *-O-CO-, *-CO-OAa32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 Examples include -O-CO-. Among them, *-CO-O- and *-CO-OA a32 -CO-O- or *-OA a32 -CO-O- is desirable.

[0126] Examples of alkanedyl groups include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, pentane-1,4-diyl groups, and 2-methylbutane-1,4-diyl groups. A a32 It is preferable that it be a methylene group or an ethylene group.

[0127] A a30 Silver, single bond, *-CO-O- or *-CO-OA a32 It is preferable that it be -CO-O-, more preferable that it be a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferable that it be a single bond or *-CO-O-.

[0128] la is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl groups, and the following groups (* indicates the bonding site). Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, and phenanthryl groups. Examples of combined groups include a group combining the aforementioned alkyl group and an alicyclic hydrocarbon group (e.g., a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesithyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. In particular, R a36 Examples include alkyl groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups formed by combining these.

[0129] R a34 It is, preferably, a hydrogen atom. R a35 The is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36The hydrocarbon group 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 a combination thereof, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. a36 In the above, it is preferable that the alkyl group and the alicyclic hydrocarbon group are unsubstituted. R a36 The aromatic hydrocarbon group in the above is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0130] -OC(R in structural unit (a1-4) a34 )(R a35 )-OR a36 Silver comes into contact with an acid (e.g., p-toluenesulfonic acid) and detaches to form a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It is preferable for the silver to bond to the o-position or p-position of the benzene ring, and it is more preferable for it to bond to the p-position.

[0131] As for the structural unit (a1-4), for example, a structural unit derived from a monomer described in Japanese Patent Publication No. 2010-204646 may be used. Preferably, the structural unit represented by each of formulas (a1-4-1) to (a1-4-18) and R in the structural unit (a1-4) a32 Structural units in which a hydrogen atom corresponding to is substituted with a halogen atom, a haloalkyl group, or an alkyl group may be used, and more preferably, structural units represented by formulas (a1-4-1) to (a1-4-5), (a1-4-10), (a1-4-13), and (a1-4-14), respectively may be used.

[0132] When the resin (A) has structural units (a1-4), the content thereof is preferably 10 to 95 mol% with respect to the total sum of the structural units of the resin (A), more preferably 15 to 90 mol%, even more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

[0133] As a structural unit derived from a (meth)acrylic monomer having a group (2), a structural unit represented by formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) may also be cited. Among equations (a1-5), R a8 It represents a carbon-1 to carbon-6 alkyl group that may have a halogen atom, a hydrogen atom, or a halogen atom. Z a1 silver, single bond or *-(CH2) h3 -CO-L 54 - represents, h3 represents any integer from 1 to 4, and * represents L 51 It represents the bonding hand with. L 51 , L 52 , L 53 and L 54 Each represents -O- or -S- independently. s1 represents any one integer from 1 to 3. s1' represents any integer from 0 to 3.

[0134] Examples of halogen atoms include fluorine atoms and chlorine atoms, and fluorine atoms are preferred. Examples of alkyl groups having 1 to 6 carbon atoms that may have halogen atoms include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, fluoromethyl groups, and trifluoromethyl groups. In equation (a1-5), R a8Silver, hydrogen atoms, methyl groups, or trifluoromethyl groups are preferred. L 51 Silver and oxygen atoms are desirable. L 52 and L 53 It is desirable that one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 Silver, single bonds, or *-CH2-CO-O- are preferred.

[0135] As for the structural unit (a1-5), for example, a structural unit derived from a monomer described in Japanese Patent Publication No. 2010-61117 may be used. Among these, the structural unit represented by formulas (a1-5-1) to (a1-5-4) is preferred, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferred.

[0136] When the resin (A) has structural units (a1-5), the content is preferably 1 to 50 mol% with respect to the total structural units of the resin (A), more preferably 3 to 45 mol%, even more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol%.

[0137] In addition, the following structural units may be used as structural units (a1).

[0138] When the resin (A) includes structural units such as (a1-3-1) to (a1-3-7) above, the content is preferably 10 to 95 mol% with respect to the total structural units of the resin (A), more preferably 15 to 90 mol%, even more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

[0139] <Structural Unit(s)> Structural units(s) are derived from a monomer that does not have an acid instability group (hereinafter referred to as "monomer(s)"). The monomer deriving the structural units(s) may be a monomer that does not have an acid instability group known in the resist field. As for the structural unit(s), it is preferable to have a hydroxyl group or a lactone ring. If a resin having a structural unit having a hydroxyl group and not having an acid unstable group (hereinafter referred to as “structural unit (a2)”) and / or a structural unit having a lactone ring and not having an acid unstable group (hereinafter referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0140] <Structural Unit (a2)> The hydroxyl group of the structural unit (a2) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. When manufacturing a resist pattern from the resist composition of the present invention, if a high-energy light source such as a KrF excimer laser (248 nm), electron beam, or EUV (ultraviolet light) is used as the exposure light source, a structural unit (a2) having a phenolic hydroxyl group is preferred as the structural unit (a2), and it is more preferable to use the structural unit (a2-A) described below. In addition, if an ArF excimer laser (193 nm) is used, a structural unit (a2) having an alcoholic hydroxyl group is preferred as the structural unit (a2), and it is more preferable to use the structural unit (a2-1) described below. As for the structural unit (a2), one type may be included alone, or two or more types may be included.

[0141] As a structural unit having a phenolic hydroxyl group in the structural unit (a2), the structural unit represented by formula (a2-A) (hereinafter referred to as “structural unit (a2-A)”) may be cited. [Equation (a2-A), R a50 It represents a carbon 1 to 6 alkyl group that may have a hydrogen atom, a halogen atom, or a halogen atom. R a51 It represents silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 silver, single bond, or *-X a51 -(A a52 -X a52 ) nb It represents -, and * is -R a50 This represents the bond loss with the carbon atom it bonds with. A a52 represents an alkandyl group having 1 to 6 carbon atoms. X a51 and X a52 Each represents -O-, -CO-O-, or -O-CO- independently. nb represents 0 or 1. mb represents any integer from 0 to 4. If mb is any integer greater than or equal to 2, multiple R a51 They may be identical or different.

[0142] R a50 and R a51 Examples of halogen atoms in this include fluorine atoms, chlorine atoms, and bromine atoms. R a50Examples of alkyl groups having 1 to 6 carbon atoms that may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, and perfluorohexyl group. R a50 Silver, a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. R a51 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl or ethyl group, and even more preferably a methyl group. R a51 Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51 Examples of the alkoxyalkyl groups include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a51Examples of the alkoxyalkoxy groups include methoxymethoxy groups, methoxymethoxy groups, ethoxymethoxy groups, ethoxymethoxy groups, propoxymethoxy groups, isopropoxymethoxy groups, butoxymethoxy groups, sec-butoxymethoxy groups, and tert-butoxymethoxy groups. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and is more preferably a methoxymethoxy group or an ethoxymethoxy group. R a51 Examples of alkyl carbonyl groups include acetyl groups, propionyl groups, and butyryl groups. An alkyl carbonyl group having 2 to 3 carbon atoms is preferred, and an acetyl group is more preferred. R a51 Examples of alkyl carbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. An alkyl carbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a51 Silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms are preferred, a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxymethoxy group, or an ethoxymethoxy group are more preferred, and a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxymethoxy group are even more preferred.

[0143] *-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 Examples include -O-CO-. Among them, *-CO-O- and *-CO-OA a52 -CO-O- or *-OAa52 -CO-O- is desirable.

[0144] Examples of alkanedyl groups include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, pentane-1,4-diyl groups, and 2-methylbutane-1,4-diyl groups. A a52 It is preferable that it be a methylene group or an ethylene group.

[0145] A a50 Silver, single bond, *-CO-O- or *-CO-OA a52 It is preferable that it be -CO-O-, more preferable that it be a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferable that it be a single bond or *-CO-O-.

[0146] mb is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. It is preferable for the hydroxyl group to be attached to the ortho or para position of the benzene ring, and more preferable for it to be attached to the para position.

[0147] As for the structural unit (a2-A), the structural unit derived from the monomer described in Japanese Patent Publication No. 2010-204634 and Japanese Patent Publication No. 2012-12577 may be cited. As for the structural unit (a2-A), R in the structural unit (a2-A) in the structural unit represented by equations (a2-2-1) to (a2-2-16) and the structural unit represented by equations (a2-2-1) to (a2-2-16). a50Examples of structural units in which a methyl group corresponding to is substituted with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group may be used. 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), a structural unit represented by formula (a2-2-8), a structural unit represented by formulas (a2-2-12) to (a2-2-14), and a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and a structural unit represented by formulas (a2-2-12) to (a2-2-14), wherein R in structural unit (a2-A) a50 It is preferable that the structural unit is one in which a methyl group corresponding to is substituted with a hydrogen atom, and in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), the structural unit represented by formulas (a2-2-12) to (a2-2-14), the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-8), and the structural unit represented by formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A). a50 It is more preferable that the structural unit is one in which a methyl group corresponding to is substituted with a hydrogen atom, and in the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2-8), R in the structural unit (a2-A). a50 It is more preferable that the methyl group equivalent to is a structural unit substituted with a hydrogen atom.

[0148] When a structural unit (a2-A) is included in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol% with respect to the total structural unit, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%. The structural unit (a2-A) can be incorporated into the resin (A) by polymerizing, for example, using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Additionally, the structural unit (a2-A) can be incorporated into the resin (A) by polymerizing using acetoxystyrene and then treating with an alkali such as tetramethylammonium hydroxide.

[0149] As a structural unit having an alcoholic hydroxyl group in the structural unit (a2), the structural unit represented by formula (a2-1) (hereinafter referred to as “structural unit (a2-1)”) may be used. In Equation (a2-1), L a3 은, -O- or *-O-(CH2) k2 Representing -CO-O-, k2 represents any integer from 1 to 7. * represents the bonding loss with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each represents, independently, a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents any integer from 0 to 10.

[0150] In equation (a2-1), L a3 silver, preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any one integer from 1 to 4), more preferably -O-. R a14is preferably a methyl group. R a15 It is, preferably, a hydrogen atom. R a16 It is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer from 0 to 3, more preferably 0 or 1.

[0151] As for the structural unit (a2-1), for example, a structural unit derived from a monomer described in Japanese Patent Publication No. 2010-204646 may be used. 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.

[0152] When the resin (A) contains a structural unit (a2-1), the content is typically 1 to 45 mol% with respect to the total structural unit of the resin (A), preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%.

[0153] <Structural Unit (a3)> The lactone ring having a structural unit (a3) ​​may be a single ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring between a single lactone ring and another ring. Preferably, a cross-linked ring (e.g., a structural unit represented by the following formula (a3-2)) including a γ-butyrolactone ring, an adamantan lactone ring, or a γ-butyrolactone ring structure may be used.

[0154] The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). It may contain one of these alone or two or more. [Among Equations (a3-1), (a3-2), (a3-3) and (a3-4), L a4 , L a5 and L a6 are, respectively, -O- or *-O-(CH2) k3 It represents a group represented as -CO-O-(k3 represents any integer from 1 to 7). L a7 은, -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- represents. L a8 and L a9 Each independently represents an alkandyl group having 1 to 6 carbon atoms. * indicates the binding site with the carbonyl group. R a18 , R a19 and R a20 Each represents, independently, a hydrogen atom or a methyl group. R a24 represents a carbon-1 to carbon-6 alkyl group that may have a halogen atom, a hydrogen atom, or a halogen atom. X a3 It represents -CH2- or oxygen atoms. R a21 It represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25Each represents, independently, a carboxyl group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any one integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 They may be identical or different.

[0155] R a21 , R a22 , R a23 and R a25 Examples of aliphatic hydrocarbon groups in this include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl groups. R a24 Examples of halogen atoms in this include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R a24 Examples of alkyl groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups or ethyl groups. R a24 Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, triiodomethyl, etc. L a8 and La9 Examples of alkanedyl groups in this include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, pentane-1,4-diyl groups, and 2-methylbutane-1,4-diyl groups.

[0156] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently, preferably -O- or, *-O-(CH2) k3 In -CO-O-, k3 is an integer from 1 to 4, more preferably -O- and *-O-CH2-CO-O-, even more preferably an oxygen atom. R a18 ~R a21 It is preferably a methyl group. R a22 and R a23 Each is independently, preferably a carboxyl group, a cyano group, or a methyl group. p1, q1 and r1 are each independently, preferably one integer from 0 to 2, and more preferably 0 or 1.

[0157] In equation (a3-4), R a24 The is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a25 is preferably a carboxyl group, a cyano group, or a methyl group. L a7 silver, preferably -O- or *-OL a8 -CO-O-, and more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer from 0 to 2, and more preferably 0 or 1. In particular, regarding Equation (a3-4), Equation (a3-4)' is preferred. (during food, R a24 , L a7 ...indicates the same meaning as above.)

[0158] As a structural unit (a3), examples include a structural unit derived from the monomer described in Japanese Patent Publication No. 2010-204646, the monomer described in Japanese Patent Publication No. 2000-122294, and the monomer described in Japanese Patent Publication No. 2012-41274. As a structural unit (a3), examples include a structural unit represented by any one of formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and formulas (a3-4-1) to (a3-4-12), and in the above structural unit, R in formulas (a3-1) to (a3-4). a18 , R a19 , R a20 and R a24 A structural unit in which a methyl group equivalent to is substituted with a hydrogen atom is preferred.

[0159]

[0160] When the resin (A) contains structural units (a3), the total content is typically 5 to 70 mol% with respect to the total structural units of the resin (A), preferably 10 to 65 mol%, and more preferably 10 to 60 mol%. In addition, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is preferably 5 to 60 mol% with respect to the total structural unit of the resin (A), more preferably 5 to 50 mol%, and even more preferably 10 to 50 mol%.

[0161] <Structural Unit (a4)> The following structural units may be used as structural units (a4). [Equation (a4), R 41 It represents a silver, hydrogen atom, or methyl group. R 42 ...represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the -CH2- included in the said saturated hydrocarbon group may be substituted with -O- or -CO-.] R 42 Saturated hydrocarbon groups represented by [the above] include chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these.

[0162] Examples of chain hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; polycyclic alicyclic hydrocarbon groups such as decahedronaphthyl, adamantyl, norvonyl groups and the following groups (* indicates a bond loss). 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, and examples include -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0163] As a structural unit (a4), at least one structural unit selected from the group consisting of equation (a4-0), equation (a4-1), equation (a4-2), equation (a4-3) and equation (a4-4) may be used. [Equation (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a It represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanidiyl group having 1 to 8 carbon atoms or a perfluorocycloalkanidiyl group having 3 to 12 carbon atoms. R 6 It represents silver, hydrogen atoms, or fluorine atoms.

[0164] L 4a Examples of divalent aliphatic saturated hydrocarbon groups include straight-chain alkanedyl groups such as methylene groups, ethylene groups, propane-1,3-diyl groups, and butane-1,4-diyl groups, and branched alkanedyl groups such as ethane-1,1-diyl groups, propane-1,2-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, and 2-methylpropane-1,2-diyl groups. L 3a As perfluoroalkanedyl groups in the above, difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, Examples include perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group, etc. L 3aExamples of perfluorocycloalkanediyl groups in this include perfluorocyclohexanediyl groups, perfluorocyclopentanediyl groups, perfluorocycloheptanediyl groups, perfluoroadamantanediyl groups, etc.

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

[0166] As for the structural unit (a4-0), R in the structural unit (a4-0) among the structural units shown below and the structural unit (a4-0) below 5 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can be cited.

[0167] [Equation (a4-1), R a41 It represents a silver, hydrogen atom, or methyl group. R a42 ... represents a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and the -CH2- included in the saturated hydrocarbon group may be substituted with -O- or -CO-. A a41 ... represents an alkandyl group having 1 to 6 carbon atoms that may have substituents, or a group represented by the formula (a-g1). provided that A a41 and R a42 At least one of them has a halogen atom (preferably a fluorine atom) as a substituent. [In Equation (a-g1), s represents 0 or 1. A a42 and A a44Each represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms that may have a substituent, independently. A a43 It represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms that may have single bonds or substituents. X a41 and X a42 Each represents -O-, -CO-, -CO-O-, or -O-CO- independently. However, A a42 , A a43 , A a44 , X a41 and X a42 The sum of the carbon atoms is 7 or less. * is a bonding hand, and the * on the right is -O-CO-R a42 It is a combined hand with.]

[0168] R a42 Examples of saturated hydrocarbon groups in this case include chain-type saturated hydrocarbon groups, monocyclic or polycyclic alicyclic saturated hydrocarbon groups, and groups formed by combining these. Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornyl groups, and the following groups (* indicates a bond loss). 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 saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0169] R a42 As a substituent that may be present, at least one selected from a halogen atom and a group represented by formula (a-g3) may be included. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and preferably fluorine atoms. [Equation (a-g3), X a43 It represents silver, an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms that may contain a halogen atom. * indicates R a42 [Represents the bonding loss with.] However, R a42 -X a43 -A a45 In this regard, R a42 In the case where it does not have a halogen atom, A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0170] A a45Examples of aliphatic hydrocarbon groups 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 decahedronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bond loss). 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, and examples include -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0171] R a42 The aliphatic hydrocarbon group that may have a halogen atom is preferred, and the aliphatic hydrocarbon group having an alkyl group having a halogen atom and / or a group represented by the formula (a-g3) is more preferred. R a42 When the aliphatic hydrocarbon group having a halogen atom is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, even 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 perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, and perfluorooctyl groups. Examples of perfluorocycloalkyl groups include perfluorocyclohexyl groups. R a42a. In the case of an aliphatic hydrocarbon group having a group represented by formula (a-g3), including the number of carbon atoms included in the group represented by formula (a-g3), R a42 The total number of carbon atoms is preferably 15 or less, and more preferably 12 or less. When having a group represented by formula (a-g3) as a substituent, the number is preferably 1.

[0172] R a42 In the case where is an aliphatic hydrocarbon group having the group represented by the formula (a-g3), R a42 is, more preferably, a group represented by the formula (a-g2). [Equation (a-g2), A a46 It represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms that may have halogen atoms. X a44 represents **-O-CO- or **-CO-O- (** is A a46 (Indicates the bonding hand of). A a47 It represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms that may have halogen atoms. However, A a46 , A a47 and X a44 The sum of the carbon atoms of is 18 or less, and A a46 and A a47 At least one of them has at least one halogen atom. * indicates the bonding loss with the carbonyl group.

[0173] A a46 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 6, and more preferably 1 to 3. A a47 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 4 to 15, and more preferably 5 to 12, and A a47 Silver, a cyclohexyl group, or an adamantyl group is more preferable.

[0174] The preferred structure of the group represented by formula (a-g2) is the following structure (* indicates a bond with the carbonyl group).

[0175] A a41 Examples of alkanedyl groups include straight-chain alkanedyl groups such as methylene groups, ethylene groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, and hexane-1,6-diyl groups; and branched alkanedyl groups such as propane-1,2-diyl groups, butane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, 1-methylbutane-1,4-diyl groups, and 2-methylbutane-1,4-diyl groups. A a41 Examples of substituents in the alkandyl group include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. A a41 The group is preferably an alkanedyl group having 1 to 4 carbon atoms, more preferably an alkanedyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0176] A in the group represented by equation (a-g1). a42 , A a43 and A a44 Examples of divalent saturated hydrocarbon groups represented by include straight-chain or branched alkanedyl groups and single-ring divalent alicyclic hydrocarbon groups, and groups formed by combining alkanedyl groups and divalent alicyclic hydrocarbon groups. Specifically, examples include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, 1-methylpropane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, etc. A a42 , A a43 and A a44 Examples of substituents for the divalent saturated hydrocarbon group shown include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. It is preferable that s be 0.

[0177] In the group represented by equation (a-g1), X a42 Examples of groups in which is -O-, -CO-, -CO-O-, or -O-CO- include the following groups. In the following examples, * and ** each represent a bonding hand, and ** is -O-CO-R a42 It is a combined hand with.

[0178] As for the structural unit represented by Equation (a4-1), the structural unit shown below and R in the structural unit represented by Equation (a4-1) among the structural units below a41 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can be cited.

[0179]

[0180] As for the structural unit represented by Equation (a4-1), the structural unit represented by Equation (a4-2) is preferred. [Equation (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkandyl group having 1 to 6 carbon atoms, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO-. R f6 It represents a saturated hydrocarbon group having fluorine atoms with 1 to 20 carbon atoms. However, L 44 and R f6 The upper limit of the total number of carbons is 21.

[0181] L 44 The alkandic group having 1 to 6 carbon atoms is A a41 One can cite the same type of device as exemplified by the Alkandi diary in this regard. Rf6 The saturated hydrocarbon group of is, R a42 One can cite the same energy as exemplified by [the example]. L 44 As for the alkanedyl group having 1 to 6 carbon atoms, an alkanedyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0182] As structural units represented by Equation (a4-2), examples include the structural units represented by Equations (a4-1-1) to (a4-1-11), respectively. R in the structural unit (a4-2). f5 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can also be cited as structural units represented by formula (a4-2).

[0183] As a structural unit (a4), the structural unit represented by equation (a4-3) can be cited. [Equation (a4-3), R f7 It represents a silver, hydrogen atom, or methyl group. L 5 represents an alkandyl group having 1 to 6 carbon atoms. A f13 It represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms that may have fluorine atoms. X f12 represents *-O-CO- or *-CO-O- (* is A f13 Indicates the bonding hand with.). A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms that may have fluorine atoms. However, A f13 and A f14 At least one of them has a fluorine atom, and L 5 , A f13 and A f14 The upper limit of the total number of carbons is 20.

[0184] L 5As for the alkandidial group in , A a41 The same group as the alkanedyl group in the divalent saturated hydrocarbon group can be cited. A f13 The divalent saturated hydrocarbon group that may have a fluorine atom is preferably a divalent aliphatic saturated hydrocarbon group that may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group that may have a fluorine atom, and more preferably a perfluoroalkanedil group. Examples of divalent aliphatic hydrocarbon groups that may have a fluorine atom include alkanediyl groups such as methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups; and perfluoroalkanediyl groups such as difluoromethylene groups, perfluoroethylene groups, perfluoropropanediyl groups, perfluorobutanediyl groups, and perfluoropentanediyl groups. A divalent alicyclic hydrocarbon group that may have a fluorine atom can be either monocyclic or polycyclic. Examples of monocyclic groups include cyclohexanediyl groups and perfluorocyclohexanediyl groups. Examples of polycyclic groups include adamantandilyl groups, novonandilyl groups, and perfluoroadamantandiyl groups. A f14 The saturated hydrocarbon group that may have a saturated hydrocarbon group and a fluorine atom is R a42One can cite the same energy as exemplified by [the example]. Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group, fluoroalkyl groups such as cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, Norbonyl groups, norbonyl methyl groups, perfluoroadamantyl groups, perfluoroadamantyl methyl groups, etc. are preferred.

[0185] In equation (a4-3), L 5 An ethylene group is desirable. A f13 The divalent saturated hydrocarbon group is preferably a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a divalent chain hydrocarbon group having 2 to 3 carbon atoms is more preferable. A f14 The saturated hydrocarbon group is preferably a group comprising a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and is more preferably a group comprising a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Among these, A f14 The group is preferably a group comprising a hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0186] As structural units represented by Equation (a4-3), examples include the structural units represented by Equations (a4-1'-1) to (a4-1'-11), respectively. R in the structural unit (a4-3). f7 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can also be cited as structural units represented by formula (a4-3).

[0187] As for the structural unit (a4), the structural unit represented by equation (a4-4) can also be cited. [Equation (a4-4), R f21 It represents a silver, hydrogen atom, or methyl group. A f21 은, -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 - represents. j1 to j5 each independently represent any one integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms containing a fluorine atom. R f22 The saturated hydrocarbon group of is, R a42 Examples include those identical to the saturated hydrocarbon group represented by R. f22 The alkyl group having 1 to 10 carbon atoms having a fluorine atom or the alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom is preferred, the alkyl group having 1 to 10 carbon atoms having a fluorine atom is more preferred, and the alkyl group having 1 to 6 carbon atoms having a fluorine atom is even more preferred.

[0188] In equation (a4-4), A f21 As, -(CH2) j1 - This is desirable, an ethylene group or a methylene group is more desirable, and a methylene group is even more desirable. As for the structural unit represented by Equation (a4-4), for example, in the structural unit below and the structural unit represented by the following Equation below, R in the structural unit (a4-4) f21 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can be cited.

[0189] When the resin (A) has a structural unit (a4), the content is preferably 1 to 20 mol% with respect to the total structural unit of the resin (A), more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%.

[0190] <Structural Unit (a5)> As for the non-detachable hydrocarbon group of the structural unit (a5), a group having a straight-chain, branched, or ring-shaped hydrocarbon group may be cited. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. As a structural unit (a5), for example, a structural unit represented by equation (a5-1) can be used. [Equation (a5-1), R 51 It represents a silver, hydrogen atom, or methyl group. R 52 represents a hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms included in the 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 the -CH2- included in the said saturated hydrocarbon group may be substituted with -O- or -CO-.]

[0191] R 52The alicyclic hydrocarbon group in this case may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups having 1 to 8 carbon atoms may include, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl groups. Examples of alicyclic hydrocarbon groups having substituents include 3-methyladamantyl groups. R 52 The group 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. L 55 Examples of divalent saturated hydrocarbon groups include divalent chain-type saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, and preferably, divalent chain-type saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include alkanediyl groups such as methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of monocyclic alicyclic saturated hydrocarbon groups include cycloalkanedyl groups such as cyclopentanediyl and cyclohexanedyl groups. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include adamantandiyl and novonandyl groups.

[0192] L 55As groups in which -CH2- included in the divalent saturated hydrocarbon group represented by is substituted with -O- or -CO-, examples include groups represented by formulas (L1-1) to (L1-4). In the following formulas, * and ** each represent a bond loss, and * represents a bond loss with an oxygen atom. Among the formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* is L x1 Indicates the bonding hand with.). L x1 It 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. Among the formulas (L1-2), L x3 It 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. Among the formulas (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. Among the formulas (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 It 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.

[0193] L x1 The group 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 The 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 It is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 It is, preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 The group is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 The group 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 It is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 The group 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 x9The 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 The group is preferably a divalent saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantandilyl group.

[0194] Examples of groups represented by Equation (L1-1) include the divalent groups shown below.

[0195]

[0196] Examples of groups represented by Equation (L1-2) include the divalent groups shown below.

[0197] Examples of groups represented by Equation (L1-3) include the divalent groups shown below.

[0198] Examples of groups represented by Equation (L1-4) include the divalent groups shown below.

[0199] L 55 is, preferably, a single bond or a group represented by formula (L1-1).

[0200] As for the structural unit (a5-1), R in the structural unit (a5-1) among the structural units shown below and the structural units below 51 Structural units in which a methyl group equivalent to is substituted with a hydrogen atom can be cited.

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

[0202] <Structural Unit (a6)> The structural unit (a6) is a structural unit having a -SO2- group, and it is preferable to have a -SO2- group in the side chain. A structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a ring structure having a -SO2- group (single-ring and poly-ring structures). Preferably, it is a structural unit having a ring structure having a -SO2- group, and more preferably, it is a structural unit having a ring structure containing -SO2-O- (a Sulton ring).

[0203] As for the Sulton ring, the following formula (T 1 -1), equation (T 1 -2), equation (T 1 -3) and equation (T 1 Examples include rings represented by -4). The bonding site can be at any position. The sulfonate ring may be monocyclic, but it is preferable that it be polycyclic. A polycyclic sulfonate ring refers to a cross-linked ring containing -SO2-O- as an atomic group constituting the ring, and is given by the formula (T 1 -1) and equation (T 1 An example is a ring represented by -2). A Sulton ring is given by the equation (T 1 As with the ring represented by -2), the atomic group constituting the ring may additionally include a heteroatom in addition to -SO2-O-. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms, and preferably oxygen atoms.

[0204] The sulfon ring may have substituents, and examples of substituents include an alkyl group having 1 to 12 carbon atoms that may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having 7 to 12 carbon atoms, a glycidyloxy group having 2 to 12 carbon atoms, and an alkyl carbonyl group having 2 to 4 carbon atoms.

[0205] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl groups, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably methyl groups. Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl groups, and preferably trifluoromethyl groups. Examples of alkyl groups having a hydroxyl group include hydroxymethyl and 2-hydroxyethyl hydroxyalkyl groups. Examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentyloxy groups, hexyloxy groups, heptyloxy groups, octyloxy groups, decyloxy groups, and dodecyloxy groups. Examples of aryl groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumyl, mesithyl, biphenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group. As for the alkoxycarbonyl group, examples include a group in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is combined with a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group. Examples of alkyl carbonyl groups include acetyl groups, propionyl groups, and butyryl groups.

[0206] From the perspective that it is easy to manufacture the monomer that induces the structural unit (a6), a sulfonate ring without substituents is preferred. As for the Sulton ring, the ring represented by the following equation (T1') is preferred. [Equation (T1'), X 11 It represents silver, oxygen atoms, sulfur atoms, or methylene groups. R 41 It represents an alkyl group having 1 to 12 carbon atoms that may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having 7 to 12 carbon atoms, a glycidyloxy group having 2 to 12 carbon atoms, or an alkyl carbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or greater, multiple R 41 It may be the same or different. The connection site is at an arbitrary location. X 11 The silver is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R 41 Examples include substituents identical to those of the sulfonate ring, and preferably alkyl groups having 1 to 12 carbon atoms that may have a halogen atom or a hydroxyl group.

[0207] As for the Sulton ring, the ring represented by Equation (T1) is more preferable. [Equation (T1), R 8 It represents an alkyl group having 1 to 12 carbon atoms that may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having 7 to 12 carbon atoms, a glycidyloxy group having 2 to 12 carbon atoms, or an alkyl carbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or greater, multiple R 8 It may be the same or different. The connection site is at an arbitrary location.

[0208] R 8 silver, R 41 One can cite the same thing as. ma in formula (T1') and m in formula (T1) are preferably 0 or 1, and more preferably 0.

[0209] Examples of the rings represented by Equation (T1') and the rings represented by Equation (T1) include the following rings. The connection site is at any location.

[0210] A structural unit having a sulfon ring preferably has the following group. In the following group, * indicates a bonding site.

[0211] It is desirable that the structural unit having the -SO2- group additionally has a group derived from a polymerizable group. Examples of polymerizable groups include vinyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, acryloylthio group, methacryloylthio group, etc. Among them, the monomer that induces the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.

[0212] The structural unit (a6) is, preferably, a structural unit represented by the formula (Ix). [Equation (Ix), R x represents a carbon-1 to carbon-6 alkyl group that may have a halogen atom, a hydrogen atom, or a halogen atom. A xx is, oxygen atom, -N(R c )- or represents a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- included in the said saturated hydrocarbon group is -O-, -CO-, or -N(R d It may be replaced with )-. X 11 It represents silver, oxygen atoms, sulfur atoms, or methylene groups. R 41 It represents an alkyl group having 1 to 12 carbon atoms that may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryl group having 7 to 12 carbon atoms, a glycidyloxy group having 2 to 12 carbon atoms, or an alkyl carbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or greater, multiple R 41 It may be the same or different. R c and R d represents, independently of each other, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0213] R x Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R x Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl or ethyl groups. R x Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl. R x The 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.

[0214] A x Examples of divalent saturated hydrocarbon groups include straight-chain alkanedil groups, branched alkanedil groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and a combination of two or more of these groups may also be used. Specifically, methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nonane-1,9-diyl groups, decane-1,10-diyl groups, undecane-1,11-diyl groups, dodecane-1,12-diyl groups, tridecane-1,13-diyl groups, tetradecane-1,14-diyl groups, pentadecane-1,15-diyl groups, hexadecane-1,16-diyl groups, heptadecane-1,17-diyl groups, ethane-1,1-diyl groups, propane-1,1-diyl groups, and propane-2,2-diyl groups, etc. Linear-shaped alkandi diary; Branched alkanedyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; A monocyclic divalent alicyclic saturated hydrocarbon group that is a cycloalkanedyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as nobonan-1,4-diyl group, nobonan-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0215] R 41 , X 11 and ma are equivalent to Equation (T1'). As for the Sulton ring, the above-described ones may be cited, and among them, the above-described one with a specified coupling position is preferred.

[0216] As structural units (a6), the following structural units may be used.

[0217] Among these, the structural unit represented by Equation (a6-1), Equation (a6-2), Equation (a6-6), Equation (a6-7), Equation (a6-8) and Equation (a6-12) is preferred, and the structural unit represented by Equation (a6-1), Equation (a6-2), Equation (a6-7) and Equation (a6-8) is more preferred. When the resin (A) has a structural unit (a6), the content is preferably 1 to 50 mol% with respect to the total structural unit of the resin (A), more preferably 2 to 40 mol%, and even more preferably 3 to 30 mol%.

[0218] <Structural Unit (II)> The resin (A) may additionally contain a structural unit that decomposes upon exposure to light to generate acid (hereinafter referred to as “structural unit (II)”). Specifically, the structural unit (II) may be the structural unit described in Japanese Patent Publication No. 2016-79235, and it is preferable that the structural unit has a sulfonate group or a carboxylate group and an organic cation in a side chain, or a structural unit has a sulfonio group and an organic anion in a side chain.

[0219] The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by the formula (II-2-A'). [Equation (II-2-A'), X III3 The saturated hydrocarbon group has 1 to 18 carbon atoms and represents a divalent saturated hydrocarbon group, wherein the -CH2- included in the saturated hydrocarbon group may be substituted with -O-, -S-, or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms that may have a halogen atom, or a hydroxyl group. A x1 The element represents an alkanedyl group having 1 to 8 carbon atoms, and the hydrogen atoms included in the alkanedyl 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 It represents a carbon 1 to 6 alkyl group that may have a hydrogen atom, a halogen atom, or a halogen atom. ZA + represents an organic cation.

[0220] R III3 Examples of halogen atoms represented as such include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R III3 As an alkyl group having 1 to 6 carbon atoms that may have a halogen atom represented by, R a8 Examples include alkyl groups having 1 to 6 carbon atoms that may have a halogen atom represented by . A x1 Examples of alkanediyl groups having 1 to 8 carbon atoms represented by are methylene groups, ethylene groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, ethane-1,1-diyl groups, propane-1,1-diyl groups, propane-1,2-diyl groups, propane-2,2-diyl groups, pentane-2,4-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, pentane-1,4-diyl groups, 2-methylbutane-1,4-diyl groups, etc. A x1 Examples of perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include trifluoromethyl groups, perfluoroethyl groups, perfluoropropyl groups, perfluoroisopropyl groups, perfluorobutyl groups, perfluorosec-butyl groups, perfluorotert-butyl groups, perfluoropentyl groups, perfluorohexyl groups, etc. X III3 Examples of divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by this include straight-chain or branched alkanedyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof. Specifically, linear alkanedyl groups such as methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nonane-1,9-diyl groups, decane-1,10-diyl groups, undecane-1,11-diyl groups, dodecane-1,12-diyl groups; branched alkanedyl groups such as butane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, 2-methylpropane-1,2-diyl groups, pentane-1,4-diyl groups, and 2-methylbutane-1,4-diyl groups; Examples include cycloalkanedyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group; and divalent polycyclic alicyclic saturated hydrocarbon groups such as norbonan-1,4-diyl group, norbonan-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. Examples of groups substituted with -CH2-, -O-, -S-, or -CO- within a saturated hydrocarbon group include divalent groups represented by formulas (X1) to (X53). However, the number of carbon atoms prior to substitution with -CH2-, -O-, -S-, or -CO- within the saturated hydrocarbon group is 17 or less. In the following formulas, * and ** represent bonding sites, and * represents A x1 It indicates the connection site with.

[0221] X 3 It represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 It represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 It represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 It represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0222] ZA in Equation (II-2-A') + is the cation Z1 in the salt represented by formula (B1). + One can cite the same thing as.

[0223] The structural unit represented by Equation (II-2-A') is preferably the structural unit represented by Equation (II-2-A). [Among Formula (II-2-A), R III3 , X III3 and ZA + represents the same meaning as above. z2A represents any integer from 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, and when z2A is 2 or more, a plurality of R III2 and R III4 They may be identical or different. Q a and Q b Each represents, independently, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R III2 , R III4 , Q a and Q b As a perfluoroalkyl group having 1 to 6 carbon atoms represented by, the aforementioned Q b1 Examples include perfluoroalkyl groups having 1 to 6 carbon atoms represented by [formula].

[0224] The structural unit represented by Equation (II-2-A) is preferably the structural unit represented by Equation (II-2-A-1). [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and ZA + represents the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents any integer from 0 to 6. X I2 ...represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, wherein the -CH2- included in the saturated hydrocarbon group may be substituted with -O-, -S-, or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with halogen atoms or hydroxyl groups. R III5 Examples of saturated hydrocarbon groups having 1 to 12 carbon atoms represented by are straight-chain or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. X I2 As a divalent saturated hydrocarbon group represented by, X III3 Examples include the same as the divalent saturated hydrocarbon group represented by.

[0225] As for the structural unit represented by Equation (II-2-A-1), the structural unit represented by Equation (II-2-A-2) is more preferable. [Among the formula (II-2-A-2), R III3 , R III5 and ZA + represents the same meaning as above. m and nA independently represent 1 or 2.

[0226] As a structural unit represented by Equation (II-2-A'), for example, the following structural unit, R III3 Examples include structural units in which a group corresponding to the methyl group is substituted with a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a carbon-1 to carbon-6 alkyl group that may have a halogen atom (e.g., a trifluoromethyl group, etc.), and structural units described in International Publication No. 2012 / 050015. ZA + represents an organic cation.

[0227] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by formula (II-1-1). [Equation (II-1-1), A II1 It represents a single bond or a divalent linker. R II1 It represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 They may bond with each other and form a ring together with the sulfur atoms they bond to. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. A - represents an organic anion. R II1 Examples of divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms represented by phenylene groups and naphthylene groups include phenylene groups and naphthylene groups. R II2 and R II3Examples of hydrocarbon groups represented by such groups include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. R II4 Examples of halogen atoms represented by this include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R II4 As an alkyl group having 1 to 6 carbon atoms that may have a halogen atom represented by, R a8 Examples include alkyl groups having 1 to 6 carbon atoms that may have a halogen atom represented by . A II1 As a divalent linker represented by , for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms may be cited, and the -CH2- included in said divalent saturated hydrocarbon group may be substituted with -O-, -S-, or -CO-. Specifically, X III3 Examples include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, represented as such.

[0228] As structural units containing cations in formula (II-1-1), the structural units shown below and R II4 Examples include structural units substituted with a group equivalent to a methyl group, a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc.

[0229] A - Examples of organic anions represented by include sulfonate anions, sulfonylimide anions, sulfonylmette anions, and carboxylate anions. A - The organic anion represented by is preferably a sulfonate anion, and as the sulfonate anion, it is more preferably an anion included in the salt represented by the aforementioned formula (B1). The sulfonylimide anion, sulfonylmette anion, and carboxylate anion are anions Al included in the salt represented by the aforementioned formula (I).- It is more desirable to be.

[0230] Structural units represented by Equation (II-1-1) include the structural units shown below.

[0231] In the case where the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to the total structural unit of the resin (A), more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%.

[0232] The resin (A) may have structural units other than the structural units described above, and such structural units may include structural units well known in the relevant technical field.

[0233] The resin (A) is preferably a resin composed of a structural unit (a1) and structural units (s), that is, a copolymer of monomer (a1) and monomer(s). The structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably the corresponding structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two types, and even more preferably at least two types selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). The structural unit(s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). The structural unit (a2) is preferably structural unit (a2-1) or structural unit (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). Each structural unit constituting the resin (A) may be used as a single type or in combination of two or more types, and may be manufactured according to a known polymerization method (e.g., radical polymerization method) using monomers that induce 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 obtained by gel permeation chromatography under the conditions described in the examples.

[0234] <Suzy other than Suzy (A)> The resist composition of the present invention may use a resin other than resin (A) in combination. Examples of resins other than resin (A) include a resin containing a structural unit (a4) or a structural unit (a5) (hereinafter referred to as resin (X)). As for the resin (X), among them, a resin containing a structural unit (a4) is preferred. In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more with respect to the total sum of the structural units of the resin (X), more preferably 40 mol% or more, and even more preferably 45 mol% or more. Structural units that the resin (X) may additionally possess include structural unit (a1), structural unit (a2), structural unit (a3), and other structural units derived from known monomers. Among these, it is preferable that the resin (X) be a resin composed only of structural unit (a4) and / or structural unit (a5). Each structural unit constituting the resin (X) may be used as a single type or in combination of two or more types, and may be manufactured according to a known polymerization method (e.g., radical polymerization method) using monomers that induce these structural units. The content of each structural unit in the resin (X) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as in the case of the resin (A).

[0235] When the resist composition of the present invention includes a 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, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass, with respect to 100 parts by mass of resin (A).

[0236] The content of resin (A) in the resist composition is preferably 80 mass% or more and 99 mass% or less with respect to the solid content of the resist composition, and more preferably 90 mass% or more and 99 mass% or less. In addition, if a resin other than resin (A) is included, the total content of resin (A) and the resin other than resin (A) is preferably 80 mass% or more and 99 mass% or less with respect to the solid content of the resist composition, and more preferably 90 mass% or more and 99 mass% or less. In this specification, "solid content of the resist composition" means the sum of the components excluding the solvent (E) described below from the total amount of the resist composition. The solid content of the resist composition and the content of resin therein can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0237] <Solvent(E)> The content of the solvent (E) in the resist composition is typically 90 mass% or more and 99.9 mass% or less, preferably 92 mass% or more and 99 mass% or less, and more preferably 94 mass% or more and 99 mass% or less. The content of the solvent (E) can be measured by known analytical means, such as liquid chromatography or gas chromatography.

[0238] Examples of solvents (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.

[0239] <Quencher(C)> Examples of quenchers (C) include basic nitrogen-containing organic compounds and salts that generate an acid with a lower acidity than the acid generated from an acid-generating agent (B). When a resist composition contains a quencher (C), the content of the quencher (C) is preferably about 0.01 to 15 mass% based on the amount of solids in the resist composition, more preferably about 0.01 to 10 mass%, even more preferably about 0.1 to 5 mass%, and even more preferably about 0.1 to 3 mass%. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Examples of aliphatic amines include primary amines, secondary amines, and tertiary amines.

[0240] As amines, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, Examples include 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc., preferably diisopropylaniline, and more preferably 2,6-diisopropylaniline.

[0241] 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.

[0242] The acidity of a salt that generates an acid that is less acidic than the acid generated from the acid generator (B) is expressed by an acid dissociation constant (pKa). A salt that generates an acid that is less acidic 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 typically -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of salts that generate an acid with a lower acidity than the acid generated from the acid generator (B) include the salt represented by the following formula, the salt represented by formula (D) described in Japanese Patent Publication No. 2015-147926 (hereinafter referred to as “salt within the weak acid molecule (D)”), and the salts described in Japanese Patent Publication No. 2012-229206, Japanese Patent Publication No. 2012-6908, Japanese Patent Publication No. 2012-72109, Japanese Patent Publication No. 2011-39502 and Japanese Patent Publication No. 2011-191745. The salt that generates an acid that is less acidic than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid that is less acidic than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably a salt (D) within a weak acid molecule.

[0243] The following salts may be used as salts (D) within a weak acid molecule.

[0244] Other Components The resist composition of the present invention may, if necessary, contain components other than those described above (hereinafter referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., may be used.

[0245] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing a salt (I), a resin (A), and an acid-generating agent (B), and, if necessary, a resin other than the resin (A) used, a solvent (E), a quencher (C), and other components (F). The order of mixing is optional and is not particularly limited. The mixing temperature can be selected from 10 to 40°C, depending on the type of resin, the solubility of the resin in the solvent (E), etc. The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. In addition, the means of mixing is not particularly limited and stirring mixing, etc., may be used. After mixing each component, it is preferable to filter using a filter with a hole diameter of about 0.003 to 0.2 μm.

[0246] Method for manufacturing a resist pattern The method for manufacturing a resist pattern of the present invention is, (1) A process of applying the resist composition of the present invention onto a substrate, (2) A process of drying the composition after application to form a composition layer, (3) Process of exposing the composition layer to light, (4) A process for heating the composition layer after exposure, and (5) Includes a process for developing the composition layer after heating. To apply the resist composition onto a substrate, it is possible to perform this using a commonly used device such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers and already formed resist films. Before applying the resist composition, the substrate may be cleaned, and an anti-reflective film may be formed on the substrate. By drying the composition after application, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake) or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. In addition, the pressure during vacuum drying is 1 to 1.0 × 10⁻⁶ 5 It is desirable to be around Pa. Typically, the obtained composition layer is exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As an exposure light source, various types may be used, such as emitting laser light in the ultraviolet range, like a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F2 excimer laser (wavelength 157 nm); emitting harmonic laser light in the far-ultraviolet or vacuum ultraviolet range by wavelength conversion of laser light from a solid-state laser source (such as a YAG or semiconductor laser); or irradiating electron beams or ultraviolet light (EUV). Furthermore, in this specification, the act of irradiating with these radiations may be collectively referred to as "exposure." During exposure, the exposure is typically performed through a mask corresponding to the required pattern. If the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. For the composition layer after exposure, a heat treatment (so-called PEB (post exposure bake)) is performed to promote a deprotection reaction in the acid unstable phase. The heating temperature is typically about 50 to 200°C, preferably about 70 to 150°C. A chemical treatment (silylation) to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating may also be performed. In addition, before developing, the processes of applying a resist composition, drying, exposure, and heating may be repeatedly performed on the composition layer after exposure. The composition layer after heating is typically developed using a developing device and a developing solution. Examples of developing methods include the dipping method, the puddle method, the spray method, and the dynamic dispensing method. The developing temperature is preferably, for example, 5 to 60°C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive-type resist pattern or a negative-type resist pattern can be manufactured. When preparing a positive type resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) may be used. The alkaline developer may contain a surfactant. After development, it is desirable to clean the resist pattern with ultrapure water and then remove any remaining water on the substrate and the pattern. When preparing a negative-type resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter referred to as an "organic developer") is used as the developer. Examples of organic solvents included in organic developing solutions 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. Among the organic developer, the content of the organic solvent is preferably 90 mass% or more and 100 mass% or less, more preferably 95 mass% or more and 100 mass% or less, and more preferably substantially only organic solvent. Among these, as an organic developer, a developer containing butyl acetate and / or 2-heptanone is preferred. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50 mass% or more and 100 mass% or less, more preferably 90 mass% or more and 100 mass% or less, and more preferably substantially butyl acetate and / or 2-heptanone only. Organic developers may contain surfactants. Additionally, organic developers may contain trace amounts of water. During development, the development may be stopped by replacing the organic developer with a solvent of a different type. It is desirable to wash the resist pattern after development with a rinse solution. As for the rinse solution, there are no particular restrictions as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent may be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is desirable to remove the rinse liquid remaining on the substrate and pattern.

[0247] <use> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly as a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for microfabrication of semiconductors. [Example]

[0248] The present invention will be explained in more detail with reference to examples. In the examples, "%" and "parts" indicating content or usage amount are based on mass unless otherwise specified. The weight-average molecular weight is a value obtained by gel permeation chromatography. In addition, the analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3+ guard column (Manufactured by TOSOH CORPORATION) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI Detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by TOSOH CORPORATION) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is type 1100 manufactured by Agilent Technologies, Inc., and MASS is type LC / MSD manufactured by Agilent Technologies, Inc.). In the following examples, the value of the molecular ion peak is denoted as "MASS".

[0249] Example 1: Synthesis of the salt represented by formula (I-8) Twenty parts of the compound represented by formula (I-8-a), 2.28 parts of the salt represented by formula (I-8-c), 100 parts of ethyl acetate, and 15 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 6.55 parts of the compound represented by formula (I-8-b) were added and stirred at 23°C for 18 hours. To the resulting reaction mass, 20 parts of n-heptane and 70 parts of deion-exchanged water were added and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. 60 parts of deion-exchanged water were added to the recovered organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated four times. The obtained organic layer was concentrated, and the concentrated mass was separated by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 7.48 parts of the compound represented by formula (I-8-d). 0.95 parts of the compound represented by formula (I-8-d) and 10 parts of tetrahydrofuran were mixed, stirred at 23°C for 30 minutes, cooled to 5°C, and 0.14 parts of sodium hydride were added. To the obtained mixture, 1.81 parts of the salt represented by formula (I-8-e) were added and stirred at 5°C for 3 hours. To the obtained mixture, 6.30 parts of 1N hydrochloric acid were added, the temperature was raised to 23°C, and stirred at 23°C for 6 hours. To the obtained mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. After concentrating the obtained organic layer, 1 part acetonitrile and 30 parts tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 1.52 parts of the salt represented by formula (I-8-f). 0.76 parts of the salt represented by formula (I-8-f), 1.20 parts of the salt represented by formula (I-8-g), and 20 parts of chloroform were added and stirred at 23°C for 3 hours. 15 parts of deion-exchanged water were added to the resulting reaction mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquid. 15 parts of deion-exchanged water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquid. This water washing operation was repeated 5 times. After concentrating the resulting organic layer, 1.5 parts of acetonitrile and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes; the supernatant was then removed and concentrated to obtain 1.11 parts of the salt represented by formula (I-8). MASS(ESI(+) Spectrum): M + 369.1 MASS(ESI(-) Spectrum): M - 517.1

[0250] Example 2: Synthesis of the salt represented by formula (I-312) 0.95 parts of the salt represented by formula (I-8-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes, after which 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 1.13 parts of the compound represented by formula (I-312-a) were added and stirred at 75°C for 5 hours, after which it was cooled to 23°C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. 20 parts of deion-exchanged water were added to the obtained organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.22 parts of the salt represented by formula (I-312-b) were obtained. 0.98 parts of the salt represented by formula (I-312-b), 1.02 parts of the salt represented by formula (I-8-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.29 parts of the salt represented by formula (I-312). MASS(ESI(+) Spectrum): M + 575.2 MASS(ESI(-) Spectrum): M - 517.1

[0251] Example 3: Synthesis of the salt represented by formula (I-4) 0.76 parts of the salt represented by formula (I-8-f), 0.78 parts of the salt represented by formula (I-4-g), and 20 parts of chloroform were added and stirred at 23°C for 3 hours. 15 parts of deion-exchanged water were added to the resulting reaction mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquid. 15 parts of deion-exchanged water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquid. This water washing operation was repeated 5 times. After concentrating the resulting organic layer, 1.5 parts of acetonitrile and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes; the supernatant was then removed and concentrated to obtain 1.02 parts of the salt represented by formula (I-4). MASS(ESI(+) Spectrum): M + 369.1 MASS(ESI(-) Spectrum): M - 311.0

[0252] Example 4: Synthesis of the salt represented by formula (I-308) 0.98 parts of the salt represented by formula (I-312-b), 0.66 parts of the salt represented by formula (I-4-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 0.99 parts of the salt represented by formula (I-308). MASS(ESI(+) Spectrum): M + 575.2 MASS(ESI(-) Spectrum): M - 311.0

[0253] Example 5: Synthesis of the salt represented by formula (I-320) 0.98 parts of the salt represented by formula (I-312-b), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.34 parts of the salt represented by formula (I-320). MASS(ESI(+) Spectrum): M + 575.2 MASS(ESI(-) Spectrum): M - 467.1

[0254] Example 6: Synthesis of the salt represented by formula (I-328) 0.98 parts of the salt represented by formula (I-312-b), 1.46 parts of the salt represented by formula (I-328-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.92 parts of the salt represented by formula (I-328). MASS(ESI(+) Spectrum): M + 575.2 MASS(ESI(-) Spectrum): M - 793.3

[0255] Example 7: Synthesis of the salt represented by formula (I-339) 0.98 parts of the salt represented by formula (I-312-b), 0.84 parts of the salt represented by formula (I-339-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.14 parts of the salt represented by formula (I-339). MASS(ESI(+) Spectrum): M + 575.2 MASS(ESI(-) Spectrum): M - 423.1

[0256] Example 8: Synthesis of the salt represented by formula (I-1992) 0.95 parts of the compound represented by formula (I-8-d) and 10 parts of tetrahydrofuran were mixed, stirred at 23°C for 30 minutes, cooled to 5°C, and 0.14 parts of sodium hydride were added. To the obtained mixture, 1.81 parts of the salt represented by formula (I-8-e) were added and stirred at 5°C for 3 hours, followed by further stirring at 23°C for 1 hour. To the obtained mixture, 30 parts of chloroform and 15 parts of deion-exchanged water were added and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. After concentrating the obtained organic layer, 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes; the supernatant was then removed and concentrated to obtain 1.89 parts of the salt represented by formula (I-1992-f). 0.76 parts of the salt represented by formula (I-1992-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.11 parts of the salt represented by formula (I-1992). MASS(ESI(+) Spectrum): M + 441.2 MASS(ESI(-) Spectrum): M - 467.1

[0257] Example 9: Synthesis of the salt represented by formula (I-2182) 1.01 parts of the compound represented by formula (I-2182-d) and 10 parts of tetrahydrofuran were mixed, stirred at 23°C for 30 minutes, cooled to 5°C, and 0.14 parts of sodium hydride were added. To the obtained mixture, 1.81 parts of the salt represented by formula (I-8-e) were added and stirred at 5°C for 3 hours, followed by further stirring at 23°C for 1 hour. To the obtained mixture, 30 parts of chloroform and 15 parts of deion-exchanged water were added and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. After concentrating the obtained organic layer, 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes; the supernatant was then removed and concentrated to obtain 2.02 parts of the salt represented by formula (I-2182-f). 0.78 parts of the salt represented by formula (I-2182-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.23 parts of the salt represented by formula (I-2182). MASS(ESI(+) Spectrum): M + 453.2 MASS(ESI(-) Spectrum): M - 467.1

[0258] Example 10: Synthesis of the salt represented by formula (I-1612) 2.10 parts of the compound represented by formula (I-8-d) and 20 parts of tetrahydrofuran were mixed, stirred at 23°C for 30 minutes, cooled to 5°C, and 0.28 parts of sodium hydride were added. To the obtained mixture, 1.91 parts of the salt represented by formula (I-1612-e) were added and stirred at 5°C for 3 hours. To the obtained mixture, 12.60 parts of 1N hydrochloric acid were added, the temperature was raised to 23°C, and stirred at 23°C for 6 hours. To the obtained mixture, 50 parts of chloroform and 25 parts of deion-exchanged water were added and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. After concentrating the obtained organic layer, 3 parts of acetonitrile and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 2.42 parts of the salt represented by formula (I-1612-f). 0.82 parts of the salt represented by formula (I-1612-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.29 parts of the salt represented by formula (I-1612). MASS(ESI(+) Spectrum): M + 477.1 MASS(ESI(-) Spectrum): M - 467.1

[0259] Example 11: Synthesis of the salt represented by formula (I-1232) 1.20 parts of the salt represented by formula (I-1612-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes, after which 0.32 parts of potassium carbonate and 0.10 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 1.36 parts of the compound represented by formula (I-312-a) were added and stirred at 75°C for 5 hours, after which it was cooled to 23°C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. 20 parts of deion-exchanged water were added to the obtained organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.89 parts of the salt represented by formula (I-1232-f) were obtained. 1.48 parts of the salt represented by formula (I-1232-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separating the liquids. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 2.01 parts of the salt represented by formula (I-1232). MASS(ESI(+) Spectrum): M + 889.4 MASS(ESI(-) Spectrum): M - 467.1

[0260] Example 12: Synthesis of the salt represented by formula (I-1650) 3.15 parts of the compound represented by formula (I-8-d) and 30 parts of tetrahydrofuran were mixed, stirred at 23°C for 30 minutes, cooled to 5°C, and 0.42 parts of sodium hydride were added. To the obtained mixture, 2.01 parts of the salt represented by formula (I-1650-e) were added and stirred at 5°C for 3 hours. To the obtained mixture, 18.90 parts of 1N hydrochloric acid were added, the temperature was raised to 23°C, and stirred at 23°C for 6 hours. To the obtained mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. After concentrating the obtained organic layer, 5 parts of acetonitrile and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 3.11 parts of the salt represented by formula (I-1650-f). 0.99 parts of the salt represented by formula (I-1650-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentration residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 1.43 parts of the salt represented by formula (I-1650). MASS(ESI(+) Spectrum): M + 585.1 MASS(ESI(-) Spectrum): M - 467.1

[0261] Example 13: Synthesis of the salt represented by formula (I-1270) 1.45 parts of the salt represented by formula (I-1650-f) and 30 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes, after which 0.48 parts of potassium carbonate and 0.15 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 2.04 parts of the compound represented by formula (I-312-a) were added and stirred at 75°C for 5 hours, after which it was cooled to 23°C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. 20 parts of deion-exchanged water were added to the obtained organic layer and stirred at 23°C for 30 minutes, after which the organic layer was extracted by separation. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.42 parts of the salt represented by formula (I-1270-f) were obtained. 1.98 parts of the salt represented by formula (I-1270-f), 0.91 parts of the salt represented by formula (I-320-g), 30 parts of chloroform, and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. 20 parts of deion-exchanged water were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the mixture was separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butylmethyl ether were added to the concentrated residue and stirred at 23°C for 30 minutes, after which the mixture was filtered to obtain 2.29 parts of the salt represented by formula (I-1232). MASS(ESI(+) Spectrum): M + 1203.5 MASS(ESI(-) Spectrum): M - 467.1

[0262] Synthesis of resin The compounds (monomers) used in the synthesis of resin (A) are shown below. In the following, these compounds are referred to as “monomers (a1-1-3)”, etc., according to their formula numbers.

[0263] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3), and monomer (a1-2-6) were used and mixed in a molar ratio [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6)] of 38:24:38. Furthermore, methyl isobutyl ketone was mixed into this monomer mixture in an amount 1.5 times the mass of the total monomers. Azobis-isobutyronitrile was added to the obtained mixture as an initiator in an amount of 7 mol% relative to the total molar amount of the total monomers, and polymerization was carried out by heating this at 85°C for about 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), at a mass 2.0 times the total mass of the monomers, was added to the polymerization reaction mixture and stirred for 6 hours, after which the mixture was separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and by filtration and recovery, a weight-average molecular weight of approximately 5.3 × 10⁻⁶ 3 Resin A1 (copolymer) was obtained with a yield of 78%. This resin A1 has the following structural units.

[0264] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used and mixed in a molar ratio [monomer (a1-4-2) : monomer (a1-2-6)] of 38:62. Furthermore, methyl isobutyl ketone was mixed into this monomer mixture in an amount of 1.5 times the total mass of the monomers. Azobis-isobutyronitrile was added to the obtained mixture as an initiator in an amount of 7 mol% relative to the total molar amount of the monomers, and polymerization was carried out by heating this at 85°C for about 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount of 2.0 times the total mass of the monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer is poured into a large amount of n-heptane to precipitate a resin, and by filtration and recovery, a weight-average molecular weight of approximately 5.4 × 10⁻⁶3 Resin A2 (copolymer) was obtained with a yield of 89%. This resin A2 has the following structural units.

[0265] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), and monomer (aa1-4-2) were mixed in such a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2)] of 20:35:3:15:27, and furthermore, methyl isobutyl ketone was mixed into this monomer mixture in an amount 1.5 times the mass of the total monomers. To the obtained mixture, azobis(isobutyronitrile) and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, relative to the total monomer amount, and heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), at a mass 2.0 times the total mass of the monomer, was added to the polymerization reaction mixture and stirred for 12 hours, after which the mixture was separated. The recovered organic layer was poured into a large volume of n-heptane to precipitate a resin, and by filtration and recovery, a weight-average molecular weight of approximately 5.3 × 10⁻⁶ was obtained. 3 Resin A3 was obtained with a yield of 63%. This resin A3 has the following structural units.

[0266] Synthesis Example 4 [Synthesis of Resin A4] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), and monomer (a1-4-13) were mixed in such a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13)] of 20:35:3:15:27, and furthermore, methyl isobutyl ketone was mixed into this monomer mixture in an amount 1.5 times the mass of the total monomers. To the obtained mixture, azobis(isobutyronitrile) and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, relative to the total monomer amount, and heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), at a mass 2.0 times the total mass of the monomer, was added to the polymerization reaction mixture and stirred for 12 hours, after which the mixture was separated. The recovered organic layer was poured into a large volume of n-heptane to precipitate a resin, and by filtration and recovery, a weight-average molecular weight of approximately 5.1 × 10⁻⁶ 3 Resin A4 was obtained with a yield of 61%. This resin A4 has the following structural units.

[0267] <Preparation of Resist Composition> As shown in Table 2, each of the following components was mixed, and the resulting mixture was filtered through a fluoropolymer filter with a hole diameter of 0.2 μm to prepare a resist composition. [Table 2]

[0268] <Suzy> A1~A4: Resin A1~Resin A4 <Yeom(I)> I-4: Salt represented by formula (I-4) I-8: Salt represented by formula (I-8) I-308: Salt represented by formula (I-308) I-312: Salt represented by formula (I-312) I-320: Salt represented by formula (I-320) I-328: Salt represented by formula (I-328) I-339: Salt represented by formula (I-339) I-1232: Salt represented by formula (I-1232) I-1270: Salt represented by formula (I-1270) I-1612: Salt represented by formula (I-1612) I-1650: Salt represented by formula (I-1650) I-1992: Salt represented by formula (I-1992) I-2182: Salt represented by formula (I-2182) <Acid generator> IX-1 IX-2 IX-3 <Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 <Dragon Emperor> Propylene glycol monomethyl ether acetate 400 parts 100 parts propylene glycol monomethyl ether γ-Butyrolactone Part 5

[0269] (Evaluation of electron beam exposure of resist composition) A 6-inch silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90°C for 60 seconds. A resist composition was spin-coated onto the silicon wafer such that the film thickness of the composition layer was 0.04 μm. Subsequently, a composition layer was formed by pre-baking on a direct hot plate at the temperature indicated in the column "PB" of Table 2 for 60 seconds. On the composition layer formed on the wafer, a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithograph [ELS-F125 125 keV manufactured by ELIONIX INC.] by varying the exposure amount in steps. After exposure, a post-exposure bake (PEB) was performed on a hot plate for 60 seconds at the temperature indicated in the column "PEB" of Table 2, and further, a resist pattern was obtained by performing puddle development for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

[0270] In the resist pattern obtained after development, the exposure amount at which the formed hole diameter becomes 17 nm was set as the effective sensitivity.

[0271] <CD Uniformity (CDU) Evaluation> In terms of effective sensitivity, the hole diameter of a pattern formed with a hole diameter of 17 nm was measured 24 times for a single hole, and the average value was taken as the average hole diameter of a single hole. The average hole diameter of a pattern formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations, and the standard deviation was calculated using this as the population. The results are shown in Table 3. The values ​​in the table represent the standard deviation (nm). [Table 3] When compared to comparative compositions 1 to 3, the standard deviation in compositions 1 to 14 was small, so the CD uniformity (CDU) evaluation was good.

[0272] (Electron beam exposure evaluation of resist composition: Organic solvent development) A 6-inch silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90°C for 60 seconds. A resist composition was spin-coated onto the silicon wafer such that the film thickness of the composition layer was 0.04 μm. Subsequently, a composition layer was formed by pre-baking on a direct hot plate at the temperature indicated in the column "PB" of Table 2 for 60 seconds. On the composition layer formed on the wafer, a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithograph [ELS-F125 125 keV manufactured by ELIONIX INC.] by varying the exposure amount in steps. After exposure, a post-exposure bake (PEB) was performed on a hot plate for 60 seconds at the temperature indicated in the "PEB" column of Table 2. Subsequently, the composition layer on the silicon wafer was developed by the dynamic dispensing method at 23°C for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer to obtain a resist pattern.

[0273] In the resist pattern obtained after development, the exposure amount at which the formed hole diameter becomes 17 nm was set as the effective sensitivity.

[0274] <CD Uniformity (CDU) Evaluation> In terms of effective sensitivity, the hole diameter of a pattern formed with a hole diameter of 17 nm was measured 24 times for a single hole, and the average value was taken as the average hole diameter of a single hole. The standard deviation was calculated using a population of 400 measurements of the average hole diameter of a pattern formed with a hole diameter of 17 nm within the same wafer. The results are shown in Table 4. The values ​​in the table represent the standard deviation (nm). [Table 4] Compared to comparative compositions 4 to 6, the standard deviation in compositions 15 to 28 was small, so the CD uniformity (CDU) evaluation was good. [Industrial Applicability]

[0275] The resist composition containing the salt of the present invention is suitable for microfabrication of semiconductors and is very useful industrially because it can obtain a resist pattern having good CD uniformity (CDU).

Claims

Claim 1 Salt represented by formula (I). [Equation (I), R 1 , R 2 and R 3 은, each independently, hydroxyl group, -OR 10 , -O-CO-OR 10 , or -OL 1 -CO-OR 10 Represents.R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Each represents, independently, a halogen atom, a carbon-1 to carbon-4 fluoroalkyl group, or a hydroxyl group. 1 R represents an alkandyl group having 1 to 6 carbon atoms. 10 represents the group represented by Equation (1a) or Equation (2a). 1 , X 2 and X 3 Each represents an oxygen atom or a sulfur atom independently. m1 represents any integer from 0 to 2, and when m1 is 2, the elements within the parentheses may be identical or different. m2 represents any integer from 0 to 2, and when m2 is 2, the elements within the parentheses may be identical or different. m3 represents any integer from 0 to 2, and when m3 is 2, the elements within the parentheses may be identical or different. m4 represents any integer from 0 to 2, and when m4 is 2, the multiple R 4 may be the same or different. m5 represents any integer from 0 to 2, and when m5 is 2, multiple R 5 may be the same or different. m6 represents any integer from 0 to 2, and when m6 is 2, multiple R 6 may be the same or different. m7 represents any integer from 0 to 2, and when m7 is 2, multiple R 7 may be the same or different. m8 represents any integer from 0 to 2, and when m8 is 2, multiple R 8 may be identical or different. m9 represents any integer from 0 to 2, and when m9 is 2, multiple R 9 ≤ m1 + m7 ≤ 5, ≤ m2 + m8 ≤ 4, ≤ m3 + m9 ≤ 4, and at least one of m1, m2, and m3 represents an integer greater than or equal to 1. 4 represents a single bond, -CH2-, -O-, -S-, -CO-, -SO-, or -SO2-. - represents a sulfonate anion. [In Equation (1a), R aa1 , R aa2 and R aa3 Each independently represents a C1- to C8 alkyl group that may have substituents, a C2- to C8 alkenyl group that may have substituents, a C3- to C20 alicyclic hydrocarbon group that may have substituents, or a C6- to C18 aromatic hydrocarbon group that may have substituents, or R aa1 and R aa2 They bond with each other to form alicyclic hydrocarbon groups having 3 to 20 carbon atoms together with the carbon atoms they bond to. * indicates a bond loss. [In Equation (2a), R aa1' and R aa2' Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R aa3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2' and R aa3' are combined with each other, and the -CX that they combine a - It forms a heterocyclic group having 3 to 20 carbon atoms together with -, and the -CH2- included in the said hydrocarbon group and said heterocyclic group may be substituted with -O- or -S-. a represents an oxygen or sulfur atom.* represents a bonding hand.] Claim 2 In paragraph 1, X 1 , X 2 and X 3 This oxygen atom, salt. Claim 3 In paragraph 1, R 1 , R 2 and R 3 une, each independently, -OR 10 , -O-CO-OR 10 or -OL 1 -CO-OR 10 Physitism. Claim 4 In paragraph 1, R 1 , R 2 and R 3 Salt, of which at least one is a hydroxyl group. Claim 5 In paragraph 1, a salt in which m2 is 0 or 1 and m3 is 0 or 1. Claim 6 In claim 1, the sulfonic acid anion is a salt that is an anion represented by the formula (IA). [Eating (IA) in,Q 1 and Q 2 Each represents, independently, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. 1 Y represents a saturated hydrocarbon group having 1 to 24 carbon atoms, wherein the -CH2- included in the saturated hydrocarbon group may be substituted with -O- or -CO-, and the hydrogen atoms included in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. 1 ...represents a methyl group that may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms that may have a substituent, wherein the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -SO2-, or -CO-. Claim 7 An acid-generating agent containing a salt described in any one of paragraphs 1 to 6. Claim 8 A resist composition comprising an acid generating agent as described in claim 7 and a resin having an acid unstable group, wherein the resin having an acid unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [Equations (a1-1) and (a1-2), L a1 and L a2 is, each independently, -O- or *-O-(CH2) k1 Represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bond loss with -CO-.R a4 and R a5 Each represents, independently, a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. a6 and R a7 Each represents, independently, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. m1 represents any one integer from 0 to 14. n1 represents any one integer from 0 to 10. n1' represents any one integer from 0 to 3. Claim 9 In claim 8, the resin having an acid instability group further comprises a structural unit represented by formula (a2-A). [Equation (a2-A), R a50 It represents silver, hydrogen atoms, halogen atoms, or carbon-1 to carbon-6 alkyl groups that may have halogen atoms. a51 It represents silver, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. a50 silver, single bond, or *-X a51 -(A a52 -X a52 ) nb It represents -, and * is -R a50 This represents the bond loss with the carbon atom it bonds with. a52 represents an alkandyl group having 1 to 6 carbon atoms. a51 and X a52 Each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. If mb is any integer greater than or equal to 2, multiple R a51 They may be identical or different. Claim 10 A resist composition according to claim 8, further containing a salt that generates an acid with a lower acidity than the acid generated from an acid generator. Claim 11 (1) a process of applying a resist composition described in claim 8 onto a substrate, (2) a process of drying the composition after application to form a composition layer, (3) a process of exposing the composition layer to light, (4) a process of heating the composition layer after exposure, and (5) a process of developing the composition layer after heating. A method for manufacturing a resist pattern. Claim 12 delete Claim 13 delete

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