Salt, acid generator, resin, resist composition, and method for producing resist patterns

Abstract

To provide a salt and the like and a resist composition which allow a resist pattern having good CD uniformity to be produced.SOLUTION: An acid generator contains: (I) a specific sulfonate having an unsaturated group of a specific triphenylsulfonium; or a structural unit derived from the specific sulfonate (I).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to salts, acid generators, resins, resist compositions, and methods for producing resist patterns. [Background technology]

[0002] Patent Document 1 describes a resist composition containing a resin that includes structural units derived from a salt represented by the following formula. TIFF0007943791000001.tif2772

[0003] Patent Document 2 describes a resist composition containing a resin that includes structural units derived from a salt represented by the following formula. TIFF0007943791000002.tif2772 [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-77404 [Patent Document 2] Japanese Patent Publication No. 2007-197718 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention provides a salt that forms a resist pattern with better CD uniformity (CDU) than a resist pattern formed by the above-mentioned resist composition. [Means for solving the problem]

[0006] This invention includes the following inventions. [1] An acid generator containing a salt represented by formula (I) or a structural unit represented by formula (IP). TIFF0007943791000003.tif158152[In formulas (I) and (IP), R4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms; the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2-. A 1 , A 2 and A 3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms; the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2-. m1 represents any integer of 1 to 5, and when m1 is 2 or more, the plural groups in the parentheses may be the same as or different from each other. m2 represents any integer of 0 to 5, and when m2 is 2 or more, the plural groups in the parentheses may be the same as or different from each other. m3 represents any integer of 0 to 5, and when m3 is 2 or more, the plural groups in the parentheses may be the same as or different from each other. m4 represents any integer of 0 to 5, and when m4 is 2 or more, the plural R 4 groups may be the same as or different from each other. m5 represents any integer of 0 to 5, and when m5 is 2 or more, the plural R 5 groups may be the same as or different from each other. m6 represents any integer of 0 to 5, and when m6 is 2 or more, the plural R 6 groups may be the same as or different from each other. m7 represents any integer of 0 to 4, and when m7 is 2 or more, the plural R 7 groups may be the same as or different from each other. m8 represents any integer of 0 to 5, and when m8 is 2 or more, the plural R 8 groups may be the same as or different from each other. m9 represents an integer between 0 and 5, and when m9 is 2 or greater, multiple R 9 They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. Q b1 and Q b2 Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y b1 represents a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the cycloaliphatic hydrocarbon group may be replaced with -O-, -CO-, -S-, or -SO2-. R bb1 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X 10 * represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * is R bb1 This represents the bonding site with the bonded carbon atom, and ** is L 10 This represents the connection point. L 10 This represents a hydrocarbon group having 1 to 36 carbon atoms, which may have single bonds or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -SO2-, or -CO-. [2]A 1 However, ***-X 01 -L 01 - or ***-L 01 -X 01 -and, A 2 However, ***-X 02 -L 02 - or ***-L 02 -X 02 -and, A 3 However, ***-X 03 -L 03 - or ***-L 03 -X 03 -and, X 01 , X 02 and X 03 These each independently represent -O-, -CO-, -S-, or -SO2-, L 01 , L 02 and L 03 Each of these independently represents a single bond or a hydrocarbon group with prime numbers 1 to 18. *** is S + The acid generator described in [1] represents the bonding site with the benzene ring to which it is bonded. [3]X 01 , X 02 and X 03 The acid generator described in [2] is an oxygen atom. [4]L 01 , L 02 and L 03 However, each is independently a single bond or an alkanediyl group having 1 to 6 carbon atoms [2] or [3], an acid generator. [5]Y b1 An acid generator according to any one of [1] to [4], wherein is a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group, an adamantanediyl group, or a norbornanelactonediyl group. [6]X 10 is equation (X 1 -1), formula (X 1 -2')~expression(X 1 -7'), expression (X 1 An acid generator according to any of [1] to [5], which is a group represented by any of [8]. TIFF0007943791000004.tif48155[Formula(X 1 -1), formula (X 1 -2')~expression(X 1 -7'), expression (X 1 -8) Medium, * and ** are binding sites, and ** is L 10 This represents the connection point. Rx represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. mx represents an integer between 0 and 4. [7]X 10 However, equation (X 1 -1), formula (X 1 -4) and equation (X 1 The acid generator described in [6] is a group represented by any of the following: -5). TIFF0007943791000005.tif4158[Formula(X 1 -1), formula (X 1 -4) and equation (X 1 -5) Medium, * and ** are binding sites, and ** is L 10 This represents the connection point with [the other element]. [8]L 10 The acid generator according to any one of [1] to [7], wherein the single bond or the alkanediyl group having 1 to 4 carbon atoms (however, the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-). A resist composition comprising an acid generator as described in any of [9][1] to [8].

[10] The resist composition according to [9], comprising a salt represented by formula (I) and a resin containing a structural unit (a1) having an acid-unstable group.

[11] Contains a resin comprising a structural unit represented by formula (IP), The resist composition according to [9], wherein the resin comprising a structural unit represented by formula (IP) further comprises a structural unit (a1) having an acid-unstable group.

[12] The resist composition according to

[11] , further comprising a salt represented by formula (I).

[13] The resist composition according to

[10] or

[11] , wherein the structural unit (a1) having an acid-unstable group is selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). TIFF0007943791000006.tif43141[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents a bond, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-. R a01 , R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[14] The resist composition according to any one of [9] to

[13] , further comprising a resin containing a structural unit represented by formula (a2-A). TIFF0007943791000007.tif4653[In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb -, and * represents a bond to the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same as or different from each other.] The resist composition according to any one of [9] to

[14] , further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator according to

[15] .

[16] The process for producing a resist pattern, comprising the steps of: (1) applying the resist composition according to any one of [9] to

[15] onto a substrate, (2) drying the applied composition to form a composition layer, (3) exposing the composition layer, (4) heating the composition layer after exposure, and (5) developing the composition layer after heating.

[17] The salt represented by the aforementioned formula (I).

[18] A 1 is ***-X 01 -L 01 - or ***-L 01 -X 01 -, and A2 However, ***-X 02 -L 02 - or ***-L 02 -X 02 -and, A 3 However, ***-X 03 -L 03 - or ***-L 03 -X 03 -and, X 01 , X 02 and X 03 These each independently represent -O-, -CO-, -S-, or -SO2-, L 01 , L 02 and L 03 Each of these independently represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms. *** is S + The salt described in

[17] represents the bonding site with the benzene ring to which it is bonded.

[19] X 01 , X 02 and X 03 The salt described in

[18] is an oxygen atom.

[20] L 01 , L 02 and L 03 However, each is independently a single bond or an alkanediyl group having 1 to 6 carbon atoms

[18] or

[19] salt.

[21] Y b1 The salt according to any one of

[17] to

[20] , wherein is a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, or a norbornanelactonediyl group.

[22] X 10 However, the above equation (X 1 -1), (X 1 -2')~(X 1 -7'), expression (X 1 A salt according to any of the

[17] -

[21] groups, which is represented by any of the groups in -8).

[23] X 10 However, the above equation (X 1 -1), formula (X 1 -4) and equation (X 1A salt of the group represented by any of the following

[22] (-5).

[24] L 10 The salt described in any of

[17] to

[23] , wherein the salt is a single bond or an alkanediyl group having 1 to 4 carbon atoms (wherein the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-).

[25] A resin containing the structural unit represented by the formula (IP) described above. [Effects of the Invention]

[0007] By using a resist composition containing the salt of the present invention, resist patterns can be manufactured with good CD uniformity (CDU). [Modes for carrying out the invention]

[0008] In this specification, "(meth)acrylic monomer" means at least one of acrylic monomers and methacrylic monomers. The same meaning applies to "(meth)acrylate" and "(meth)acrylic acid," etc. In the case of groups described in this specification that can take both linear and branched structures, either is acceptable. "Combined group" means a group formed by combining two or more of the exemplified groups, with their valence, bonding configuration, etc., appropriately modified. "Derived from" or "induced from" means that the polymerizable C=C bond contained in the molecule becomes a -CC- group (single bond) through polymerization. If stereoisomers exist, all stereoisomers are included. In this specification, "solid content of the resist composition" means the total amount of the resist composition excluding the solvent (E) described later.

[0009] <Salt represented by formula (I)> This invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salts (I), the negatively charged side is sometimes called the "anion (I)," and the positively charged side is sometimes called the "cation (I)." [Cation (I)] The cation (I) of the salt represented by formula (I) is the cation represented by formula (IC). TIFF0007943791000008.tif7786[In formula (IC), all symbols have the same meaning as in formula (I).]

[0010] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 In this context, a C1-C12 haloalkyl group refers to an alkyl group having a halogen atom and having C1-C12 atoms. Examples include C1-C12 alkyl fluorides, C1-C12 alkyl chlorides, C1-C12 alkyl bromides, and C1-C12 alkyl iodides. Examples of haloalkyl groups include C1-C12 perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, and perfluorobutyl group. The number of carbon atoms in the haloalkyl group is preferably 1-9, more preferably 1-4, and even more preferably 1-3. 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 and alkanediyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, and nonyl groups. Alkanediyl groups include linear or branched alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and Examples 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. The number of carbon atoms in the chain-like hydrocarbon group can be 1 to 12, preferably 1 to 9, more preferably 1 to 4, and even more preferably 1 to 3. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of alicyclic hydrocarbon groups include those listed below. The bonding site can be at any position. Specifically, monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as decahydronaphthyl, adamantyl, norbornyl, spirocyclohexane-1,2'-cyclopentane, and spiroadamantane-2,3'-cyclopentane, as well as spiro rings having cycloalkyl groups spiro-bonded to norvonyl or adamantyl 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, and binaphthyl groups. 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. Groups formed by combining two or more groups from among chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include groups formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic hydrocarbon group-*, alkyl group-aromatic hydrocarbon group-alkanediyl group-*, the -CH2- contained in the alkanediyl group and the alkyl group may be replaced with -O-, -CO-, -S- or -SO2-), and groups formed by combining an alicyclic hydrocarbon group and a chain Examples include groups combined with a compound hydrocarbon group (for example, alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*, alkyl group-alicyclic hydrocarbon group-alkanediyl group-*, the -CH2- contained in the alkanediyl group and the alkyl group may be replaced with -O-, -CO-, -S- or -SO2-), and groups combined with an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * indicates a bonding site. Examples of aromatic hydrocarbon groups - alkanediyl groups -* include aralkyl groups such as benzyl and phenethyl groups. Examples of alkyl-aromatic hydrocarbon groups-* include tolyl groups, xylyl groups, and cumenyl groups. Examples of alicyclic hydrocarbon groups - alkanediyl groups -* include cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl, and other cycloalkylalkyl groups. Examples of alkyl-alicyclic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, and cycloalkyl groups having alkyl groups such as 2-alkyladamantan-2-yl group. Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include the phenylcyclohexyl group. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include the cyclohexylphenyl group. Furthermore, in the combinations, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Also, any of these groups may be bonded to a benzene ring.

[0011] R 4 , R 5 , R 6 , R 7 , R 8 and R 9 If the -CH2- contained in the haloalkyl group or hydrocarbon group represented by is replaced by -O-, -CO-, -S-, or -SO2-, the number of carbon atoms before replacement shall be the total number of carbon atoms in the haloalkyl group or hydrocarbon group. This number may be one or two or more. Groups in which the -CH2- contained in haloalkyl groups and hydrocarbon groups is replaced with -O-, -CO-, -S-, or -SO2- include: hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced with -O-), thiol group (a group in which the -CH2- contained in a methyl group is replaced with -S-), carboxyl group (a group in which the -CH2-CH2- contained in an ethyl group is replaced with -O-CO-), alkoxy group (a group in which the -CH2- contained in an alkyl group is replaced with -O-), and alkoxycarbonyl group (a group in which the -CH2-CH2- contained in an alkyl group is replaced with -O- Groups in which -CH2- is replaced by -CO-, alkylcarbonyl group (a group in which -CH2- contained in an alkyl group having 2 to 12 carbon atoms is replaced by -CO-), alkylcarbonyloxy group (a group in which -CH2-CH2- contained in an alkyl group is replaced by -CO-O-), alkylthio group (a group in which -CH2- contained in an alkyl group is replaced by -S-), alkylsulfonyl group (a group in which -CH2- contained in an alkyl group is replaced by -SO2-), oxy group (a group in which -CH2- contained in a methylene group is replaced by -O-), carbonyl group (contained in a methylene group) (A group in which -CH2- is replaced by -CO-), thio group (A group in which -CH2- contained in a methylene group is replaced by -S-), sulfonyl group (A group in which -CH2- contained in a methylene group is replaced by -SO2-), alkanediyloxy group (A group in which -CH2- at any position in an alkanediyl group is replaced by -O-), alkanediyloxycarbonyl group (A group in which -CH2-CH2- at any position in an alkanediyl group is replaced by -O-CO-), alkanediylcarbonyl group (A group in which -CH2-CH2- at any position in an alkanediyl group (A group in which -CH2- is replaced by -CO-), Alkanediylcarbonyloxy group (A group in which -CH2-CH2- at any position in an Alkanediyl group is replaced by -CO-O-), Alkanediylthio group (A group in which -CH2- at any position in an Alkanediyl group is replaced by -S-), Alkanediylsulfonyl group (A group in which -CH2- at any position in an Alkanediyl group is replaced by -SO2-), Cycloalkoxy group, Cycloalkylalkoxy group, Alkoxycarbonyloxy group, Aromatic hydrocarbon group-carbonyloxy group,Examples include aromatic hydrocarbon groups - carbonyl groups, aromatic hydrocarbon groups - oxy groups, haloalkoxy groups (groups in which -CH2- at any position within a haloalkyl group is replaced with -O-), haloalkoxycarbonyl groups (groups in which -CH2-CH2- at any position within a haloalkyl group is replaced with -O-CO-), haloalkylcarbonyl groups (groups in which -CH2- at any position within a haloalkyl group is replaced with -CO-), haloalkylcarbonyloxy groups (groups in which -CH2-CH2- at any position within a haloalkyl group is replaced with -CO-O-), and groups that combine two or more of these groups. The alkoxy group preferably has 1 to 17 carbon atoms, and specifically includes methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups represent groups in which a carbonyl group or carbonyloxy group is bonded to an alkyl group or alkoxy group as described above. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 17 carbon atoms, such as acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. Examples of alkylthio groups include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, and undecylthio group. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkylsulfonyl groups include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, and undecylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediyloxy groups include alkanediyloxy groups having 1 to 17 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The number of carbon atoms in the alkanediyloxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediyloxycarbonyl groups include alkanediyloxycarbonyl groups having 2 to 17 carbon atoms, such as methyleneoxycarbonyl groups, ethyleneoxycarbonyl groups, propanediyloxycarbonyl groups, and butanediyloxycarbonyl groups. Examples of alkanediylcarbonyl groups include alkanediylcarbonyl groups having 2 to 17 carbon atoms, such as methylenecarbonyl groups, ethylenecarbonyl groups, propanediylcarbonyl groups, butanediylcarbonyl groups, and pentanediylcarbonyl groups. Examples of alkanediylcarbonyloxy groups include alkanediylcarbonyloxy groups having 2 to 17 carbon atoms, such as methylenecarbonyloxy groups, ethylenecarbonyloxy groups, propanediylcarbonyloxy groups, and butanediylcarbonyloxy groups. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. Examples of alkanediylthio groups include alkanediylthio groups having 1 to 17 carbon atoms, such as methylenethio groups, ethylenethio groups, and propylenethio groups. The number of carbon atoms in the alkanediylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediylsulfonyl groups include alkanediylsulfonyl groups having 1 to 18 carbon atoms, such as methylenesulfonyl groups, ethylenesulfonyl groups, and propylenesulfonyl groups. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as the cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 18 carbon atoms, such as the cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as the butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 18 carbon atoms, such as the benzoyloxy group. Examples of aromatic hydrocarbon group-carbonyl groups include aromatic hydrocarbon group-carbonyl groups having 7 to 18 carbon atoms, such as the benzoyl group. Examples of aromatic hydrocarbon group-oxy groups include aromatic hydrocarbon group-oxy groups having 6 to 16 carbon atoms, such as the phenyloxy group. Examples of haloalkoxy groups, haloalkoxycarbonyl groups, haloalkylcarbonyl groups, and haloalkylcarbonyloxy groups include haloalkoxy groups having 1 to 12 carbon atoms, haloalkoxycarbonyl groups having 2 to 12 carbon atoms, haloalkylcarbonyl groups having 2 to 12 carbon atoms, and haloalkylcarbonyloxy groups having 2 to 12 carbon atoms. For example, groups obtained by replacing one or more hydrogen atoms of the above-mentioned groups with halogen atoms are also included.

[0012] Furthermore, groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -O-, -CO-, -S-, or -SO2- include the groups shown below. The bonding site can be at any position. TIFF0007943791000010.tif46168R 4 , R 5 , R6 , R 7 , R 8 and R 9 Examples of substituents that the hydrocarbon group may have include halogen atoms and cyano groups. Examples of halogen atoms include the same groups as those described above. The hydrocarbon group may have one substituent or more substituents.

[0013] A 1 , A 2 and A 3 Examples of hydrocarbon groups include linear or branched chain hydrocarbon groups (e.g., alkanediyl groups), monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. A combination of two or more of these groups is also acceptable. Examples of linear hydrocarbon groups include linear alkane diyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl. Examples of branched alkanediyl 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. The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples include the groups shown below. The bonding site can be at any position. Specifically, monocyclic alicyclic hydrocarbon groups such as cycloalkanediyl groups, cycloalkanediyl groups, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group, and Examples include cycloalkyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, spirocyclohexane-1,2'cyclopentane, and spiroadamantane-2,3'-cyclopentane group, as well as polycyclic alicyclic hydrocarbon groups such as spiro rings having a cycloalkyl group spiro-bonded to a norbonyl group or an adamantyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, even more preferably 3 to 12, and even more preferably 3 to 10. Examples of aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, biphenylene groups, phenanthrylene groups, and other arylene groups. 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.

[0014] Groups formed by combining two or more groups include groups formed by combining an alicyclic hydrocarbon group and an alkanediyl group, groups formed by combining an aromatic hydrocarbon group and an alkanediyl group, and groups formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In the combinations, two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups may be combined. Furthermore, any of the groups may be bonded to a benzene ring. Examples of groups combining an alicyclic hydrocarbon group and an alkanediyl group include -divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-alkanediyl group-, and -alkanediyl group-divalent alicyclic hydrocarbon group-. Examples of groups combining an aromatic hydrocarbon group and an alkanediyl group include -divalent aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-alkanediyl group-, and -alkanediyl group-divalent aromatic hydrocarbon group-. Examples of groups combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, and -alicyclic hydrocarbon group-aromatic hydrocarbon group-alicyclic hydrocarbon group-.

[0015] A 1 , A 2 and A 3 If the -CH2- contained in a hydrocarbon group is replaced by -O-, -CO-, -S-, or -SO2-, the number of carbon atoms before replacement is considered the total number of carbon atoms in the hydrocarbon group. This number may be one or two or more, but it is preferably one to three. Groups in which the -CH2- contained in a hydrocarbon group is replaced with -O-, -CO-, -S-, or -SO2- include: hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced with -O-), carboxyl group (a group in which the -CH2-CH2- contained in an ethyl group is replaced with -O-CO-), thiol group (a group in which the -CH2- contained in a methyl group is replaced with -S-), alkoxy group (a group in which the -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl group (a group in which the -CH2-CH2- at any position in an alkyl group is replaced with -O-) , a group replaced by -O-CO-), alkylcarbonyl group (a group in which -CH2- at any position in the alkyl group is replaced by -CO-), alkylcarbonyloxy group (a group in which -CH2-CH2- at any position in the alkyl group is replaced by -CO-O-), alkylthio group (a group in which -CH2- at any position in the alkyl group is replaced by -S-), alkylsulfonyl group (a group in which -CH2- at any position in the alkyl group is replaced by -SO2-), oxy group (a group in which -CH2- in the methylene group is replaced by -O-) (a group in which -CH2- in the methylene group is replaced by -CO-), thio group (a group in which -CH2- in the methylene group is replaced by -S-), sulfonyl group (a group in which -CH2- in the methylene group is replaced by -SO2-), alkanediyloxy group (a group in which -CH2- at any position in the alkanediyl group is replaced by -O-), alkanediyloxycarbonyl group (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced by -O-CO-), alkanediylcarbonyl group (a (A group in which -CH2- at any position in the alkanediyl group is replaced with -CO-), alkanediylcarbonyloxy group (A group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -CO-O-), alkanediylsulfonyl group (A group in which -CH2- at any position in the alkanediyl group is replaced with -SO2-), alkanediylthio group (A group in which -CH2- at any position in the alkanediyl group is replaced with -S-), cycloalkoxy group, cycloalkylalkoxy group, alkoxycarbonyloxy group,Examples include aromatic hydrocarbon groups, carbonyloxy groups, and groups formed by combining two or more of these groups. Examples of alkoxy groups include alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups represent groups in which a carbonyl group or carbonyloxy group is bonded to an alkyl group or alkoxy group as described above. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 20 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 20 carbon atoms, such as acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 20 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. Examples of alkylthio groups include alkylthio groups having 1 to 20 carbon atoms, such as methylthio groups, ethylthio groups, propylthio groups, and butylthio groups. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkylsulfonyl groups include alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl groups, ethylsulfonyl groups, and propylsulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediyloxy groups include alkanediyloxy groups having 1 to 20 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The number of carbon atoms in the alkanediyloxy group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediyloxycarbonyl groups include alkanediyloxycarbonyl groups having 2 to 20 carbon atoms, such as methyleneoxycarbonyl groups, ethyleneoxycarbonyl groups, propanediyloxycarbonyl groups, and butanediyloxycarbonyl groups. Examples of alkanediylcarbonyl groups include alkanediylcarbonyl groups having 2 to 20 carbon atoms, such as methylenecarbonyl groups, ethylenecarbonyl groups, propanediylcarbonyl groups, butanediylcarbonyl groups, and pentanediylcarbonyl groups. Examples of alkanediylcarbonyloxy groups include alkanediylcarbonyloxy groups having 2 to 20 carbon atoms, such as methylenecarbonyloxy groups, ethylenecarbonyloxy groups, propanediylcarbonyloxy groups, and butanediylcarbonyloxy groups. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. Examples of alkanediylsulfonyl groups include alkanediylsulfonyl groups having 1 to 20 carbon atoms, such as methylenesulfonyl groups, ethylenesulfonyl groups, and propylenesulfonyl groups. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkanediylthio groups include alkanediylthio groups having 1 to 20 carbon atoms, such as methylenethio groups, ethylenethio groups, and propylenethio groups. The number of carbon atoms in the alkanediylthio group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 20 carbon atoms, such as the cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as the cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as the butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 20 carbon atoms, such as the benzoyloxy group.

[0016] Furthermore, groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -O-, -CO-, -S-, or -SO2- include the groups shown below. Also, among the groups shown below, groups in which -O- is replaced with -S- and -CO- is replaced with -SO2- are also examples. The bonding site can be at any position. TIFF0007943791000012.tif47164A 1 , A 2 and A 3 The substituents that the hydrocarbon group may have include R 4 ~R 9 The hydrocarbon group may have substituents similar to those listed above.

[0017] A 1 , A 2 and A 3 Each of these is preferably a hydrocarbon group having 1 to 20 carbon atoms (the hydrocarbon group may have substituents, and one of the -CH2- groups in the hydrocarbon group is replaced with -O-, -CO-, -S-, or -SO2-). More preferably, A 1 is ***-L 011 -X 01 -L 012 - and A 2 is ***-L 021 -X 02 -L 022 - and A 3 is ***-L 031-X 03 -L 032 -is (X 01 , X 02 and X 03 These represent -O-, -CO-, -S-, or -SO2- independently. 011 , L 012 , L 021 , L 022 , L 031 and L 032 Each of these independently represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms. However, L 011 and L 012 The total number of carbon atoms is 0 to 18, L 021 and L 022 The total number of carbon atoms is 0 to 18, L 031 and L 032 The total number of carbon atoms is 0 to 18. *** is S + This represents the bonding site with the benzene ring to which it is bonded. ) is more preferable, A 1 is, ***-X 01 -L 01 - or ***-L 01 -X 01 - and A 2 is, ***-X 02 -L 02 - or ***-L 02 -X 02 - and A 3 is, ***-X 03 -L 03 - or ***-L 03 -X 03 -is (X 01 , X 02 and X 03 These represent -O-, -CO-, -S-, or -SO2- independently. 01 , L 02 and L 03 Each of these independently represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms. *** represents S + This represents the bonding site with the benzene ring to which it is bonded. ) is even more preferable. A 1 , A 2 and A 3 It is preferable that the molecule has no substituents other than substitution with -O-, -CO-, -S-, or -SO2-. L 011 , L 012 , L 021 , L 022 , L 031 , L 032 , L 01 , L 02 and L 03 A hydrocarbon group having 1 to 18 carbon atoms (the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2-) is a hydrocarbon group having 1 to 18 carbon atoms. 1 , A 2 and A 3 Similar groups to those listed above can be cited. X 01 , X 02 and X 03 Each of these is preferably -O- or -S-, and more preferably -O-. L 011 , L 012 , L 021 , L 022 , L 031 , L 032 , L 01 , L 02 and L 03Preferably, each of them is a single-bonded hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2-), more preferably a single-bonded chain hydrocarbon group having 1 to 9 carbon atoms (the -CH2- contained in the chain hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2-), and preferably a single-bonded alkanediyl group having 1 to 6 carbon atoms (the alkanediyl group may be replaced with -O-, -CO-, -S- or -SO2-). It is even more preferable that the -CH2- contained may be replaced with -O- or -CO-, and it is even more preferable that it is a single bond, an alkanediyl group having 1 to 4 carbon atoms (the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), and it is even more preferable that it is a single bond, an alkanediyl group having 1 to 3 carbon atoms (the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-). In particular, it is preferable that it is a single bond, a methylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a carbonyl group, a carbonyloxy group, a carbonyloxymethylene group, an ethyleneoxy group, a methylenecarbonyloxymethylene group, and it is even more preferable that it is a single bond, a methylene group, and a carbonyl group. A 1 , A 2 and A 3 S + The bond position to the benzene ring to which it is bonded is S + The bond position can be any of the ortho, m, or p positions. In particular, S + It is preferable that the bond is at the p-position or m-position relative to the bond site. More specifically, when m1, m2 and m3 are 1, A 1 , A 2 and A 3 Each of them is independent of S + It is preferable that the bond is at the p-position or m-position relative to the bond site, and more preferably at the p-position. 1 , A 2 and A 3 Each of them is independent of S +It is preferable that one atom is bonded to the orthogonal or m-position, one atom is bonded to the orthogonal or m-position, and it is more preferable that two atoms are bonded to the m-position. When m1, m2 and m3 are 3, A 1 , A 2 and A 3 Each of them is independent of S + It is preferable that two are bonded to the oro or m position and one is bonded to the p or m position relative to the bonding site, and it is more preferable that two are bonded to the m position and one is bonded to the p position. When m1, m2 and m3 are 4, A 1 , A 2 and A 3 Each of them is independent of S + It is preferable that two of the atoms are bonded at the ortho or metapositional position, and two are bonded at the p or metapositional position, and it is more preferable that two are bonded at the orthoposition and two are bonded at the metapositional position. m1 is preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, even more preferably 1 or 2, and even more preferably 1. m2 is preferably 0, 1, 2, 3, or 4, more preferably 0, 1, 2, or 3, even more preferably 0, 1, or 2, and even more preferably 0 or 1. m3 is preferably 0, 1, 2, 3, or 4, more preferably 0, 1, 2, or 3, even more preferably 0, 1, or 2, and still more preferably 0 or 1. m4 is preferably 0, 1, 2, 3, or 5, and is preferably 0, 1, 2, or 5. m5 is preferably 0 or 1. m6 is preferably 0 or 1. m7 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1. m8 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1. m9 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, and even more preferably 0 or 1. Furthermore, if m1 is 2 or more, or if m2 and m3 are 1 or more, the bases within the multiple parentheses may be the same or different from each other, that is, X 1 ~X 3 When there are multiple instances of each, R 4 ~R 6 When there are multiple instances of each, they may all be identical or different from one another. R 4 , R 5 and R 6 Each of these is preferably independently a halogen atom, a C1-C4 fluorinated alkyl group, or a C1-C6 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), more preferably a halogen atom, a C1-C4 fluorinated alkyl group, or a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), even more preferably a fluorine atom, an iodine atom, a C1-C4 perfluoroalkyl group, or a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), and even more preferably a fluorine atom, an iodine atom, or a trifluoromethyl group. R 4 , R 5 and R 6 The bond positions to the benzene ring are, independently of each other, A 1 , A 2 and A 3 The bond position can be any of the or, m, or p positions. In particular, when m4, m5, and m6 are 1, R 4 , R 5 and R 6 Each of them is independently, A 1 , A 2 and A 3 It is preferable that the bond is at the p-position or m-position relative to the bond site, and more preferably at the p-position. 4 , R 5and R 6 Each of them is independently, A 1 , A 2 and A 3 It is preferable that one atom is bonded to the orthogonal or m-position, one atom is bonded to the p-position or m-position, and it is more preferable that two atoms are bonded to the m-position. When m4, m5 and m6 are 3, R 4 , R 5 and R 6 Each of them is independently, A 1 , A 2 and A 3 It is preferable that two are bonded to the oro or m position and one is bonded to the p or m position relative to the bonding site, and more preferably that two are bonded to the m position and one is bonded to the p position. When m4, m5 and m6 are 4, R 4 , R 5 and R 6 Each of them is independently, A 1 , A 2 and A 3 It is preferable that two atoms are bonded to the ortho or m position and two atoms are bonded to the p or m position relative to the bonding site, and it is more preferable that two atoms are bonded to the m position, one atom is bonded to the ortho position and one atom is bonded to the p position. R 7 , R 8 and R 9 Each of these is preferably independently a halogen atom, a C1-C4 fluorinated alkyl group, or a C1-C6 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), more preferably a halogen atom, a C1-C4 fluorinated alkyl group, or a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), even more preferably a fluorine atom, an iodine atom, a C1-C4 perfluoroalkyl group, or a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), and even more preferably a fluorine atom, an iodine atom, or a trifluoromethyl group. R 7 , R 8 and R 9The bond positions to the benzene ring are, independently of each other, S + The bond position can be any of the or, m, or p positions. In particular, when m7, m8, and m9 are 1, R 7 , R 8 and R 9 Each of them is independent of S + It is preferable that the bond is at the p-position or m-position relative to the bond site, and more preferably at the p-position. 7 , R 8 and R 9 Each of them is independent of S + It is preferable that one atom is bonded to the orthogonal or m-position and one atom is bonded to the p-position or m-position relative to the bonding site, and more preferably that one atom is bonded to the m-position and one atom is bonded to the p-position. When m7, m8 and m9 are 3, R 7 , R 8 and R 9 Each of them is independent of S + It is preferable that two are bonded to the oro or m position and one is bonded to the p or m position relative to the bonding site, and it is more preferable that two are bonded to the m position and one is bonded to the p position. When m7, m8 and m9 are 4, R 7 , R 8 and R 9 Each of them is independent of S + It is preferable that two atoms are bonded to the ortho or m position and two atoms are bonded to the p or m position relative to the bonding site, and it is more preferable that two atoms are bonded to the m position, one atom is bonded to the ortho position and one atom is bonded to the p position.

[0018] Examples of cations represented by formula (IC) include the cation represented by formula (IC-1) (hereinafter sometimes referred to as "cation (IC-1)"). TIFF0007943791000013.tif78107 [In formula (IC-1), R 4 , R 5 , R 6 , R 7 , R 8 , R 9, m1, m2, m3, m4, m5, m6, m7, m8, m9, L 01 , L 02 , L 03 , X 01 , X 02 and X 03 The symbol has the same meaning as described above.

[0019] X 01 , X 02 and X 03 It is preferable that it be -O-. X 01 , X 02 and X 03 The bond positions to the benzene ring are, respectively, A 1 , A 2 , A 3 This is similar to the bond position to the benzene ring.

[0020] Examples of cation (I) include the following cations: TIFF0007943791000014.tif237162

[0021] TIFF0007943791000015.tif229157

[0022] TIFF0007943791000016.tif119153

[0023] TIFF0007943791000017.tif115165

[0024] TIFF0007943791000018.tif235164

[0025] TIFF0007943791000019.tif168161

[0026] [Anion (I)] The anion (I) of the salt represented by formula (I) is the same anion represented by formula (IA). TIFF0007943791000020.tif2679[In formula (IA), all signs have the same meaning as in formula (I).]

[0027] Q b1 and Q b2 Examples of perfluoroalkyl groups represented by include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, and perfluorohexyl group. Q b1 and Q b2 For alkyl groups represented by , the same basic principles as described above can be used for alkyl groups having 1 to 12 carbon atoms. The acid generator (B) is preferably a fluorine-containing acid generator, Q b1 and Q b2 Preferably, at least one of them contains a fluorine atom or a perfluoroalkyl group, more preferably independently a fluorine atom or a perfluoroalkyl group, even more preferably a fluorine atom or a trifluoromethyl group, and even more preferably both being fluorine atoms.

[0028] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups, branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. Groups formed by combining two or more of these groups may also be used. Specifically, linear alkane diyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; Monocyclic, divalent, alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0029] L b1 Examples of groups in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO- include the group represented by any of the formulas (b1-1) to (b1-3). In the groups represented by formulas (b1-1) to (b1-3) and their specific examples, the groups represented by formulas (b1-4) to (b1-11), * and ** represent the bonding site, and * is -Y b1 This represents a combination of two things.

[0030] TIFF0007943791000021.tif23103 [In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0031] In groups represented by formulas (b1-1) to (b1-3), if the -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before the replacement shall be the number of carbon atoms of the saturated hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups.

[0032] L b2 These are preferably a single bond, a methylene group, -CH(CF3)-, and -C(CF3)2-. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. Lb4 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms in the divalent saturated hydrocarbon group may be substituted with fluorine atoms, and it is preferably a methylene group, -CH(CF3)-, or -C(CF3)2-. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7 Preferably, the saturated hydrocarbon group is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- groups in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0033] L b1 As for the group in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferred. The groups represented by formula (b1-1) include those represented by formulas (b1-4) to (b1-8), respectively. TIFF0007943791000022.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, Lb9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms 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. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms 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. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atoms 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.

[0034] L b8This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is 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 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is 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 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is 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.

[0035] The groups represented by formula (b1-3) include those represented by formulas (b1-9) to (b1-11), respectively. TIFF0007943791000023.tif23139 formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy group may be substituted with a hydroxyl group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy 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. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy 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.

[0036] Furthermore, in the case of the groups represented by formulas (b1-9) to (b1-11), if a hydrogen atom in a saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution shall be the number of carbon atoms in the saturated hydrocarbon group. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, butyryloxy group, cyclohexylcarbonyloxy group, and adamantylcarbonyloxy group.

[0037] The following are examples of bases represented by formula (b1-4): TIFF0007943791000024.tif16154

[0038] The following are examples of bases represented by formula (b1-5): TIFF0007943791000025.tif68152

[0039] The following are examples of bases represented by formula (b1-6): TIFF0007943791000026.tif29150

[0040] The following are examples of bases represented by formula (b1-7): TIFF0007943791000027.tif57146

[0041] The following are examples of bases represented by formula (b1-8): TIFF0007943791000028.tif23150

[0042] The following are examples of bases represented by formula (b1-2): TIFF0007943791000029.tif31161

[0043] The following are examples of bases represented by formula (b1-9): TIFF0007943791000030.tif44137

[0044] The following are examples of bases represented by formula (b1-10): TIFF0007943791000031.tif92165

[0045] The following are examples of bases represented by formula (b1-11): TIFF0007943791000032.tif84164

[0046] Y b1 Examples of alicyclic hydrocarbon groups in which the -CH2- contained in the alicyclic hydrocarbon group represented by is not replaced by -O-, -S-, -SO2-, or -CO- include the groups represented by formulas (Y1) to (Y11) and (Y36) to (Y38). Y b1 When the -CH2- contained in the alicyclic hydrocarbon group represented by is replaced by -O-, -S-, -SO2-, or -CO-, the number of replacements may be one or two or more. Examples of such groups include those represented by formulas (Y12) to (Y35) and (Y39) to (Y43). The -O- or -CO- in the groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43) may also be replaced by -S- or -SO2-.

[0047] TIFF0007943791000033.tif83167Y b1The alicyclic hydrocarbon group represented is preferably a group represented by any of formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y43), more preferably a group represented by formula (Y11), (Y15), (Y16), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42), or (Y43), and even more preferably a group represented by formula (Y11), (Y15), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42), or (Y43).

[0048] Y b1 Substituents for the alicyclic hydrocarbon group represented by include halogen atoms, hydroxyl groups, C1-C16 alkyl groups which may be substituted with hydroxyl groups (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), C3-C16 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, C7-C21 aralkyl groups, glycidyloxy groups, and -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 ) represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and the -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -SO2-, or -CO-, and the hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced with a hydroxyl group or a fluorine atom. ja represents an integer from 0 to 4. ) are some examples.

[0049] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group. Alicyclic hydrocarbon groups may also have chain hydrocarbon groups, such as methylcyclohexyl group and dimethylcyclohexyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, phenanthryl groups, and other aryl groups. Aromatic hydrocarbon groups may have a chain-type hydrocarbon group or an alicyclic hydrocarbon group. Preferred aromatic hydrocarbon groups are those having a chain-type hydrocarbon group with 1 to 18 carbon atoms (e.g., tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (e.g., p-adamantylphenyl group, p-cyclohexylphenyl group). 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 methyl, ethyl, propyl, isopropyl, 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 6, and even more preferably 1 to 4. Examples of alkyl groups substituted with a hydroxyl group include hydroxymethyl groups, hydroxyethyl groups, and other hydroxyalkyl groups. Examples of aralkyl groups include benzyl groups, phenethyl groups, phenylpropyl groups, naphthylmethyl groups, and naphthylethyl groups. Groups in which the -CH2- group in an alkyl group is replaced with -O-, -SO2-, or -CO- include alkoxy groups, alkylsulfonyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, or combinations thereof. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, 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, and propylsulfonyl groups. The number of carbon atoms in the sulfonyl 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, and butoxycarbonyl groups. 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 alkylcarbonyl groups include acetyl groups, propionyl groups, and butyryl groups. 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. Examples of alkylcarbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups combining an alkoxy group and an alkyl group, groups combining two alkoxy groups, groups combining an alkoxy group and an alkylcarbonyl group, and groups combining an alkoxy group and an alkylcarbonyloxy 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 groups formed by combining alkoxy groups include alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy. 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 alkylcarbonyl group include alkoxyalkylcarbonyl groups such as methoxyacetyl group, methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group. The number of carbon atoms in the alkoxyalkylcarbonyl 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 alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, and ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Groups in which the -CH2- group in an alicyclic hydrocarbon group is replaced with -O-, -SO2-, or -CO-, etc., include the groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43).

[0050] Y b1Preferably, is an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents, even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, and even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, and even more preferably an alicyclic cyclohexanediyl group having substituted, an alicyclic adamantanediyl group having substituted, an alicyclic norbornanediyl group having substituted, and the -CH2- constituting the alicyclic hydrocarbon group, cyclohexanediyl group, adamantanediyl group or norbornanediyl group may be replaced with -O-, -S-, -CO- or -SO2-. Y b1 The substituents that may be present include hydroxyl groups, halogen atoms, cyano groups, C1-C6 alkyl groups, or C1-C6 alkoxy groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. Among these, fluorine atoms, hydroxyl groups, methyl groups, and ethyl groups are preferred.

[0051] R bb1 The halogen atom is R 4 ~R 9 The same halogen atoms listed above can be cited. bb1 Alkyl alkyl groups that may have halogen atoms are, as long as the upper limit of the number of carbon atoms allows, R 4 ~R 9 Examples include the same alkyl groups and haloalkyl groups listed in the examples above. R bb1 This is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X 10 However, in the case of a group represented by *-Ax-Ph-Ay-**, it is preferable that it be a linking group represented by the following formula (X10). In formula (X10) TIFF0007943791000034.tif3351, Ax is R 10The symbol represents the bonded carbon atom and the bond species, and it represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay is L 10 This represents the type of bond that binds to a given element, and is selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. If either Ax or Ay is a single bond, it is preferable that the other is one selected from the group consisting of ether bonds, ester bonds, and carbonate ester bonds. Rx represents a halogen atom, a hydroxyl group, a C1-C6 alkyl fluoride or C1-C18 alkyl group, or a C1-C6 alkoxy group. Among these, a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, and an ethyl group are preferred. mx represents an integer between 0 and 4, preferably 0, 1, or 2. If mx is an integer greater than or equal to 2, multiple Rx values ​​may be the same or different from one another. The bond position of Ay on the phenylene group is preferably at the m-position or p-position relative to Ax, and more preferably at the p-position. X 10 For example, the following equation (X 1 -1), formula (X 1 -2')~expression(X 1 -7') and equation (X 1 The group represented by -8) is an example. 10 This indicates the bonding position with the carbon atom to which it is bonded. ** represents L 10 This represents the bond position that connects with [another element]. TIFF0007943791000035.tif51156 expression (X 1 -2')~expression(X 1 The following are specific examples of groups represented by -7'): TIFF0007943791000036.tif79122 Among them, X 10 is the equation (X 1 -1)~Formula(X 1 A group represented by formula (X) is preferred, and formula (X 1 -1), formula (X 1 -3), formula (X1 -4) or formula (X 1 It is more preferable that the group is represented by formula (X 1 The base represented by (X -1), formula (X 1 (X) is represented by a base or formula (X 1 It is even more preferable that the group be represented by (-5).

[0052] L 10 Examples of divalent hydrocarbon groups having 1 to 36 carbon atoms include divalent aliphatic hydrocarbon groups (divalent chain hydrocarbon groups such as alkanediyl groups, alkeniyl groups, and alkynediyl groups, as well as divalent alicyclic hydrocarbon groups), divalent aromatic hydrocarbon groups, etc., and divalent hydrocarbon groups may also be formed by combining two or more of these groups.

[0053] Examples of alkanediyl groups include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; Examples of branched alkanediyl 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. Examples of alkenediyl groups include ethendiyl group, propendiyl group, isopropendiyl group, butendiyl group, isobutendiyl group, tert-butendiyl group, pentendiyl group, hexendiyl group, heptendiyl group, octindiyl group, isooctindiyl group, and nonendiyl group. Examples of alkynediyl groups include ethindiyl group, propindiyl group, isopropindiyl group, butindiyl group, isobutindiyl group, tert-butindiyl group, pentindiyl group, hexindiyl group, octindiyl group, and nonindiyl group. The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. The divalent alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic. Examples of divalent alicyclic hydrocarbon groups include those listed below. The bonding site can be at any position. Specifically, examples of monocyclic divalent alicyclic hydrocarbon groups include monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclohexene-3,6-diyl, and cyclooctane-1,5-diyl, while examples of polycyclic divalent alicyclic hydrocarbon groups include polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, 5-norbornene-2,3-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl. The number of carbon atoms in the divalent alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12. Examples of divalent aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, biphenylene groups, and phenanthrylene groups. 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. Examples of hydrocarbon groups combining two or more types include groups combining an alkanediyl group with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, such as -alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-alicyclic hydrocarbon group-, -alkanediyl group-alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, and -aromatic hydrocarbon group-alkanediyl group-.

[0054] L 10The -CH2- group in the hydrocarbon group having 1 to 36 carbon atoms may be replaced with -O-, -S-, -CO-, or -SO2-. L 10 If a hydrocarbon group having 1 to 36 carbon atoms has substituents, or if the -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-, the number of carbon atoms before the replacement shall be considered the number of carbon atoms in the hydrocarbon group. Groups in which the -CH2- contained in a hydrocarbon group is replaced with -O-, -S-, -SO2-, or -CO- include: hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced with -O-), carboxyl group (a group in which the -CH2-CH2- contained in an ethyl group is replaced with -O-CO-), thiol group (a group in which the -CH2- contained in a methyl group is replaced with -S-), alkoxy group (a group in which the -CH2- at any position in an alkyl group is replaced with -O-, -S-, -SO2-, or -CO-). Groups in which -O- is replaced, alkoxycarbonyl group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -O-CO-), alkylcarbonyl group (a group in which -CH2- at any position in the alkyl group is replaced with -CO-), alkylcarbonyloxy group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -CO-O-), alkanediyloxy group (in which the alkanediyl group is replaced Examples include groups in which -CH2- at any position in an alkanediyl group is replaced by -O-, alkanediyloxycarbonyl groups (groups in which -CH2-CH2- at any position in an alkanediyl group is replaced by -O-CO-), alkanediylcarbonyl groups (groups in which -CH2- at any position in an alkanediyl group is replaced by -CO-), alkanediylcarbonyloxy groups (groups in which -CH2-CH2- at any position in an alkanediyl group is replaced by -CO-O-), alkylthio groups (groups in which -CH2- at any position in an alkyl group is replaced by -S-), alkylsulfonyl groups (groups in which -CH2- at any position in an alkyl group is replaced by -SO2-), cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, aromatic hydrocarbon group-carbonyloxy groups, and groups that combine two or more of these groups. Examples of alkoxy groups include alkoxy groups having 1 to 17 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4 or 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups represent groups in which a carbonyl group or carbonyloxy group is bonded to an alkyl group or alkoxy group as described above. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl, alkylcarbonyl, and alkylcarbonyloxy groups is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 to 3. Examples of alkanediyloxy groups include alkanediyloxy groups having 1 to 17 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The number of carbon atoms in the alkanediyloxy group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4 or 1 to 3. Examples of alkanediyloxycarbonyl groups include alkanediyloxycarbonyl groups having 2 to 17 carbon atoms, such as methyleneoxycarbonyl group, ethyleneoxycarbonyl group, propanediyloxycarbonyl group, and butanediyloxycarbonyl group. Examples of alkanediylcarbonyl groups include alkanediylcarbonyl groups having 2 to 18 carbon atoms, such as methylenecarbonyl group, ethylenecarbonyl group, propanediylcarbonyl group, butanediylcarbonyl group, and pentanediylcarbonyl group. Examples of alkanediylcarbonyloxy groups include alkanediylcarbonyloxy groups having 2 to 17 carbon atoms, such as methylenecarbonyloxy group, ethylenecarbonyloxy group, propanediylcarbonyloxy group, and butanediylcarbonyloxy group. The number of carbon atoms in the alkanediyloxycarbonyl group, alkanediylcarbonyl group, and alkanediylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4 or 2 to 3. Examples of alkylthio groups include alkylthio groups having 1 to 17 carbon atoms, such as methylthio groups, ethylthio groups, and propylthio groups. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4 or 1 to 3. Examples of alkylsulfonyl groups include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl groups, ethylsulfonyl groups, and propylsulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4 or 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as the cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as the cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as the butoxycarbonyloxy group. The number of carbon atoms in the cycloalkoxy group and cycloalkylalkoxy group is preferably 3 to 11, more preferably 3 to 6. The number of carbon atoms in the alkoxycarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 to 3. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as the benzoyloxy group. Furthermore, the following groups are examples of groups in which the -CH2- contained in an alicyclic hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-. The positions of the -O- or -CO- in the following groups may also be replaced with -S- or -SO2-, respectively. The bonding site can be at any position. TIFF0007943791000038.tif46168

[0055] L 10 Examples of substituents that the hydrocarbon group may have include halogen atoms and cyano groups. L 10 The group in which the -CH2- contained in the hydrocarbon group is replaced by -O- or -CO- is L 10 It can substantially have substituents of hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. L 10 The divalent hydrocarbon group having 1 to 36 carbon atoms may have one substituent or more substituents.

[0056] L 10 This includes single bonds, C1-C4 alkanediyl groups (where the -CH2- in the alkanediyl group may be replaced with -O- or -CO-), C3-C18 alicyclic hydrocarbon groups (where the -CH2- in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO2- or -CO-), C6-C18 aromatic hydrocarbon groups which may have substituents, and groups formed by combining a C1-C4 alkanediyl group and a C3-C18 alicyclic hydrocarbon group (where the alkanediyl The -CH2- contained in the yl group may be replaced with -O- or -CO-, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO2- or -CO-.) or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents (however, the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-), and preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (however (The -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-.) A cycloaliphatic hydrocarbon group having 3 to 18 carbon atoms (however, the -CH2- contained in the cycloaliphatic hydrocarbon group may be replaced with -O- or -CO-.) A phenylene group which may have substituents A group formed by combining an alkanediyl group having 1 to 4 carbon atoms and a cycloaliphatic hydrocarbon group having 3 to 18 carbon atoms (however, the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-, and the cycloaliphatic hydrocarbon group may be replaced with -O- or -CO-.) It is more preferable that the group is a combination of a C1-C4 alkanediyl group and a phenylene group which may have substituents (however, the C1-C4 alkanediyl group may have substituents), and it is even more preferable that it is a single bond or a C1-C4 alkanediyl group (however, the C1-C4 alkanediyl group may have substituents).

[0057] Examples of anions (I) include the following: TIFF0007943791000039.tif83168

[0058] In the anions represented by equations (Ia-1) to (Ia-14), the R in equation (I) 10 Anions in which the corresponding methyl group is replaced by a hydrogen atom can also be given as specific examples of anion (I). Among these, the anions represented by formulas (Ia-1) to (Ia-6) are preferred.

[0059] Examples of salt(I) include salts formed by arbitrarily combining the cations and anions mentioned above. Specific examples of salt(I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the anion or cation described above. For example, salt (I-1) is a salt consisting of the anion represented by formula (Ia-1) and the cation represented by formula (Ic-1), and is the salt shown below. TIFF0007943791000040.tif32121 [Table 1] TIFF0007943791000042.tif239159 TIFF0007943791000043.tif197157

[0060] In particular, salt (I) is divided into salt (I-1) to salt (I-6), salt (I-15) to salt (I-20), salt (I-29) to salt (I-34), salt (I-43) to salt (I-48), salt (I-57) to salt (I-62), salt (I-71) to salt (I-76), salt (I-85) to salt (I-90), and salt (I-9 9) ~Salt (I-104), Salt (I-113) ~Salt (I-118), Salt (I-127) ~Salt (I-132), Salt (I-141) ~Salt (I-146), Salt (I-155) ~Salt (I-160), Salt (I-169) ~Salt (I-174), Salt (I-183) ~Salt (I-188), Salt (I-1 97) ~ Salt (I-202), Salt (I-211) ~ Salt (I-216), Salt (I-225) ~ Salt (I-230), Salt (I-239) ~ Salt (I-244), Salt (I-253) ~ Salt (I-258), Salt (I-267) ~ Salt (I-272), Salt (I-281) ~ Salt (I-286), Salt (I- 295)~Salt (I-300), Salt (I-309)~Salt (I-314), Salt (I-323)~Salt (I-328), Salt (I-337)~Salt (I-342), Salt (I-351)~Salt (I-356), Salt (I-365)~Salt (I-370), Salt (I-379)~Salt (I-384), Salt (I -393)~Salt (I-398), Salt (I-407)~Salt (I-412), Salt (I-421)~Salt (I-426), Salt (I-435)~Salt (I-440), Salt (I-449)~Salt (I-454), Salt (I-463)~Salt (I-468), Salt (I-477)~Salt (I-482), Salt ( I-491)~Salt (I-496), Salt (I-505)~Salt (I-510), Salt (I-519)~Salt (I-524), Salt (I-533)~Salt (I-538), Salt (I-547)~Salt (I-552), Salt (I-561)~Salt (I-566), Salt (I-575)~Salt (I-580), Salt (I-589)~Salt(I-594), Salt(I-603)~Salt(I-608), Salt(I-617)~Salt(I-622), Salt(I-632)~Salt(I-636), Salt(I-645)~Salt(I-650), Salt(I-659)~Salt(I-664), Salt(I-673)~Salt(I-678), Salt (I-687)~Salt (I-720), Salt (I-701)~Salt (I-706), Salt (I-715)~Salt (I-720), Salt (I-729)~Salt (I-734), Salt (I-743)~Salt (I-748), Salt (I-757)~Salt (I-762), Salt (I-771)~Salt (I-7765,Salt (I-785) ~ Salt (I-790), Salt (I-799) ~ Salt (I-804), Salt (I-813) ~ Salt (I-818), Salt (I-827) ~ Salt (I-832), Salt (I-841) ~ Salt (I-846), Salt (I-855) ~ Salt (I-860), Salt (I-869) ~ Salt (I-874), Salt (I-883) ~ Salt (I-888), Salt (I-911) ~ Salt (I-916), Salt (I-925) ~ Salt (I-930), Salt (I-939) ~ Salt (I-944), Salt (I-953) ~ Salt (I-958), Salt (I-967) ~ Salt (I-972), Salt (I-981) ~ Salt (I-986), Salt (I-995) ~ Salt (I-1000), Salt (I-1009) ~ Salt (I-1014), Salt (I-1023) ~ Salt (I-1028) , salt(I-1037)~salt(I-1042), salt(I-1051)~salt(I-1056), salt(I-1065)~salt(I-1070), salt(I-1079)~salt(I-1084), salt(I-1093)~salt(I-1098), salt(I-1107)~salt(I-1112), salt(I-1121)~salt(I-1126), salt(I-1135)~salt(I-1140), salt(I-1149)~salt(I-1154), salt(I-1163)~salt(I-1168), salt(I-1177)~salt(I-1182) , salt(I-1191)~salt(I-1196), salt(I-1205)~salt(I-1210), salt(I-1219)~salt(I-1224), salt(I-1233)~salt(I-1238), salt(I-1247)~salt(I-1252), salt(I-1261)~salt(I-1266), salt(I-1275)~salt(I-1280), salt(I-1289)~salt(I-1294), salt(I-1303)~salt(I-1308), salt(I-1317)~salt(I-1322), salt(I-1331)~salt(I-1336) , salt(I-1345)~salt(I-1350), salt(I-1359)~salt(I-1364), salt(I-1373)~salt(I-1378), salt(I-1387)~salt(I-1392), salt(I-1401)~salt(I-1406), salt(I-1415)~salt(I-1420), salt(I-1429)~salt(I-1434), salt(I-1443)~salt(I-1448), salt(I-1457)~salt(I-1462), salt(I-1471)~salt(I-1476), salt(I-1485)~salt(I-1490),It is preferable that the salt is between (I-1499) and (I-1504).

[0061] <Method for producing salt (I)> Salt (I) can be produced by reacting the salt represented by formula (Ia) with the compound represented by formula (Ib) in a solvent in the presence of a catalyst. TIFF0007943791000044.tif140154 [where R 4 , R 5 , R 6 , R 7 ,R 8 , R 9 , m1, m2, m3, m4, m5, m6, m7, m8, m9, A 1 , A 2 , A 3 Q b1 Q b2 , L b1 , Y b1 , L 10 , X 10 , R bb1 The symbols represent the same meanings as described above. ] L b2 L b1 -(CO) from the end (1-nn) Represents the base excluding -O-. nn represents 0 or 1. Examples of catalysts include carbonyldiimidazole and base catalysts (dimethylaminopyridine). Examples of solvents include chloroform, monochlorobenzene, and acetonitrile. The reaction temperature is typically between 15°C and 80°C, and the reaction time is typically between 0.5 and 24 hours.

[0062] Examples of salts represented by formula (Ia) include those represented by the following formula. These salts can be easily produced by a method similar to the method described in Japanese Patent Publication No. 2020-15713, or by a known method. TIFF0007943791000045.tif109148

[0063] TIFF0007943791000046.tif72128

[0064] TIFF0007943791000047.tif181140

[0065] TIFF0007943791000048.tif247142

[0066] TIFF0007943791000049.tif191163

[0067] Examples of compounds represented by formula (Ib) include those represented by the following formula. These compounds can be readily obtained from the market or can be readily manufactured by known methods. TIFF0007943791000050.tif33163

[0068] [Resin containing structural units (IP) derived from the salt represented by formula (I)] The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (Ap)") that contains structural units derived from a salt represented by formula (I) (hereinafter sometimes referred to as "structural units (IP)"). TIFF0007943791000051.tif75142[In formula (IP), R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R bb1 , m1, m2, m3, m4, m5, m6, m7, m8, m9, A 1 , A 2 , A 3 Q b1 Q b2 , L b1 , Y b1 , X 10 , L 10 The symbols represent the same meanings as described above. The structural unit (IP) is CH2=CR contained in the group represented by the salt (I). bb1 This shows the state in which the double bond has been cleaved. The resin (Ap) may be a homopolymer containing one structural unit (IP), or a copolymer containing two or more structural units (IP). Furthermore, the resin (Ap) may contain structural units other than structural units (IP). Examples of structural units other than structural units (IP) include structural units having acid-unstable groups (hereinafter sometimes referred to as "structural unit (a1)"), structural units not having acid-unstable groups (hereinafter sometimes referred to as "structural unit (s)"), other structural units (hereinafter sometimes referred to as "structural unit (t)"), and structural units known in the art, as will be described later. Here, "acid-unstable group" means a group that has a leaving group, and upon contact with an acid, the leaving group is removed, converting the structural unit into a structural unit having a hydrophilic group (for example, a hydroxyl group or a carboxyl group). The content of structural units (IP) is typically 0.1 to 100 mol%, preferably 0.5 to 50 mol%, more preferably 0.8 to 30 mol%, and even more preferably 1 to 10 mol%, relative to the total amount of resin (Ap).

[0069] In particular, when the resin (Ap) is used in a resist composition, as will be described later, it may further contain structural units (a1) in addition to structural units (IP). Furthermore, as will be described later, when resin (Ap) is used in a resist composition, it may be used in combination with resins containing structural unit (a1) (hereinafter sometimes referred to as "resin (A)") and / or resins other than resin (A), regardless of whether or not it contains structural unit (a1). Hereinafter, resin (Ap) and / or resin (A) may be referred to as "resin (A), etc." It is preferable that resin (Ap) and resin (A) each further contain structural units other than structural unit (a1). Structural units other than structural unit (a1) include structural units that do not have acid-unstable groups (hereinafter sometimes referred to as "structural unit (s)"), other structural units (hereinafter sometimes referred to as "structural unit (t)"), and structural units known in the art.

[0070] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-unstable group (hereinafter sometimes referred to as "monomer (a1)"). The acid-unstable groups contained in resin (A), etc., are 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)). TIFF0007943791000052.tif1988[In formula (1), R a1 , R a2 and R a3 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. a1 and R a2 These atoms bond with each other, forming a non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, along with the carbon atoms to which they bond. ma and na each independently represent either 0 or 1, and at least one of ma and na represents 1. * indicates a connection site. TIFF0007943791000053.tif2171[In formula (2), R a1’ and R a2’ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ and R a3’ These atoms bond to each other, forming a heterocycle with 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and the -CH2- contained in the hydrocarbon group and the heterocycle may be replaced with -O- or -S-. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a connection site.

[0071] R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. R a1 , Ra2 and R a3 Examples of alkenyl groups in this context include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). a1 , R a2 and R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16. TIFF0007943791000054.tif10150R a1 , R a2 and R a3 Examples of aromatic hydrocarbon groups in this context include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of non-aromatic hydrocarbon rings include the following rings. The non-aromatic hydrocarbon rings preferably have 3 to 12 carbon atoms. * indicates a bond site with -O-. TIFF0007943791000055.tif30138

[0072] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these are R a1 , R a2 and R a3 The same types of elements mentioned above can be cited. R a2’ and R a3’ When they bond with each other and form a heterocycle with the carbon atoms and X to which they are bonded, -C(R a1’ )(R a2’ )-XR a3’ The following rings are examples. * indicates a bonding site. TIFF0007943791000056.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0073] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 A group in which the parentheses is an alkyl group, ma=0, and na=1. A tert-butoxycarbonyl group is preferred as the group. In equation (1), R a1 , Ra2 However, these combine with the carbon atoms to which they bond to form an adamantyl group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 This is an adamantyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates a bonding site. TIFF0007943791000057.tif154163

[0074] The following are specific examples of group (2). * indicates a bonding site. TIFF0007943791000058.tif55153

[0075] 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.

[0076] Among (meth)acrylic monomers having acid-unstable groups, those having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are preferred. If a resin (A) or the like having structural units derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0077] Structural units derived from (meth)acrylic monomers having group (1) include structural units represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), structural units represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)), or structural units represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-0), structural unit (a1-1), and structural unit (a1-2), and more preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used individually or in combination of two or more. TIFF0007943791000059.tif44143[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents a bond, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-. R a01 , R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0078] R a01 , R a4 and R a5 This is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 It is -CO-O- (where k01 is preferably an integer from 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04 The alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof in this group are R of group (1). a1 , R a2 and R a3 Similar groups to those listed above can be cited. R a6 and R a7 The alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof in formula (1) are R a1 , R a2 and R a3 Similar groups to those listed above can be cited. R a02 , R a03 , and R a04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and even more preferably an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group, or a 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. In groups formed by combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and alicyclic hydrocarbon group is 18 or less. In groups formed by combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and 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 an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. R a6 and R a7 Each of these groups is independently preferably a C1-C6 alkyl group, a C2-C6 alkenyl group, or a C6-C12 aromatic hydrocarbon group, more preferably a methyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group, or naphthyl group, and even more preferably an ethyl group, isopropyl group, t-butyl group, ethenyl group, or phenyl group. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0079] Examples of structural units (a1-0) include structural units represented by any of the formulas (a1-0-1) to (a1-0-18) and R in structural unit (a1-0). a01 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group are given, and structural units represented by any of formulas (a1-0-1) to (a1-0-10), (a1-0-13), or (a1-0-14) are preferred. TIFF0007943791000060.tif88160

[0080] Examples of structural units (a1-1) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646. In particular, structural units represented by any of formulas (a1-1-1) to (a1-1-7) and R in structural unit (a1-1) a4 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is preferred, and a structural unit represented by any of formulas (a1-1-1) to (a1-1-4) is more preferred. TIFF0007943791000061.tif38168

[0081] The structural unit (a1-2) is a structural unit represented by any of the formulas (a1-2-1) to (a1-2-14) and R in the structural unit (a1-2). a5 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of the formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-14). TIFF0007943791000062.tif67163

[0082] When resin (A) contains structural units (a1-0) and / or structural units (a1-1) and / or structural units (a1-2), the total content of these is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, and even more preferably 30 mol% or more, relative to the total structural units of resin (A). Alternatively, it may be 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 70 mol% or less. Specifically, it can be 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, even more preferably 25 to 70 mol%, and even more preferably 30 to 70 mol%. When resin (A) contains structural units (a1-0), the content of these units is 5 mol% or more, preferably 10 mol% or more, relative to the total structural units of resin (A). It is also 80 mol% or less, preferably 75 mol% or less, and more preferably 70 mol% or less. Specifically, it is 5 to 80 mol%, preferably 5 to 75 mol%, and more preferably 10 to 70 mol%. When resin (A) contains structural units (a1-1) and / or structural units (a1-2), the total content of these units is 10 mol% or more, preferably 15 mol% or more, and more preferably 20 mol% or more, relative to the total structural units of resin (A). Alternatively, it may be 90 mol% or less, preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 75 mol% or less, and even more preferably 70 mol% or less. Specifically, it is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, even more preferably 20 to 75 mol%, and even more preferably 20 to 70 mol%.

[0083] Examples of structural units having a base (2) in structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007943791000063.tif4564[In formula (a1-4), R a32 This represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a33 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -( A a32 -X a32 ) nc - represents -R a32 This represents the bonding site with the carbon atom to which it is bonded. A a32 This represents an alkanediyl group with 1 to 6 carbon atoms. X a31 and X a32 These represent -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents an integer between 0 and 4. If la is an integer greater than or equal to 2, multiple R a33 They may be the same or different from each other. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 These atoms bond with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the -CH2- contained in this hydrocarbon group and the divalent hydrocarbon group may be replaced with -O- or -S-.

[0084] R a32 and R a33Examples of halogen atoms in this context include fluorine atoms, chlorine atoms, and bromine atoms. R a32 Examples of C1-C6 alkyl groups that may have halogen atoms include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, and perfluorohexyl groups. R a32 The 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 context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. R a33 Examples of alkoxy groups in this compound include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. R a33 Examples of alkoxyalkyl groups in this context include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a carbon-2 to carbon-8 alkoxyalkyl group, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. Ra33 Examples of alkoxyalkoxy groups in this context include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, with methoxyethoxy or ethoxyethoxy being more preferred. R a33 Examples of alkylcarbonyl groups in this compound include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 3 carbon atoms, with acetyl being more preferred. R a33 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably one having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 The group is preferably a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0085] *-X a31 -( A a32 -X a32 ) nc - for example, *-O-, *-CO-O-, *-O-CO-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO- is one example. In particular, *-CO-O- and *-CO-OA a32 -CO-O- or *-OAa32 -CO-O- is preferred.

[0086] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. A a32 It is preferable that this is a methylene group or an ethylene group.

[0087] A a30 These are single bonds, *-CO-O- or *-CO-OA a32 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0088] 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 context 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. Alicyclic hydrocarbon groups may be 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, and the following groups (* indicates a bonding site). Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as 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.

[0089] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, this is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group 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 hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. a36 The alkyl groups and alicyclic hydrocarbon groups in R are preferably unsubstituted. a36In this context, the aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0090] -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 It is eliminated upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It is preferable that the compound is bonded to the m- or p-position of the benzene ring.

[0091] Examples of structural units (a1-4) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204646. Preferably, structural units represented by formulas (a1-4-1) to (a1-4-24) and R in structural unit (a1-4). a32 Examples of structural units include those in which the hydrogen atom corresponding to is replaced by a halogen atom, a haloalkyl group, or an alkyl group, and more preferably, structural units represented by formulas (a1-4-1) to (a1-4-5), (a1-4-10), (a1-4-13), (a1-4-14), (a1-4-19), and (a1-4-20), respectively. TIFF0007943791000065.tif125159

[0092] If the resin (A) contains structural units (a1-4), the content of these units is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, even more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol% relative to the total amount of all structural units of the resin (A).

[0093] Structural units derived from (meth)acrylic monomers having group (2) include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007943791000066.tif4558 formula (a1-5), R a8 This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents, h3 represents an integer from 1 to 4, and * represents L 51 This represents the connection point. L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0094] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may contain halogen atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl, and trifluoromethyl groups. In equation (a1-5), R a8 The preferred element is a hydrogen atom, a methyl group, or a trifluoromethyl group. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, 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 A single bond or *-CH2-CO-O- is preferred.

[0095] Examples of structural units (a1-5) include monomer-derived structural units described in Japanese Patent Publication No. 2010-61117. Among these, structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or (a1-5-2) are more preferred. TIFF0007943791000067.tif33133

[0096] If the resin (A) contains structural units (a1-5), the content of these units is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, even more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol%, relative to the total structural units of the resin (A).

[0097] In addition, the following structural units (a1) can also be listed. TIFF0007943791000068.tif31162

[0098] When resin (A) contains structural units such as (a1-3-1) to (a1-3-7), the content of these structural units is preferably 10 to 95 mol%, 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% relative to the total structural units of resin (A).

[0099] In addition, the following structural units (a1) can also be listed. TIFF0007943791000069.tif5195 When resin (A), etc. contains structural units such as (a1-6-1) to (a1-6-3), the content thereof is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, even more preferably 20 to 50 mol%, even more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol% relative to the total structural units of resin (A), etc.

[0100] <Structural unit (s)> Structural units (s) are derived from monomers that do not have acid-unstable groups (hereinafter sometimes referred to as "monomers (s)"). Monomers that do not have acid-unstable groups and are known in the field of photoresists can be used to derive structural units (s). The structural unit (s) preferably has a hydroxyl group or a lactone ring. If a resin having a structural unit having a hydroxyl group and no acid-unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-unstable group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0101] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) may be either 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 beam such as a KrF excimer laser (248 nm), electron beam, or EUV (ultra-ultraviolet light) is used as the exposure light source, a structural unit (a2) having a phenolic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-A) described later. Furthermore, if an ArF excimer laser (193 nm) or the like is used, a structural unit (a2) having an alcoholic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may consist of one type alone, or it may consist of two or more types.

[0102] A structural unit having a phenolic hydroxyl group in structural unit (a2) is the structural unit represented by formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007943791000070.tif4653[In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. Ra51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -( A a52 -X a52 ) nb - represents -R a50 This indicates the bonding position with the carbon atom to which it is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, multiple R a51 They may be the same or different from each other.

[0103] R a50 and R a51 Examples of halogen atoms in this context include fluorine atoms, chlorine atoms, and bromine atoms. R a50 Examples of C1-C6 alkyl groups that may have halogen atoms include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, and perfluorohexyl groups. R a50The 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 in this context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. R a51 Examples of alkoxy groups in this compound include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. R a51 Examples of alkoxyalkyl groups in this context include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a carbon-2 to carbon-8 alkoxyalkyl group, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of alkoxyalkoxy groups in this context include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, with methoxyethoxy or ethoxyethoxy being more preferred. R a51 Examples of alkylcarbonyl groups in this compound include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 3 carbon atoms, with acetyl being more preferred. R a51Examples of alkylcarbonyloxy groups in this context include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably one having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 The group is preferably a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0104] *-X a51 -( A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-O-CO-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO- is one example. In particular, *-CO-O- and *-CO-OA a52 -CO-O- or *-OA a52 -CO-O- is preferred.

[0105] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. A a52 It is preferable that this is a methylene group or an ethylene group.

[0106] A a50These are single bonds, *-CO-O- or *-CO-OA a52 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0107] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. The hydroxyl group is preferably bonded to the m- or p-position of the benzene ring. If two or more hydroxyl groups are present, it is preferable that the two hydroxyl groups are bonded to the m- and p-positions, respectively.

[0108] Examples of structural units (a2-A) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204634 and Japanese Patent Publication No. 2012-12577. The structural unit (a2-A) is the structural unit represented by formulas (a2-2-1) to (a2-2-24), and the R in the structural unit (a2-A) in the structural unit (a2-A) represented by formulas (a2-2-1) to (a2-2-24). a50 Examples of structural units in which the methyl group corresponding to is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. Structural unit (a2-A) is a structural unit represented by formula (a2-2-1) to formula (a2-2-4), formula (a2-2-6), formula (a2-2-8), formula (a2-2-12) to formula (a2-2-18), and in structural units represented by formula (a2-2-1) to formula (a2-2-4), formula (a2-2-6), formula (a2-2-8), and formula (a2-2-12) to formula (a2-2-18), the R in structural unit (a2-A) is a50Preferably, the structural unit is one in which the corresponding methyl group is replaced by a hydrogen atom, and in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-4), 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 (a2-2-18), and the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-4), the structural unit represented by formula (a2-2-8), the structural unit represented by formulas (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-18), the R in structural unit (a2-A) a50 It is more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit represented by formula (a2-2-3), formula (a2-2-4), formula (a2-2-8), and in the structural unit represented by formula (a2-2-3), formula (a2-2-4), and formula (a2-2-8), the R in structural unit (a2-A) a50 It is even more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit. TIFF0007943791000071.tif80168

[0109] When structural units (a2-A) are included in resin (A), the content of structural units (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more, relative to the total structural units. Furthermore, it is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%. The structural unit (a2-A) can be incorporated into resin (A), for example, by polymerizing using structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into resin (A), for example, by polymerizing using acetoxystyrene and then treating with an alkali such as tetramethylammonium hydroxide.

[0110] A structural unit having an alcoholic hydroxyl group in structural unit (a2) is the structural unit represented by formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). TIFF0007943791000072.tif4562 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents the associative position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0111] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 The result is -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0112] Examples of structural units (a2-1) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646. Structural units represented by any of formulas (a2-1-1) to (a2-1-6) are preferred, structural units represented by any of formulas (a2-1-1) to (a2-1-4) are more preferred, and structural units represented by formula (a2-1-1) or (a2-1-3) are even more preferred. JPEG0007943791000073.jpg47132

[0113] When the resin (A) contains structural units (a2-1), the content of these units is preferably 1 mol% or more, and more preferably 2 mol% or more, relative to the total structural units of the resin (A). Also, it is preferably 45 mol% or less, more preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 20 mol% or less, and even more preferably 10 mol% or less. Specifically, it is 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%.

[0114] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or it may be a fused ring of a monocyclic lactone ring and another ring. Preferably, it may be a γ-butyrolactone ring, an adamantane lactone ring, or a bridging ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

[0115] The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). One of these may be included alone, or two or more may be included. TIFF0007943791000074.tif48155[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and La6 These are, independently, -O- or *-O-(CH2) k3 This represents a base represented by -CO-O-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O- L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently represents a carboxyl group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 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 the same or different from each other.

[0116] Ra21 , R a22 , R a23 and R a25 Examples of aliphatic hydrocarbon groups in this context include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl groups. R a24 Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. R a24 Examples of alkyl groups in this context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups, with alkyl groups having 1 to 4 carbon atoms being preferred, and methyl or ethyl groups being more preferred. R a24 Examples of alkyl groups having halogen atoms in this context include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl groups.

[0117] L a8 and L a9 Examples of alkanediyl groups in this compound include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0118] In equations (a3-1) to (a3-3), L a4 ~L a6 These are each independently, preferably -O- or *-O-(CH2) k3In -CO-O-, k3 is an integer from 1 to 4, more preferably -O- and *-O-CH2-CO-O-, and even more preferably an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a methyl group. p1, q1, and r1 are each independently, preferably integers from 0 to 2, and more preferably 0 or 1.

[0119] In equation (a3-4), R a24 Preferably, it is 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 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 It is -CO-O-, and more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007943791000075.tif3848 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0120] Examples of structural units (a3) ​​include those derived from monomers described in Japanese Patent Publication No. 2010-204646, Japanese Patent Publication No. 2000-122294, and Japanese Patent Publication No. 2012-41274. Examples of structural units (a3) ​​include those represented by any of the formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and (a3-4-1) to (a3-4-12), and in the said structural units, R in formulas (a3-1) to (a3-4). a18 , R a19 , R a20 and R a24 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom is preferred.

[0121] TIFF0007943791000076.tif116165

[0122] When the resin (A) contains structural units (a3), the total content of these units is 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total structural units of the resin (A). Alternatively, it may be 70 mol% or less, preferably 65 mol% or less, and more preferably 60 mol% or less. Specifically, it is 1 to 70 mol%, preferably 3 to 65 mol%, and more preferably 5 to 60 mol%. Furthermore, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3), or structural unit (a3-4) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the total structural units of resin (A), etc. Also preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less. Specifically, 1 to 60 mol% is preferred, 3 to 50 mol% is more preferred, and 5 to 50 mol% is even more preferred.

[0123] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007943791000077.tif2962[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. R 42 The saturated hydrocarbon groups represented by include chain-type saturated hydrocarbon groups, monocyclic or polycyclic alicyclic saturated hydrocarbon groups, and groups formed by combining these.

[0124] 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 saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). TIFF0007943791000078.tif10146 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0125] Examples of structural units (a4) include the structural unit represented by formula (a4-0), the structural unit represented by formula (a4-1), and the structural unit represented by formula (a4-4). TIFF0007943791000079.tif4551[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 64 This represents a hydrogen atom or a fluorine atom.

[0126] L 4a Examples of alkanediyl groups in this context include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0127] L 3a The perfluoroalkanediyl groups in this product include difluoromethylene, perfluoroethylene, perfluoroethylfluoromethylene, perfluoropropane-1,3-diyl, perfluoropropane-1,2-diyl, perfluoropropane-2,2-diyl, perfluorobutane-1,4-diyl, perfluorobutane-2,2-diyl, perfluorobutane-1,2-diyl, perfluoropentane-1,5-diyl, perfluoropentane-2,2-diyl, and perfluoropentane-3 Examples include 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, and perfluorooctane-4,4-diyl group. L 3aExamples of perfluorocycloalkanediyl groups in this context include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, and perfluoroadamantanediyl group.

[0128] L 4a Preferably, it is a single bond, a methylene group, or an ethylene group, and more preferably a single bond and a methylene group. L 3a The group is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0129] The structural units (a4-0) are the structural units shown below and the R in the structural units (a4-0) within the structural units below. 54 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. TIFF0007943791000080.tif97165 An example of a structural unit (a4) is the structural unit represented by formula (a4-1). TIFF0007943791000081.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. A a41 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a group represented by formula (a-g1). However, A a41 and R a42 At least one of these atoms has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007943791000082.tif1487 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44Each of these independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have substituents. A a43 This represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. X a41 and X a42 These represent -O-, -CO-, -CO-O-, or -O-CO-, respectively, independently. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates a binding site, and the * on the right is -O-CO-R a42 This is the junction site.

[0130] R a42 Examples of saturated hydrocarbon groups in this context include chain-like hydrocarbon groups, monocyclic or polycyclic saturated alicyclic hydrocarbon groups, and groups formed by combining these.

[0131] Examples of chain-like hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of monocyclic or polycyclic saturated alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). TIFF0007943791000083.tif10160 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more saturated alicyclic hydrocarbon groups, such as -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group.

[0132] R a42 The substituents on the compound include at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3). Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. TIFF0007943791000084.tif855[In formula (a-g3), X a43 * represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. * is R a42 This represents the connection point with [the other element]. However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom.

[0133] A a45 Examples of saturated hydrocarbon groups in this context include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups; Examples include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). TIFF0007943791000085.tif10160 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0134] R a42 A saturated hydrocarbon group which may have a halogen atom is preferred, and a saturated hydrocarbon group which has an alkyl group having a halogen atom and / or a group represented by formula (a-g3) is more preferred. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, 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 group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, and perfluorooctyl group. Examples of perfluorocycloalkyl groups include perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then R is calculated including the number of carbon atoms in the group represented by formula (a-g3). a42 The total number of carbon atoms is preferably 15 or less, and more preferably 12 or less. If the atom has a substituent represented by formula (a-g3), the number of substituents is preferably one.

[0135] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 More preferably, the group is represented by formula (a-g2). TIFF0007943791000086.tif871[In formula (a-g2), A a46 This represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. X a44 This represents **-O-CO- or **-CO-O- (where ** is A a46 This represents the connection site. A a47This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 At least one of them has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0136] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, A a47 A cyclohexyl group or an adamantyl group is more preferable.

[0137] The preferred structure of the group represented by formula (a-g2) is as follows (* indicates the bonding site with the carbonyl group). TIFF0007943791000087.tif14160

[0138] A a41 Examples of alkanediyl groups in this context include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. A a41 Examples of substituents on the alkanediyl group represented by include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. A a41 The group is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0139] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of divalent saturated hydrocarbon groups represented by include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, as well as divalent saturated hydrocarbon groups formed by combining alkanediyl groups and divalent alicyclic saturated 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, and 2-methylpropane-1,2-diyl groups. A a42 , A a43 and A a44 Examples of substituents on the divalent saturated hydrocarbon group represented by include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0140] In the group represented by formula (a-g1), X a42 The following are examples of groups whose -O-, -CO-, -CO-O-, or -O-CO-. In the following examples, * and ** represent the bonding site, and ** is -O-CO-R a42 This is the junction site. TIFF0007943791000088.tif47140

[0141] The structural units represented by formula (a4-1) are the structural units shown below and the R in the structural units represented by formula (a4-1) in the structural units below. a41 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. JPEG0007943791000089.jpg99145

[0142] TIFF0007943791000090.tif132150

[0143] Examples of structural units (a4) include the structural unit represented by formula (a4-2) and the structural unit represented by formula (a4-3). TIFF0007943791000091.tif4356[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0144] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 Similar to the examples given earlier, the same types of bases can be cited. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this compound, an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0145] Examples of structural units represented by equation (a4-2) include those represented by equations (a4-1-1) to (a4-1-11), respectively. f5 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom can also be cited as a structural unit represented by formula (a4-2).

[0146] TIFF0007943791000092.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection site. A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0147] L 5 The alkanediyl group in A is a41 Examples of groups similar to those exemplified by the alkanediyl group include the following.

[0148] A f13 The divalent saturated hydrocarbon group which may have a fluorine atom is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of divalent chain-type saturated hydrocarbon groups that may contain a fluorine atom include methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups, as well as perfluoroalkanediyl groups such as difluoromethylene groups, perfluoroethylene groups, perfluoropropanediyl groups, perfluorobutanediyl groups, and perfluoropentanediyl groups. The divalent alicyclic saturated hydrocarbon group, which may contain a fluorine atom, may be monocyclic or polycyclic. Examples of monocyclic groups include cyclohexanediyl and perfluorocyclohexanediyl groups. Examples of polycyclic groups include adamantanediyl, norbornanediyl, and perfluoroadamantanediyl groups.

[0149] A f14The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of are the same groups as those exemplified for R a42 Examples include the same groups as those exemplified above. Among them, fluorinated alkyl groups such as trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group and the like are preferred.

[0150] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of is preferably a group comprising a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group of is preferably a group comprising a chain saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group comprising a chain saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 is preferably a group comprising an alicyclic saturated 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.

[0151] Examples of the structural unit represented by formula (a4-3) include the structural units respectively represented by formula (a4-1'-1) to formula (a4-1'-11). R in structural unit (a4-3) f7 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also mentioned as a structural unit represented by formula (a4-3).

[0152] Examples of the structural unit (a4) also include the structural unit represented by formula (a4-4). TIFF0007943791000093.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH₂) j1 -, -(CH₂) j2 -O-(CH₂) j3 - or -(CH₂) j4 -CO-O-(CH₂) j5 -. j1 to j5 each independently represent any integer of 1 to 6. R f22 represents a C1-C10 saturated hydrocarbon group having a fluorine atom.]

[0153] Examples of the saturated hydrocarbon group for R f22 include the same saturated hydrocarbon groups as those represented by R a42 . R f22 is preferably a C1-C10 alkyl group having a fluorine atom or a C1-C10 alicyclic saturated hydrocarbon group having a fluorine atom, more preferably a C1-C10 alkyl group having a fluorine atom, and even more preferably a C1-C6 alkyl group having a fluorine atom.

[0154] In formula (a4-4), A f21 is preferably -(CH₂) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0155] As a structural unit represented by formula (a4-4), for example, the following structural unit and the structural unit represented by the following formula, R in structural unit (a4-4) f21 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. TIFF0007943791000094.tif87159

[0156] If the resin (A) has structural units (a4), the content of these units is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total structural units of the resin (A).

[0157] <Structural Unit (a5)> Examples of non-eliminating hydrocarbon groups in structural unit (a5) include groups having linear, branched, or cyclic hydrocarbon groups. Among these, structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. An example of a structural unit (a5) is the structural unit represented by formula (a5-1). TIFF0007943791000095.tif3351[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in this alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.

[0158] R 52 The alicyclic hydrocarbon group in this compound may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl groups. Examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. Examples of substituted alicyclic hydrocarbon groups include the 3-methyladamantyl group. R 52 Preferably, it is an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably, an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0159] L 55 Examples of divalent saturated hydrocarbon groups in this context include divalent chain-type saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, with divalent chain-type saturated hydrocarbon groups being preferred. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups, which are all types of alkanediyl groups. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic saturated hydrocarbon groups include cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include adamantanediyl and norbornanediyl.

[0160] L 55 Groups in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO- include, for example, the groups represented by formulas (L1-1) to (L1-4). In the following formulas, * and ** represent bonding sites, respectively, and * represents the bonding site with the oxygen atom. TIFF0007943791000096.tif18164 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 This represents the connection site. L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0161] L x1 Preferably, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 Preferably, it is 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 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 Preferably, it is 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 Preferably, this is a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0162] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007943791000097.tif53136

[0163] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007943791000098.tif23130

[0164] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007943791000099.tif15148

[0165] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007943791000100.tif13167

[0166] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0167] The structural units (a5-1) are the structural units shown below and the R in the structural unit (a5-1) within the structural units below. 51 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. TIFF0007943791000101.tif111150 When resin (A) etc. has structural units (a5), the content of these units is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol%, relative to the total structural units of resin (A) etc.

[0168] <Structural Unit (a6)> The structural unit (a6) is a structural unit having an -SO2- group, and it is preferable that it has an -SO2- group in its side chain. A structural unit having an -SO2- group may have a linear structure having an -SO2- group, a branched structure having an -SO2- group, or a cyclic structure (monocyclic and polycyclic) having an -SO2- group. Preferably, it is a structural unit having a cyclic structure having an -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0169] As a sultone ring, the following equation (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 A ring represented by (T-4) is an example. The bonding site can be at any position. The sultone ring may be monocyclic, but it is preferably polycyclic. A polycyclic sultone ring means a bridging ring containing -SO2-O- as the atomic group constituting the ring, and is represented by formula (T 1 -1) and formula (T1 A ring represented by equation (T) is an example. A Sultone ring is given by equation (T 1 As shown in (2), the ring may contain heteroatoms in addition to -SO2-O- as part of the atomic group constituting the ring. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms, with oxygen atoms being preferred. TIFF0007943791000102.tif3087

[0170] The sultone ring may have substituents, and examples of substituents include C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group, halogen atoms, hydroxyl groups, cyano groups, C1-C12 alkoxy groups, C6-C12 aryl groups, C7-C12 aralkyl groups, glycidyloxy groups, C2-C12 alkoxycarbonyl groups, and C2-C4 alkylcarbonyl groups.

[0171] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. 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, with trifluoromethyl being preferred. Examples of alkyl groups having a hydroxyl group include hydroxymethyl groups and 2-hydroxyethyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups. Examples of the aryl group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group. Examples of the alkoxycarbonyl group include groups in which an alkoxy group such as methoxycarbonyl group and ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or less carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include acetyl group, propionyl group and butyryl group.

[0172] From the viewpoint of easy production of the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferable. As the sultone ring, a ring represented by the following formula (T1') is preferable. TIFF0007943791000103.tif3072[In formula (T1'), X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer of 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R 41 Examples include substituents similar to those of the sultone ring described above, and C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group are preferred. ma is preferably 0 or 1, and more preferably 0.

[0173] The following rings can be represented by equation (T1'). The bonding site is at an arbitrary position. TIFF0007943791000104.tif47145

[0174] Structural units having a sultone ring preferably have the following groups. * in the following groups indicates a bonding site. TIFF0007943791000105.tif45144

[0175] The structural unit having the -SO2- group preferably further 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, and methacryloylthio group. In particular, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.

[0176] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007943791000106.tif4956[In formula (Ix), R x This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. A xx is an oxygen atom, -N(R c )- or represents a sulfur atom. A x represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -N(R d)- may be replaced with this. X 11 , R 41 And ma have the same meaning as above. R c and R d Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0177] R x Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. 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 Preferably, it is 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.

[0178] A x Examples of divalent saturated hydrocarbon groups include linear alkanediyl groups, branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups are also acceptable. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group Linear alkanediyl groups such as dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; Branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; Monocyclic, divalent, alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0179] The following are examples of structural units (a6): TIFF0007943791000107.tif93150

[0180] In particular, structural units represented by formulas (a6-1), (a6-2), (a6-6), (a6-7), (a6-8), and (a6-12) are preferred, and structural units represented by formulas (a6-1), (a6-2), (a6-7), and (a6-8) are more preferred. If the resin (A) has structural units (a6), the content of these units is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and even more preferably 3 to 30 mol%, relative to the total structural units of the resin (A).

[0181] Resin (A), etc., is preferably a resin containing structural unit (a1). In particular, resin (Ap) is more preferably a resin consisting of structural unit (IP), structural unit (a1), and structural unit (s), that is, a copolymer of salt (I), monomer (a1), and monomer (s). Resin (A) that does not contain structural unit (IP) is preferably a resin consisting of structural unit (a1) and structural unit (s). 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 a structural unit having a cyclohexyl group or a cyclopentyl group), more preferably at least two, and even more preferably at least two 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 units (a2) and structural units (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 structural units represented by formula (a3-1), structural units represented by formula (a3-2), and structural units represented by formula (a3-4).

[0182] Each structural unit constituting resin (A), etc., may be used individually or in combination of two or more types, and these structural units can be produced by known polymerization methods (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in resin (A), etc., can be adjusted by the amount of monomer used in polymerization. The weight-average molecular weight of resin (A), etc., 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 the value obtained by gel permeation chromatography under the conditions described in the examples. The structural unit (IP) may constitute a dimer, trimer, or a compound with a weight-average molecular weight of less than 2,000.

[0183] [Acid Generator] The acid generator of the present invention contains a salt (I) or a structural unit (IP). The structural unit (IP) may be contained as a compound or resin formed by the polymerization of multiple units. In the acid generator, the salt (I) may be used alone or in combination of two or more types. The compound or resin containing the structural unit (IP) may be used alone or in combination of two or more types. The structural unit (IP) may be used alone or in combination of two or more types. Furthermore, the acid generator of the present invention may contain both the salt (I) and the structural unit (IP). The acid generator of the present invention may contain, in addition to salt (I), an acid generator known in the resist field (hereinafter sometimes referred to as "acid generator (B)" or "second acid generator"). Acid generator (B) will be described later. When the acid generator contains salt (I) and acid generator (B), the ratio of the content of salt (I) to acid generator (B) (mass ratio, salt (I): acid generator (B)) is usually 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, even more preferably 15:85 to 85:15, and particularly preferably 10:90 to 40:60.

[0184] [Resist composition] The resist composition of the present invention contains the acid generator of the present invention. The acid generator here may be a resin (Ap) containing a structural unit (IP). The resist composition of the present invention may contain an acid generator (B) that does not contain the acid generator of the present invention, or it may contain a resin that does not contain a structural unit (IP). Here, the resin that does not contain a structural unit (IP) may be a resin containing a structural unit (a1) having an acid-unstable group, or it may be a resin that does not contain a structural unit (a1). However, the resist composition of the present invention contains at least one of the salt (I) and the structural unit (IP), and may contain both. That is, the resist composition of the present invention may contain an acid generator containing the structural unit (IP) of the present invention or the salt (I) of the present invention. The structural unit (IP) may be in any form, such as a compound or a resin. In other words, the resist composition of the present invention may contain a resin (Ap) and / or resin (A) and a salt (I) as the acid generator. It is preferable that the resist composition of the present invention contains a resin containing a structural unit (a1) having an acid-unstable group. That is, (a) containing salt (I) and resin (A), (b) A resin (Ap) containing structural units (IP) and structural units (a1) having acid-unstable groups, (c) Preferably, the resist composition contains a resin (Ap) containing structural units (IP) and a resin (A). In particular, the resist composition described in (b) above is preferred. It may also contain two or more types of resin (A) and / or resin (Ap). The resist composition of the present invention preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). Furthermore, the resist composition of the present invention may further contain resins other than the resin (A) etc. described above.

[0185] <Resins other than resin (A), etc.> The resist composition of the present invention may also contain resins other than resin (Ap) and resin (A). Examples of resins other than resin (Ap) and resin (A) include resin (AX) which has the same structural units as resin (A) except that it does not contain structural unit (a1), and resins which contain structural unit (a4) and / or structural unit (a5) (however, they do not contain structural unit (IP) and structural unit (a1). Hereinafter, this may be referred to as "resin (X)"). Examples of resin (AX) include resins containing structural unit (a2), and resins containing structural unit (a2-A) are preferred. In resin (AX), the content of structural unit (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total amount of all structural units in resin (AX). Furthermore, it is preferably 80 mol% or less, and more preferably 70 mol% or less. Further structural units that resin (X) may have include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. In particular, resin (X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5), and more preferably a resin consisting only of structural unit (a4). When resin (X) contains structural units (a4), the content of structural units (a4) is preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, relative to the total amount of all structural units in resin (X). Also, it is preferably 100 mol% or less, more preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, it is preferably 20 to 100 mol%, more preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. When resin (X) contains structural units (a5), the content of structural units (a5) is preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, relative to the total amount of all structural units in resin (X). Furthermore, a value of 100 mol% or less is cited, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, a value of 20 to 100 mol% is cited, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. Also, if the resin (X) contains structural units (a4) and structural units (a5), the total content of structural units (a4) and structural units (a5) is cited as 40 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total of all structural units of the resin (X). Furthermore, a value of 100 mol% or less is cited. Specifically, a value of 40 to 100 mol% is cited, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%. Each structural unit constituting resin (AX) and resin (X) may be used individually or in combination of two or more types, and these structural units can be produced by known polymerization methods (e.g., radical polymerization) using monomers that induce these structural units. The content of each structural unit in resin (AX) and resin (X) can be adjusted by the amount of monomer used in polymerization. The weight-average molecular weights of resin (AX) and resin (X) are preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight-average molecular weights of resin (AX) and resin (X) are the same as in the case of resin (A).

[0186] If the resist composition of the present invention contains resin (X), the content of resin (X) 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, per 100 parts by mass of resin (A), etc.

[0187] The content of resin (A) in the resist composition is preferably 80% to 99% by mass, and more preferably 90% to 99% by mass, relative to the solid content of the resist composition. The content of resin (Ap) is preferably 80% to 99% by mass, and more preferably 90% to 99% by mass, relative to the solid content of the resist composition. Furthermore, if resins other than resin (A) are included, the total content of resin (A) and other resins is preferably 80% to 99% by mass, and more preferably 90% to 99% by mass, relative to the solid content of the resist composition. The solid content of the resist composition and the resin content thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0188] <Acid Generator> The acid generator contained in the resist composition of the present invention may be either an acid generator containing only salt (I) and / or structural unit (IP), or an acid generator containing salt (I) and / or structural unit (IP) and acid generator (B). Acid generator (B) may be used alone or in combination of two or more types.

[0189] The acid generator (B) may be either nonionic or ionic. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxiimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Typical ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of onium salt anions include sulfonic acid anions, sulfonylimide anions, and sulfonylmethide anions.

[0190] As the acid generator (B), compounds that generate acid by radiation as described in Japanese Patent Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, U.S. Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Compounds manufactured by known methods may also be used. Two or more types of acid generators (B) may be used in combination.

[0191] The acid generator (B) is preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007943791000108.tif3058[In formula (B1), Q b1 and Q b2 Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y represents a methyl group which may have substituents or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO2- or -CO-. Z + This represents an organic cation.

[0192] Q b1 Q b2 , L b1 And Y is the Q of the anion in equation (I). b1 Q b2 , L b1 and Y b1 Examples similar to those exemplified earlier can be given.

[0193] In particular, Y is preferably a C3-C24 alicyclic hydrocarbon group which may have substituents, more preferably a C3-C20 alicyclic hydrocarbon group which may have substituents, even more preferably a C3-C18 alicyclic hydrocarbon group which may have substituents, and even more preferably an adamantyl group or norbornyl group which may have substituents, and the -CH2- constituting the alicyclic hydrocarbon group, adamantyl group or norbornyl group may be replaced with -CO-, -SO2- or -CO-. Specifically, the following are examples. TIFF0007943791000109.tif117159

[0194] TIFF0007943791000110.tif53155

[0195] Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, a norbornane lactone group, or a group represented by formula (Y42), formula (Y100) to formula (Y114), formula (Y134) to formula (Y139).

[0196] The anions in the salt represented by formula (B1) are preferably those represented by formulas (B1-A-1) to (B1-A-65) (hereinafter, they may be referred to as "anion (B1-A-1)" etc. depending on the formula number), and more preferably those represented by any of formulas (B1-A-1) to (B1-A-4), (B1-A-9), (B1-A-10), (B1-A-24) to (B1-A-33), (B1-A-36) to (B1-A-40), or (B1-A-47) to (B1-A-65). TIFF0007943791000111.tif205164

[0197] TIFF0007943791000112.tif247165

[0198] TIFF0007943791000113.tif212163 Here R i2 ~R i7 These are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. i8 For example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by a combination thereof, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 This is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 This expresses the same meaning as above. Specific examples of anions in the salt represented by formula (B1) include those described in Japanese Patent Publication No. 2010-204646.

[0199] Preferred anions in the salt represented by formula (B1) are the anions represented by formulas (B1a-1) to (B1a-43), respectively. TIFF0007943791000114.tif237167

[0200] TIFF0007943791000115.tif111154

[0201] Among these, anions represented by any of the following formulas are preferred: (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-38). Furthermore, the following are examples of sulfonylimid anions. Examples of sulfonylmethide anions include TIFF0007943791000116.tif23136. TIFF0007943791000117.tif26133

[0202] Z + 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 aryl sulfonium cations are more preferred. Specifically, examples include cations represented by any of formulas (b2-1) to (b2-4) (hereinafter, depending on the formula number, they may be referred to as "cation (b2-1)," etc.). In formulas (b2-1) to (b2-4) of TIFF0007943791000118.tif48169, R b4 ~R b6Each of these independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atoms 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. The hydrogen atoms in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atoms 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, an alkyl fluoride group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or greater, multiple R b8 They may be the same or different. R b9 and R b10 Each of these independently represents either a chain-like hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b11 This represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. Rb12 This represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 These may be bonded to each other and form a ring including the -CH-CO- groups to which they are bonded, and the -CH2- groups included in the ring may be replaced by -O-, -S-, or -CO-. R b13 ~R b18 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, and when r2 is 2 or more, multiple R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 They are the same or different, and when t2 is 2 or more, multiple R b18 They are either the same or different. Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain-type hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. In particular, Rb9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be 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. TIFF0007943791000119.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. 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, methylnorbornyl group, and isobornyl group. In alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. A fluorinated alkyl group refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom, such as a fluoromethyl group, difluoromethyl group, trifluoromethyl group, and perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenyl, naphthyl, and phenanthryl groups. Aromatic hydrocarbon groups may also have chain hydrocarbon groups or alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups having chain hydrocarbon groups with 1 to 18 carbon atoms (tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.) and aromatic hydrocarbon groups having alicyclic hydrocarbon groups with 3 to 18 carbon atoms (p-cyclohexylphenyl, p-adamantylphenyl, etc.). When the aromatic hydrocarbon group has chain hydrocarbon groups or alicyclic hydrocarbon groups, chain hydrocarbon groups with 1 to 18 carbon atoms and alicyclic hydrocarbon groups with 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include the p-methoxyphenyl group. Examples of chain-like hydrocarbon groups in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group. R b4 and R b5The ring formed by the bonding of these atoms to each other and the sulfur atoms to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of such rings include those with 3 to 18 carbon atoms, preferably those with 4 to 18 carbon atoms. Furthermore, examples of sulfur atom-containing rings include those with 3 to 12 membered rings, preferably those with 3 to 7 membered rings, and the following rings are examples. * indicates a bonding site. TIFF0007943791000120.tif23144R b9 and R b10 The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxatian-4-ium ring. R b11 and R b12 The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include oxocycloheptane rings, oxocyclohexane rings, oxonorbornane rings, and oxoadamantane rings.

[0203] Among cations (b2-1) to (b2-4), cation (b2-1) is preferred. The following cations can be considered as cations (b2-1): TIFF0007943791000121.tif130163 The following cations can be considered as cations (b2-2): TIFF0007943791000122.tif18150 The following cations can be considered as cations (b2-3): TIFF0007943791000123.tif26139 The following cations can be considered as cations (b2-4): TIFF0007943791000124.tif120170

[0204] The acid generator (B) is a combination of the anion and the organic cation described above, and these can be combined arbitrarily. Preferred examples of the acid generator (B) include a combination of an anion represented by any of the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), (B1a-22) to (B1a-38) and a cation (b2-1), cation (b2-2), cation (b2-3), or cation (b2-4).

[0205] Preferably, the acid generator (B) is represented by formulas (B1-1) to (B1-60), among which those containing arylsulfonium cations are preferred, and those represented by formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), and (B1-31) to (B1-60) are particularly preferred. JPEG0007943791000125.jpg214167

[0206] TIFF0007943791000126.tif235159

[0207] TIFF0007943791000127.tif237165

[0208] In the resist composition of the present invention, the content of the acid generator is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 45% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and even more preferably 3% by mass or more and 40% by mass or less, based on the solid content of the resist composition. When resin (A) etc. is included, the content of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and even more preferably 3 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of resin (A) etc.

[0209] <Solvent (E)> The content percentage of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content percentage of the solvent (E) can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0210] Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One type of the solvent (E) may be used alone, or two or more types may be used in combination.

[0211] <Quencher (C)> Examples of the quencher (C) include the salt (I), a salt that generates an acid having a lower acidity than the acid generated from the structural unit (IP) and the acid generator (B), and a basic nitrogen-containing organic compound. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass, based on the solid content of the resist composition.

[0212] <Salt that generates an acid having a lower acidity than the acid generated from the acid generator> The acidity of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is usually a salt in which the acid dissociation constant of the acid generated from the salt satisfies -3 < pKa, preferably a salt satisfying -1 < pKa < 7, and more preferably a salt satisfying 0 < pKa < 5. Examples of salts that generate an acid weaker in acidity than the acid generated from the acid generator (B) include the salt represented by the following formula, the salt represented by formula (D) described in Japanese Patent Publication No. 2015-147926 (hereinafter sometimes referred to as "weak acid intramolecular salt (D)"), and the salts described in Japanese Patent Publication Nos. 2012-229206, 2012-6908, 2012-72109, 2011-39502 and 2011-191745. Preferably, the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt that generates a carboxylic acid weaker in acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), more preferably a weak acid intramolecular salt (D), and even more preferably a weak acid intramolecular salt (D). TIFF0007943791000128.tif107170

[0213] The weak acid intramolecular salt (D) is preferably a diphenyliodonium salt having an iodonium cation to which two phenyl groups are bonded and a carboxyanion to which at least one of the two phenyl groups bonded to the iodonium cation is substituted, and examples of salts represented by the following formula include: TIFF0007943791000129.tif1593 [In formula (D), R D1 and R D2 Each of these independently represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom. m' and n' each independently represent an integer from 0 to 4, and if m' is 2 or greater, multiple R D1 They may be the same or different, and if n' is 2 or more, there may be multiple R D2 They may be the same or different. R D1 and R D2 Examples of hydrocarbon groups include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combinations thereof. Examples of chain-type hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and nonyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be saturated or unsaturated. Examples include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and cyclododecyl groups, as well as norbonyl and adamantyl groups. Examples of aromatic hydrocarbon groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and aryl groups such as 2-methyl-6-ethylphenyl. Groups formed by combining these include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, and aralkyl groups (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.). Examples of alkoxy groups include methoxy groups and ethoxy groups. Examples of acyl groups include acetyl groups, propanoyl groups, benzoyl groups, and cyclohexanecarbonyl groups. Examples of acyloxy groups include groups in which an oxy group (-O-) is bonded to the above-mentioned acyl group. Examples of alkoxycarbonyl groups include groups in which a carbonyl group (-CO-) is bonded to the above-mentioned alkoxy group. Examples of halogen atoms include fluorine, chlorine, and bromine atoms. R D1 and R D2 Each of these is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom. m' and n' are each independently preferably integers between 0 and 2, and more preferably 0. If m' is 2 or greater, multiple R D1 They may be the same or different, and if n' is 2 or more, there may be multiple R D2 They may be the same or different. More specifically, the following salts are examples: TIFF0007943791000130.tif72165

[0214] Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, and tributylamine. Amine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methylddecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethylddecylamine Min, 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)ethanol Examples include 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, and the like. Preferably, aromatic amines such as diisopropylaniline are included, and more preferably, 2,6-diisopropylaniline is included. 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.

[0215] <Other ingredients> The resist composition of the present invention may optionally contain components other than those described above (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., can be used.

[0216] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing a resin containing a salt represented by formula (I) or a structural unit represented by formula (I-1), optionally a resin (A), an acid generator (B), a resin other than resin (A), a solvent (E), a quencher (C), and other components (F). The mixing order is arbitrary and 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. There are no particular restrictions on the mixing method, and stirring or other methods can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm.

[0217] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. The resist composition can be applied to a substrate using commonly used equipment such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers, and organic substrates with a resist film or the like formed on their surface. Before applying the resist composition, the substrate may be cleaned, or an anti-reflective film or the like may be formed on the substrate. The solvent is removed and a composition layer is formed by drying the coated composition. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. The pressure when drying under reduced pressure is 1 to 1.0 × 10⁻⁶. 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Various types of exposure light sources can be used, including those that emit ultraviolet laser light such as KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm), those that emit far-ultraviolet or vacuum-ultraviolet harmonic laser light by wavelength conversion of laser light from a solid-state laser light source (such as a YAG or semiconductor laser), electron beams, and those that irradiate with ultra-ultraviolet (EUV) light. In this specification, the irradiation of these radiations is sometimes collectively referred to as "exposure." During exposure, exposure is usually performed through a mask corresponding to the desired pattern. If the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is subjected to heat treatment (so-called post-exposure bake) to promote the deprotection reaction at acid-unstable groups. The heating temperature is usually around 50 to 200°C, preferably around 70 to 150°C. After heating, a chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition. Alternatively, before development, the process of coating the resist composition, drying, exposure, and heating may be repeated on the composition layer after exposure. The heated composition layer is typically developed using a developing apparatus and a developing solution. Development methods include the dip method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as described below, a positive-type resist pattern or a negative-type resist pattern can be manufactured. When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer can be any alkaline aqueous solution used in this field. For example, aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) can be used. The alkaline developer may also contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove any remaining water on the substrate and pattern. When manufacturing a negative-type resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially composed of only organic solvents. Among these, organic developers containing butyl acetate and / or 2-heptanone are preferred. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially butyl acetate and / or 2-heptanone alone. Organic developers may contain surfactants. Furthermore, organic developers may contain trace amounts of water. During development, the development process may be stopped by substituting a different type of solvent for the organic developer. It is preferable to wash the developed resist pattern with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0218] <Application> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, an ArF excimer laser exposure, an electron beam (EB) exposure, or an EUV exposure, and is particularly suitable as a resist composition for electron beam (EB) exposure or an EUV exposure, and is useful for semiconductor microfabrication. [Examples]

[0219] The present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are based on mass unless otherwise specified. The weight-average molecular weight was determined by gel permulation chromatography. The analytical conditions for gel permulation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / 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: Agilent 1100, MASS: Agilent LC / MSD). In the following examples, the value of this molecular ion peak is indicated as "MASS".

[0220] Example 1: Synthesis of the salt represented by formula (I-1) TIFF0007943791000131.tif62152 Mix 6.56 parts of the salt represented by formula (I-1-a) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 2.50 parts of the compound represented by formula (I-1-c) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 4.21 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 407.1

[0221] Example 2: Synthesis of the salt represented by formula (I-2) TIFF0007943791000132.tif71152 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 6.42 parts of the salt represented by formula (I-2-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate the organic layer to remove it. Add 25 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate the organic layer to remove it. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 6.94 parts of the salt represented by formula (I-2). MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 407.1

[0222] Example 3: Synthesis of the salt represented by formula (I-3) TIFF0007943791000133.tif66149 Mix 2.36 parts of the compound represented by formula (I-3-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 6.42 parts of the salt represented by formula (I-2-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 3.89 parts of the salt represented by formula (I-3). MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 423.1

[0223] Example 4: Synthesis of the salt represented by formula (I-4) TIFF0007943791000134.tif68154 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 7.10 parts of the salt represented by formula (I-4-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 6.89 parts of the salt represented by formula (I-4). MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 475.1

[0224] Example 5: Synthesis of the salt represented by formula (I-492) TIFF0007943791000135.tif94151 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 7.78 parts of the salt represented by formula (I-492-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 8.84 parts of the salt represented by formula (I-492). MASS(ESI(+)Spectrum):M + 617.0 MASS(ESI(-)Spectrum):M - 407.1

[0225] Example 6: Synthesis of the salt represented by formula (I-520) TIFF0007943791000136.tif92153 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 7.43 parts of the salt represented by formula (I-520-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 8.43 parts of the salt represented by formula (I-520). MASS(ESI(+)Spectrum):M + 581.0 MASS(ESI(-)Spectrum):M - 407.1

[0226] Example 7: Synthesis of the salt represented by formula (I-617) TIFF0007943791000137.tif64135 Mix 6.70 parts of the salt represented by formula (I-617-a) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 2.50 parts of the compound represented by formula (I-1-c) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to obtain 8.09 parts of the salt represented by formula (I-617). MASS(ESI(+)Spectrum):M + 495.0 MASS(ESI(-)Spectrum):M - 407.1

[0227] Example 8: Synthesis of the salt represented by formula (I-618) TIFF0007943791000138.tif72153 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 6.57 parts of the salt represented by formula (I-618-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to obtain 7.21 parts of the salt represented by formula (I-618). MASS(ESI(+)Spectrum):M + 495.0 MASS(ESI(-)Spectrum):M - 407.1

[0228] Example 9: Synthesis of the salt represented by formula (I-620) TIFF0007943791000139.tif71156 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 7.25 parts of the salt represented by formula (I-620-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. The supernatant was then removed and concentrated to obtain 6.88 parts of the salt represented by formula (I-620). MASS(ESI(+)Spectrum):M + 495.0 MASS(ESI(-)Spectrum):M - 475.1

[0229] Example 10: Synthesis of the salt represented by formula (I-730) TIFF0007943791000140.tif74153 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 7.98 parts of the salt represented by formula (I-730-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and to the concentration residue, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to obtain 7.21 parts of the salt represented by formula (I-730). MASS(ESI(+)Spectrum):M + 636.9 MASS(ESI(-)Spectrum):M - 407.1

[0230] Example 11: Synthesis of the salt represented by formula (I-1290) TIFF0007943791000141.tif87155 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 9.34 parts of the salt represented by formula (I-1290-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The resulting organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentration residue. The mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and the mixture was concentrated to obtain 9.79 parts of the salt represented by formula (I-1290). MASS(ESI(+)Spectrum):M + 772.9 MASS(ESI(-)Spectrum):M - 407.1

[0231] Example 12: Synthesis of the salt represented by formula (I-1304) TIFF0007943791000142.tif81153 Mix 2.64 parts of the compound represented by formula (I-2-c) and 50 parts of chloroform, stir at 23°C for 30 minutes, then add 1.62 parts of the compound represented by formula (I-1-b), raise the temperature to 50°C, and stir at 50°C for 2 hours. Add 9.348 parts of the salt represented by formula (I-1304-a) to the resulting reaction mixture and stir at 50°C for 10 hours. After cooling the resulting reaction mixture to 23°C, add 25 parts of deionized water and stir at 23°C for 30 minutes, then separate the organic layer to remove it. Add 25 parts of deionized water to the obtained organic layer and stir at 23°C for 30 minutes, then separate the organic layer to remove it. Repeat this washing procedure five times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentration residue. The mixture was stirred at 23°C for 30 minutes, and the supernatant was removed and concentrated to obtain 9.46 parts of the salt represented by formula (I-1304). MASS(ESI(+)Spectrum):M + 772.9 MASS(ESI(-)Spectrum):M - 407.1

[0232] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. Hereafter, these compounds will be referred to as "monomers (a1-1-3)," etc., according to their formula numbers. TIFF0007943791000143.tif187166

[0233] TIFF0007943791000144.tif68156

[0234] Example 13 [Synthesis of Resin A1] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-1)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A1 was obtained in a yield of 58%. This resin A1 has the following structural units. TIFF0007943791000145.tif50164

[0235] Example 14 [Synthesis of Resin A2] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-2)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.5 × 10⁶. 3 Resin A2 was obtained in a yield of 64%. This resin A2 has the following structural units. TIFF0007943791000146.tif49162

[0236] Example 15 [Synthesis of Resin A3] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-3) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-3)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.7 × 10⁶. 3 Resin A3 was obtained with a yield of 66%. This resin A3 has the following structural units. TIFF0007943791000147.tif54157

[0237] Example 16 [Synthesis of Resin A4] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-4) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-4)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.4 × 10⁶. 3 Resin A4 was obtained with a yield of 60%. This resin A4 has the following structural units. TIFF0007943791000148.tif51163

[0238] Example 17 [Synthesis of Resin A5] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13):monomer (I-2)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.4 × 10⁶. 3 Resin A5 was obtained with a yield of 61%. This resin A5 has the following structural units. TIFF0007943791000149.tif54161

[0239] Example 18 [Synthesis of Resin A6] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-2)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution in an amount 2.0 times the total mass of the monomers, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A6 was obtained with a yield of 84%. This resin A6 has the following structural units. TIFF0007943791000150.tif57159

[0240] Example 19 [Synthesis of Resin A7] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13):monomer (I-2)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.4 × 10⁶. 3 Resin A7 was obtained with a yield of 78%. This resin A7 has the following structural units. TIFF0007943791000151.tif62152

[0241] Example 20 [Synthesis of Resin A8] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-19), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-19):monomer (I-2)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5 wt%) relative to the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.6 × 10⁶. 3 Resin A8 was obtained in a yield of 75%. This resin A8 has the following structural units. TIFF0007943791000152.tif56157

[0242] Example 21 [Synthesis of Resin A9] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-20), and (I-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-20):monomer (I-2)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount equal to 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A9 was obtained in a yield of 68%. This resin A9 has the following structural units. TIFF0007943791000153.tif58161

[0243] Example 22 [Synthesis of Resin A10] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-492) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-492)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A10 was obtained in a yield of 67%. This resin A10 has the following structural units. TIFF0007943791000154.tif56165

[0244] Example 23 [Synthesis of Resin A11] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-520) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-520)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.6 × 10⁶. 3 Resin A11 was obtained with a yield of 63%. This resin A11 has the following structural units. TIFF0007943791000155.tif56164

[0245] Example 24 [Synthesis of Resin A12] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-617) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-617)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A12 was obtained with a yield of 63%. This resin A12 has the following structural units. TIFF0007943791000156.tif54168

[0246] Example 25 [Synthesis of Resin A13] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-618) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-618)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, a 2.5% by weight aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution in an amount 2.0 times the total mass of the monomers, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.2 × 10⁶. 3 Resin A13 was obtained with a yield of 66%. This resin A13 has the following structural units. TIFF0007943791000157.tif55166

[0247] Example 26 [Synthesis of Resin A14] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-620) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-620)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.5 × 10⁶. 3 Resin A14 was obtained with a yield of 59%. This resin A14 has the following structural units. TIFF0007943791000158.tif56166

[0248] Example 27 [Synthesis of Resin A15] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-730) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-730)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A15 was obtained with a yield of 64%. This resin A15 has the following structural units. TIFF0007943791000159.tif54168

[0249] Example 28 [Synthesis of Resin A16] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-618) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13):monomer (I-618)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution in an amount 2.0 times the total mass of the monomers, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A16 was obtained in a yield of 62%. This resin A16 has the following structural units. TIFF0007943791000160.tif56163

[0250] Example 29 [Synthesis of Resin A17] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-618) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-618)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution in an amount 2.0 times the total mass of the monomers, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A17 was obtained with a yield of 88%. This resin A17 has the following structural units. TIFF0007943791000161.tif62163

[0251] Example 30 [Synthesis of Resin A18] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-618) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-13):monomer (I-618)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A18 was obtained in a yield of 84%. This resin A18 has the following structural units. TIFF0007943791000162.tif64156

[0252] Example 31 [Synthesis of Resin A19] Monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-19), and (I-618) were used as monomers, and they were mixed in a molar ratio [monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-19):monomer (I-618)] of 55:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount equal to 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁶. 3 Resin A19 was obtained in a yield of 81%. This resin A19 has the following structural units. TIFF0007943791000163.tif62161

[0253] Example 32 [Synthesis of Resin A20] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1290) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-1290)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.5 × 10⁶. 3 Resin A20 was obtained with a yield of 66%. This resin A20 has the following structural units. TIFF0007943791000164.tif57168

[0254] Example 33 [Synthesis of Resin A21] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1304) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (I-1304)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, a 2.5% by weight aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution in an amount 2.0 times the total mass of the monomers, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.2 × 10⁶. 3 Resin A21 was obtained in a yield of 62%. This resin A21 has the following structural units. TIFF0007943791000165.tif57168

[0255] Synthesis Example 1 [Synthesis of Resin AX1] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (AX-1) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (AX-1)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.5 × 10⁶. 3 Resin AX1 was obtained in a yield of 66%. This resin AX1 has the following structural units. TIFF0007943791000166.tif52168

[0256] Synthesis Example 2 [Synthesis of Resin AX2] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (AX-2) were used as monomers, and they were mixed in a molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3):monomer (a3-4-2):monomer (a1-4-2):monomer (AX-2)] of 20:35:3:12:25:5. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount 2.0 times the total mass of the monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.4 × 10⁶. 3 Resin AX2 was obtained in a yield of 60%. This resin AX2 has the following structural units. TIFF0007943791000167.tif51167

[0257] Synthesis Example 3 [Synthesis of Resin AA1] Monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), and (a1-4-2) were used as monomers, and they were mixed in 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. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at concentrations of 1.2 mol% and 3.6 mol%, respectively, relative to the total amount of monomers, and these mixtures were heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) in an amount 2.0 times the total mass of monomers was added to the polymerization reaction solution, and after stirring for 12 hours, the solution was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.5 × 10⁶. 3 Resin AA1 was obtained in a yield of 68%. This resin AA1 has the following structural units. TIFF0007943791000168.tif38161

[0258] <Preparation of the resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition. [Table 2] TIFF0007943791000170.tif233167

[0259] <Resin> A1~A21, AX1, AX2, AA1: Resin A1~Resin A21, Resin AX1, Resin AX2, Resin AA1 <Salt (I)> I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-3: Salt represented by formula (I-3) I-4: Salt represented by formula (I-4) I-492: Salt represented by formula (I-492) I-520: Salt represented by formula (I-520) I-617: Salt represented by formula (I-617) I-618: Salt represented by formula (I-618) I-620: Salt represented by formula (I-620) I-730: Salt represented by formula (I-730) I-1290: Salt represented by formula (I-1290) I-1304: Salt represented by formula (I-1304) <Acid Generator> B1-25: Salt represented by formula (B1-25); synthesized by the method described in Japanese Patent Publication No. 2011-126869. TIFF0007943791000171.tif2667IX-1: Synthesized by the method described in Japanese Patent Publication No. 2010-77404 IX-2: Synthesized by the method described in Japanese Patent Publication No. 2007-197718 TIFF0007943791000172.tif47114<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007943791000173.tif4146<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0260] (Electron beam exposure evaluation of resist compositions) A 6-inch silicon wafer was treated with hexamethyldisilazane at 90°C for 60 seconds on a direct hot plate. A resist composition was spin-coated onto this silicon wafer such that the film thickness of the composition layer was 0.04 μm. Thereafter, pre-baking was performed on the direct hot plate for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. Using an electron beam lithography system ["ELS-F125 125keV" manufactured by Elionix Inc.], a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer while changing the exposure dose stepwise. After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 2. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer at 23°C for 20 seconds by a dynamic dispense method, thereby obtaining a resist pattern.

[0261] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter reached 17 nm was defined as the effective sensitivity.

[0262] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times per one hole, and the average value thereof was defined as the average hole diameter of one hole. The standard deviation was determined using the population of 400 measured points of the average hole diameter of the pattern formed with a hole diameter of 17 nm within the same wafer. The results are shown in Table 3 and Table 4. The numerical values in the tables indicate the standard deviation (nm). [Table 3] [Table 4] Compared to comparative compositions 1-8, compositions 1-53 showed smaller standard deviations and better CD uniformity (CDU) evaluation. [Industrial applicability]

[0263] The resist composition of the present invention is suitable for semiconductor microfabrication and is extremely useful in industry because it can produce resist patterns with good CD uniformity (CDU).

Claims

1. An acid generator containing a salt represented by formula (I) or a structural unit represented by formula (IP). [In formulas (I) and (IP), R4 represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, wherein the -CH2- contained in the haloalkyl group may be replaced with -O-, -CO-, -S-, or -SO2-, and the hydrocarbon group may have substituents, with the -CH2- contained in the hydrocarbon group being replaced with -O-. R ５ , R ６ , R ７ , R ８ and R ９ Each of these independently represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, and the hydrocarbon group may have substituents, and the haloalkyl group or the hydrocarbon group contains -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. A １ A represents ***-X01-L01- or ***-L01-X01-, A2 represents ***-X02-L02- or ***-L02-X02-, A3 represents ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 represent oxygen atoms, L01, L02 and L03 each independently represent a single bond or a hydrocarbon group having 1 to 18 carbon atoms, and *** represents the bonding site with the benzene ring to which S+ is bonded. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 5, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 5, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents any integer from 1 to 5, and when m4 is 2 or more, a plurality of R ４ may be the same as or different from each other. m5 represents an integer from 0 to 5, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 5, and when m6 is 2 or greater, multiple R ６ They may be identical or different from one another. m7 represents an integer from 0 to 4, and when m7 is 2 or greater, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 5, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. m9 represents an integer from 0 to 5, and when m9 is 2 or greater, multiple R ９ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. Q ｂ１ and Q ｂ２ Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y ｂ１ represents a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms, which may have single bonds or substituents, and the cycloaliphatic hydrocarbon group contains -CH ２ - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. R ｂｂ１ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X １０ This represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * is R ｂｂ１ The symbol represents the bonding site with the carbon atom to which it is bonded, and ** represents L １０ This represents the connection point. L １０ This represents a hydrocarbon group having 1 to 36 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-.

2. L ０１ , L ０２ and L ０３ The acid generator according to claim 1, wherein each is independently a single bond or an alkanediyl group having 1 to 6 carbon atoms.

3. Y ｂ１ The acid generator according to claim 1, wherein the group is a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, or a norbornanelactonediyl group.

4. X １０ is equation (X １ -1), formula (X １ -2') ~Formula (X １ -7'), formula (X １ The acid generator according to claim 1, wherein the group is represented by any of (-8). [Formula (X)] １ -1), Equation (X) １ -2') ~ formula (X １ -7'), Equation (X) １ -8) Middle * and ** are binding sites, and ** is L 1０ This represents the connection point. Rx represents a halogen atom, a hydroxyl group, a C1-C6 alkyl fluoride or a C1-C18 alkyl group, or a C1-C6 alkoxy group. mx represents an integer between 0 and 4.

5. X １０ However, equation (X １ -1), formula (X １ -4) and formula (X １ The acid generator according to claim 4, which is a group represented by any of (-5). [Formula (X １ -1), formula (X １ -4) and formula (X １ -5) Medium, * and ** are binding sites, and ** is L 1０ This represents the connection point with [the other element].

6. L １０ However, a single bond or an alkanediyl group having 1 to 4 carbon atoms (provided that the alkanediyl group contains -CH 2 The acid generator according to claim 1, wherein - may be replaced with -O- or -CO-.

7. A resist composition comprising the acid generator according to any one of claims 1 to 6.

8. The salt represented by formula (I), The resist composition according to claim 7, comprising a resin containing a structural unit (a1) having an acid-unstable group.

9. It contains a resin that includes a structural unit represented by formula (IP), The resist composition according to claim 7, wherein the resin containing a structural unit represented by formula (IP) further comprises a structural unit (a1) having an acid-unstable group.

10. The resist composition according to claim 9, further comprising a salt represented by formula (I).

11. The resist composition according to claim 8 or 9, wherein the structural unit (a1) having an acid-unstable group is selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). [In formulas (a1-0), (a1-1), and (a1-2), L a01 , L ａ１ and L ａ２ These are, independently, -O- or *-O- (CH ２ ) ｋ１ This represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bonding site with -CO-. R a01 , R ａ４ and R ａ５ Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R ａ６ and R ａ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

12. The resist composition according to claim 7, further comprising a resin containing a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 - (A a52 -X a52 ) nｂ - represents -R a50 This represents the bonding relationship between the carbon atom and the bonded carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent, independently, -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, then multiple R a51 They may be identical or different from one another.

13. The resist composition according to claim 7, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

14. (1) A step of applying the resist composition according to claim 7 onto a substrate, (2) A step of drying the coated composition to form a composition layer, (3) Exposure step of the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

15. A salt represented by formula (I). [In formula (I), R4 represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, wherein the -CH2- contained in the haloalkyl group may be replaced with -O-, -CO-, -S-, or -SO2-, and the hydrocarbon group may have substituents, with the -CH2- contained in the hydrocarbon group being replaced with -O-. R ５ , R ６ , R ７ , R ８ and R ９ Each of these independently represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, and the hydrocarbon group may have substituents, and the haloalkyl group or the hydrocarbon group contains -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. A １ A represents ***-X01-L01- or ***-L01-X01-, A2 represents ***-X02-L02- or ***-L02-X02-, A3 represents ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 represent oxygen atoms, L01, L02 and L03 each independently represent a single bond or a hydrocarbon group having 1 to 18 carbon atoms, and *** represents the bonding site with the benzene ring to which S+ is bonded. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 5, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 5, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer from 1 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another. m5 represents an integer from 0 to 5, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 5, and when m6 is 2 or greater, multiple R ６ They may be identical or different from one another. m7 represents an integer from 0 to 4, and when m7 is 2 or greater, multiple R ７ They may be identical or different from one another. m8 represents any integer from 0 to 5, and when m8 is 2 or more, a plurality of R ８ may be the same or different from each other. m9 represents an integer from 0 to 5, and when m9 is 2 or greater, multiple R ９ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. Q ｂ１ and Q ｂ２ Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y ｂ１ represents a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, and -CH contained in the alicyclic hydrocarbon group ２ - may be replaced with -O-, -CO-, -S- or -SO ２ -. R ｂｂ１ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X １０ This represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * is R ｂｂ１ The symbol represents the bonding site with the carbon atom to which it is bonded, and ** represents L １０ This represents the connection point. L １０ This represents a hydrocarbon group having 1 to 36 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-.

16. L ０１ , L ０２ and L ０３ The salt according to claim 15, wherein each is independently a single bond or an alkanediyl group having 1 to 6 carbon atoms.

17. Y ｂ１ The salt according to claim 15 or 16, wherein is a cyclohexanediyl group, an adamantanediyl group, an adamantanelactonediyl group, a norbornanediyl group, or a norbornanelactonediyl group.

18. X １０ is equation (X １ -1), formula (X １ -2') ~Formula (X １ -7'), formula (X １ The salt according to claim 15 or 16, wherein the group is represented by any of (-8). [Formula (X)] １ -1), Equation (X) １ -2') ~ formula (X １ -7'), Equation (X) １ -8) Middle * and ** are binding sites, and ** is L 1０ This represents the connection point. Rx represents a halogen atom, a hydroxyl group, a C1-C6 alkyl fluoride or a C1-C18 alkyl group, or a C1-C6 alkoxy group. mx represents an integer between 0 and 4.

19. X １０ However, equation (X １ -1), formula (X １ -4) and formula (X １ The salt according to claim 18, wherein the group is represented by any of (-5). [Formula (X １ -1), formula (X １ -4) and formula (X １ -5) Medium, * and ** are binding sites, and ** is L 1０ This represents the connection point with [the other element].

20. L １０ However, a single bond or an alkanediyl group having 1 to 4 carbon atoms (provided that the alkanediyl group contains -CH 2 The salt according to claim 15 or 16, wherein - may be replaced by -O- or -CO-.

21. A resin containing structural units represented by formula (IP). [In the formula (IP), R4 represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, wherein the -CH2- contained in the haloalkyl group may be replaced with -O-, -CO-, -S-, or -SO2-, and the hydrocarbon group may have substituents, with the -CH2- contained in the hydrocarbon group being replaced with -O-. R ５ , R ６ , R ７ , R ８ and R ９ Each of these independently represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, and the hydrocarbon group may have substituents, and the haloalkyl group or the hydrocarbon group contains -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. A １ A represents ***-X01-L01- or ***-L01-X01-, A2 represents ***-X02-L02- or ***-L02-X02-, A3 represents ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 represent oxygen atoms, L01, L02 and L03 each independently represent a single bond or a hydrocarbon group having 1 to 18 carbon atoms, and *** represents the bonding site with the benzene ring to which S+ is bonded. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 5, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 5, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer from 1 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another. m5 represents an integer from 0 to 5, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 5, and when m6 is 2 or greater, multiple R ６ They may be identical or different from one another. m7 represents an integer from 0 to 4, and when m7 is 2 or greater, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 5, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. m9 represents an integer from 0 to 5, and when m9 is 2 or greater, multiple R ９ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. Q ｂ１ and Q ｂ２ Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y ｂ１ represents a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms, which may have single bonds or substituents, and the cycloaliphatic hydrocarbon group contains -CH ２ - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. R ｂｂ１ This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X １０ This represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * is R ｂｂ１ The symbol represents the bonding site with the carbon atom to which it is bonded, and ** represents L １０ This represents the connection point. L １０ This represents a hydrocarbon group having 1 to 36 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-.

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