Method for manufacturing carboxylates, carboxylic acid generating agents, resins, resist compositions, and resist patterns.

Abstract

The object of this invention is to provide a carboxylic acid generator, resin, and resist composition comprising a carboxylic acid salt, etc., capable of producing a resist pattern with good line edge roughness. A carboxylic acid generator, resin, and resist composition comprising a carboxylic acid salt represented by formula (I) or structural units derived therefrom. [In the formula, R4 to R9 represent halogen atoms, haloalkyl groups, etc. A1 to A3 represent hydrocarbon groups. m1 represents an integer from 1 to 5, m2 to m6, m8, and m9 represent integers from 0 to 5, and m7 represents an integer from 0 to 4, wherein 1≦m1+m7≦5, 0≦m2+m8≦5, and 0≦m3+m9≦5. X0 represents a single bond, a substituted / unsubstituted hydrocarbon group. Rbb1 represents a hydrogen atom, a halogen atom, etc. X10 represents a single bond, *-O-**, *-CO-O-**, etc.] L 10 indicates a single bond or a substituted / unsubstituted hydrocarbon group.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a carboxylate, a carboxylic acid generating agent, a resin, a resist composition, and a resist pattern. Prior Technology

[0002] Patent Document 1 describes an anti-corrosion composition containing a resin comprising structural units derived from carboxylate salts represented by the following formula. [Existing Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2011-037834 Summary of the Invention

[0004] [The problem that the invention aims to solve]

[0005] The present invention provides a carboxylate that forms a resist pattern with better line edge roughness (LER) than a resist pattern formed by a resist composition containing a resin comprising structural units derived from the carboxylate. [Methods for solving problems]

[0006] This invention includes the following inventions. [1] A carboxylic acid generating agent containing a carboxylate represented by formula (I) or a structural unit represented by formula (IP). In equations (I) and (IP), R4, R5, R6, R7, R8 and R9 each independently represent a halogen atom, a haloalkyl group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. A1, A2 and A3 independently represent hydrocarbon groups with 1 to 20 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. m1 represents any integer from 1 to 5. When m1 is 2 or higher, the bases within the parentheses can be the same or different. m2 represents any integer from 0 to 5. When m2 is 2 or higher, the bases within the parentheses can be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 0 to 5. When m4 is 2 or higher, multiple R4s can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, multiple R5s can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, multiple R6s can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, multiple R7s can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, multiple R8s can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, multiple R9s can be the same or different. Among them, 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5. X 0 represents a single bond, a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, and the -CH 2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2-. R bb1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. X 10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenyl group that can have substituents. Ax represents a group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. Ay represents a bond type selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to R bb1, and ** indicates the bonding site with L 10. L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- group may be replaced by -O-, -S-, -SO2- or -CO-. [2] The carboxylic acid generating agent as described in [1], wherein A1 is ***-X 01-L 01- or ***-L 01-X 01-. A2 is either ***-X 02-L 02- or ***-L 02-X 02-. A3 is either ***-X 03-L 03- or ***-L 03-X 03-. X01, X02, and X03 independently represent -O-, -CO-, -S-, or -SO2-, respectively. L01, L02, and L03 each independently represent a single bond or a hydrocarbon group with 1 to 18 carbon atoms. *** indicates the bonding site of the benzene ring bonded to S+. [3] The carboxylic acid generating agent as described in [2], wherein X01, X02 and X03 are oxygen atoms. [4] The carboxylic acid generating agent as described in [2] or [3], wherein L01, L02 and L03 are each independently a single bond or an alkyl diol with 1 to 6 carbon atoms. [5] The carboxylic acid generating agent as described in any one of [1] to [4], wherein R4, R5 and R6 are each independently a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. [6] A carboxylic acid generating agent as described in any one of [1] to [5], wherein X0 is an aliphatic hydrocarbon group with 1 to 72 carbon atoms that may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) or an aromatic hydrocarbon group with 6 to 36 carbon atoms that may have substituents. [7] The carboxylic acid generating agent as described in any one of [1] to [6], wherein X0 comprises an alicyclic hydrocarbon group having fluorine atom, a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group having 3 to 36 carbons (the -CH 2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO 2-), a group consisting of an alicyclic hydrocarbon group having 3 to 36 carbons and a chain hydrocarbon group having 1 to 18 carbons (the -CH 2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO 2-, the -CH 2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, the alicyclic hydrocarbon group and the chain hydrocarbon group may have fluorine atom, a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group having fluorine atom, a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group having 6 to 36 carbons. [8] A carboxylic acid generating agent as described in any one of [1] to [7], wherein X0 comprises the alicyclic hydrocarbon group, The alicyclic hydrocarbon group is a cycloalkanediyl group with 5 or 6 carbon atoms (the -CH 2- contained in the cycloalkanediyl group can be replaced by -O- or -CO-, and the cycloalkanediyl group can also be an acetal ring). The polycyclic alicyclic hydrocarbon group includes adamantyl or norbornanediyl, adamantyl and a cycloalkanediyl group with 5 or 6 carbon atoms bonded to the adamantyl by a helical bond (the -CH 2- contained in the adamantyl, norbornanediyl and cycloalkanediyl can be replaced by -O- or -CO-, the -CH 2-CH 2- contained in the adamantyl and norbornanediyl can be replaced by -O-CO-, and the cycloalkanediyl group can also be an acetal ring). [9] A carboxylic acid generating agent as described in any one of [1] to [8], wherein X 10 is a single bond or a group represented by any one of the formulas (X 1-1), (X 1-2') to (X 1-7'), and (X 1-8). In equations (X1-1), (X1-2') to (X1-7'), and (X1-8), * and ** represent the bonding sites, and ** indicates the bonding site with L 10. Rx represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. [mx represents any integer from 0 to 4]

[10] The carboxylic acid generating agent as described in [9], wherein X 10 is a single bond, a group represented by any one of the formulas (X 1-1), (X 1-4) and (X 1-5). In equations (X1-1), (X1-4), and (X1-5), * and ** represent the bonding sites, with ** indicating the bonding site with L10.

[11] The carboxylic acid generating agent as described in any one of [1] to

[10] , wherein L 10 is a single bond or an alkyl diester with 1 to 4 carbon atoms (wherein the -CH 2- contained in the alkyl diester may be replaced with -O- or -CO-).

[12] The carboxylic acid generating agent as described in any one of [1] to

[11] , wherein X0 is a phenyl group that may have substituents. L 10 is a single bond, and X 10 is a single bond or a base represented by formula (X 1-1).

[13] An anti-corrosion composition comprising a carboxylic acid generating agent as described in any one of [1] to

[12] .

[14] The resist composition as described in

[13] contains the salt represented by formula (I), and A resin containing structural units (a1) with acid-instable groups.

[15] The resist composition as described in

[13] or

[14] contains a resin comprising a structural unit represented by the formula (IP). The resin containing the structural unit represented by the formula (IP) further contains structural units (a1) having acid-instable groups.

[16] The resist composition as described in

[15] further comprises a salt represented by formula (I).

[17] The resist composition as described in any one of

[14] to

[16] , wherein the structural unit (a1) having an acid-instable group comprises at least one selected from the group consisting of the structural unit represented by formula (a1-0), the structural unit represented by formula (a1-1), and the structural unit represented by formula (a1-2). In equations (a1-0), (a1-1), and (a1-2), La01, La1, and La2 independently represent -O- or *-O-(CH2) k1-CO-O-, where k1 represents any integer from 1 to 7, and * represents the bonding site with -CO-. Ra01, Ra4, and Ra5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Ra02, Ra03, and Ra04 each independently represent 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 composed of these. Ra6 and Ra7 respectively represent alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 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. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. [n1' represents any integer from 0 to 3]

[18] The resist composition as described in any one of

[13] to

[17] further comprises a resin containing a structural unit represented by formula (a2-A). In formula (a2-A), Ra50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Ra51 represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkoxyalkyl group with 2 to 12 carbon atoms, alkoxyalkoxy group with 2 to 12 carbon atoms, alkyl carbonyl group with 2 to 4 carbon atoms, alkyl carbonyloxy group with 2 to 4 carbon atoms, acryloxy group or methacryloxy group. A a50 represents a single bond or *-X a51-(A a52-X a52) nb-, * represents a bonded carbon atom to -R a50. A a52 represents an alkyldiyl group with 1 to 6 carbon atoms. X a51 and X a52 independently represent -O-, -CO-O-, or -O-CO-, respectively. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer greater than 2, multiple Ra51 values ​​can be the same or different.

[19] The resist composition as described in any one of

[13] to

[18] further comprises a salt represented by formula (B1). In formula (B1), Qb1 and Qb2 independently represent hydrogen atoms, fluorine atoms, perfluoroalkyl groups having 1 to 6 carbon atoms, or alkyl groups having 1 to 6 carbon atoms, respectively. L b1 represents a divalent saturated hydrocarbon group with 1 to 24 carbon atoms. The -CH 2- in this divalent saturated hydrocarbon group can be replaced with -O- or -CO-, and the hydrogen atom in this divalent saturated hydrocarbon group can be replaced with a fluorine atom or a hydroxyl group. Y represents a methyl group that may have substituents or an alicyclic hydrocarbon group with 3 to 24 carbon atoms that may have substituents, wherein the -CH 2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO 2- or -CO-. Z+ indicates an organic cation.

[20] A method for manufacturing a resist pattern, comprising: (1) The step of coating a resist composition as described in any one of

[13] to

[19] onto a substrate; (2) The step of drying the coated composition to form a composition layer; (3) The step of exposing the constituent layers; (4) The step of heating the exposed constituent layer; and (5) The step of developing the heated composition layer.

[21] A carboxylate, represented by formula (I). In formula (I), R4, R5, R6, R7, R8 and R9 each independently represent a halogen atom, a haloalkyl group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. A1, A2 and A3 independently represent hydrocarbon groups with 1 to 20 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. m1 represents any integer from 1 to 5. When m1 is 2 or higher, the bases within the parentheses can be the same or different. m2 represents any integer from 0 to 5. When m2 is 2 or higher, the bases within the parentheses can be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 0 to 5. When m4 is 2 or higher, multiple R4s can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, multiple R5s can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, multiple R6s can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, multiple R7s can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, multiple R8s can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, multiple R9s can be the same or different. Among them, 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5. X 0 represents a single bond or a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH 2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2-. R bb1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. X 10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenyl group that can have substituents. Ax represents a group selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. Ay represents a bond type selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to R bb1, and ** indicates the bonding site with L 10. L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- group may be replaced by -O-, -S-, -SO2- or -CO-.

[22] The carboxylate as described in

[21] , wherein A1 is ***-X 01-L 01- or ***-L 01-X 01-. A2 is either ***-X 02-L 02- or ***-L 02-X 02-. A3 is either ***-X 03-L 03- or ***-L 03-X 03-. X01, X02, and X03 independently represent -O-, -CO-, -S-, or -SO2-, respectively. L01, L02, and L03 each independently represent a single bond or a hydrocarbon group with 1 to 18 carbon atoms. *** indicates the bonding site of the benzene ring bonded to S+.

[23] The carboxylate as described in

[22] , wherein X01, X02 and X03 are oxygen atoms.

[24] The carboxylate as described in

[22] or

[23] , wherein L01, L02 and L03 are each independently a single bond or an alkyl group having 1 to 6 carbon atoms.

[25] The carboxylate as described in any one of

[21] to

[24] , wherein R4, R5 and R6 are each independently a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

[26] The carboxylate as described in any one of

[21] to

[25] , wherein X0 is a single bond or an aliphatic hydrocarbon group with 1 to 72 carbon atoms that may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) or an aromatic hydrocarbon group with 6 to 36 carbon atoms that may have substituents.

[27] The carboxylate as described in

[26] , wherein X0 comprises a single bond, an alicyclic hydrocarbon group of 3 to 36 carbons having a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group (the -CH 2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO 2-), a group composed of an alicyclic hydrocarbon group of 3 to 36 carbons and a chain hydrocarbon group of 1 to 18 carbons (the -CH 2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO 2-, the -CH 2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group), or an aromatic hydrocarbon group of 6 to 36 carbons having a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group.

[28] The carboxylate as described in

[26] , wherein X0 comprises the alicyclic hydrocarbon group, The alicyclic hydrocarbon group is a cycloalkanediyl group with 5 or 6 carbon atoms (the -CH 2- contained in the cycloalkanediyl group can be replaced by -O- or -CO-, and the cycloalkanediyl group can also be an acetal ring). The polycyclic alicyclic hydrocarbon group includes adamantyl or norbornanediyl, adamantyl and a cycloalkanediyl group with 5 or 6 carbon atoms bonded to the adamantyl by a helical bond (the -CH 2- contained in the adamantyl, norbornanediyl and cycloalkanediyl can be replaced by -O- or -CO-, the -CH 2-CH 2- contained in the adamantyl and norbornanediyl can be replaced by -O-CO-, and the cycloalkanediyl group can also be an acetal ring).

[29] The carboxylate as described in any one of

[21] to

[28] , wherein X10 is a single bond or a base represented by any one of the formulas (X1-1), (X1-2') to (X1-7'), and (X1-8).

[30] The carboxylate as described in

[29] , wherein X10 is a single bond, a base represented by any of the formulas (X1-1), (X1-4) and (X1-5).

[31] The carboxylate as described in any one of

[21] to

[30] , wherein L10 is a single bond or an alkyl diester with 1 to 4 carbon atoms (wherein the -CH2- contained in the alkyl diester may be replaced with -O- or -CO-).

[32] A resin comprising the structural unit represented by the formula (IP). [The effects of the invention]

[0007] By using a resist composition that utilizes the carboxylate of the present invention, resist patterns can be manufactured with good line edge roughness (LER). Simple Explanation of the Diagram

[0008] none Implementation

[0009] In this specification, "(meth)acrylate monomer" means "at least one of acrylic monomers and methacrylate monomers". The terms "(meth)acrylate" and "(meth)acrylic acid" also have the same meaning. Among the groups described in this specification, those that can achieve both linear and branched structures can be either one. When -CH₂- in hydrocarbon groups is replaced by -O-, -S-, -CO-, or -SO₂-, it is assumed that the same example applies to all groups. "Combined group" refers to a group formed by bonding two or more of the illustrated groups, the valence of which can be appropriately changed according to the bonding morphology. "Derived from" or "derived from" means that the polymerizable C=C bond in the molecule is polymerized to become a -CC- group (single bond). In the case of stereoisomers, all stereoisomers are included. In this specification, the term "solid component of the resist composition" refers to the total amount of components after removing the solvent (E) described later from the total amount of the resist composition.

[0010] [The carboxylate represented by formula (I)] This invention relates to a carboxylate salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salts (I), the side with the negative charge is sometimes called "anion (I)" and the side with the positive charge is called "cation (I)".

[0011] [Cation (I)] The cation (I) of the salt represented by formula (I) is the cation represented by formula (IC). [In formula (IC), all symbols have the same meaning as in formula (I)]

[0012] Halogen atoms in R4, R5, R6, R7, R8 and R9 can be listed as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, etc. The term "haloalkyl group" in R4, R5, R6, R7, R8, and R9, referring to alkyl groups with 1 to 12 carbon atoms, indicates an alkyl group having 1 to 12 carbon atoms. Examples include fluorinated alkyl groups, chlorinated alkyl groups, brominated alkyl groups, and iodinated alkyl groups. Examples of haloalkyl groups include perfluoroalkyl groups (trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, etc.), 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, and 3,3,4,4,4-pentafluorobutyl, chloromethyl, bromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and perfluorobutyl. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, more preferably 1 to 4, and even more preferably 1 to 3. Examples of hydrocarbon groups with 1 to 18 carbon atoms in R4, R5, R6, R7, R8 and R9 include: alkyl, alkyldiyl and other chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and groups formed by combining these. Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, and dodecyl. As alkyl dienes, which can be straight-chain or branched, examples include: methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and other straight-chain alkyl dienes; and Ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc. The chain hydrocarbon group preferably has 1 to 9 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. As an alicyclic hydrocarbon group, it can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include the groups represented below. The bonding site can be set at any position. Specifically, examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl cycloalkyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, spirocyclohexane-1,2'-cyclopentyl, spiroadamantane-2,3'-cyclopentyl cycloalkyl groups, and spirocyclic rings having cycloalkyl groups bonded to norbornyl or adamantyl respectively by a helical bond. The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16, and even more preferably 3 to 12. Examples of aromatic hydrocarbon groups include: phenyl, naphthyl, biphenyl, anthraceneyl, phenanthryl, and binatyl. The number of carbon atoms in an aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.

[0013] Examples of groups formed by combining two or more of the following: chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups include: groups formed by combining an aromatic hydrocarbon group with a chain hydrocarbon group (e.g., aromatic hydrocarbon-alkadiyl-*, alkyl-aromatic hydrocarbon-*, alkyl-aromatic hydrocarbon-alkadiyl-*, where the -CH 2- contained in the alkadiyl group and the alkyl group can be replaced with -O-, -CO-, -S-, or -SO 2-); and groups formed by combining an alicyclic hydrocarbon group with a chain hydrocarbon group (e.g., alicyclic hydrocarbon-alkadiyl-*, alkyl-alicyclic hydrocarbon-*, alkyl-alicyclic hydrocarbon-alkadiyl-*, where the -CH 2- contained in the alkadiyl group and the alkyl group can be replaced with -O-, -CO-, -S-, or -SO 2-). 2-) A group formed by combining an aromatic hydrocarbon group with an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group-alicyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * indicates the bonding site. As aromatic hydrocarbon groups - alkyl dieryl -*, examples include benzyl, phenethyl, and other arylalkyl groups. Examples of alkyl-aromatic hydrocarbon groups (-*) include: tolyl, xylyl, cumene, etc. Examples of alicyclic hydrocarbon groups (-alkyldiyl-*) include: cyclohexylmethyl, cyclohexylethyl, 1-(adamantane-1-yl)methyl, 1-(adamantane-1-yl)-1-methylethyl, and other cycloalkylalkyl groups. Examples of alkyl-alicyclic hydrocarbon groups include: methylcyclohexyl, dimethylcyclohexyl, 2-alkyladamantane-2-yl, and other cycloalkyl groups containing alkyl groups. Examples of aromatic hydrocarbon groups (allicyclic hydrocarbon groups) include phenylcyclohexyl. Examples of alicyclic hydrocarbon groups (aromatic hydrocarbon groups) include cyclohexylphenyl. Furthermore, in the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups can be combined. In addition, any group can be bonded to the benzene ring.

[0014] When the -CH 2- in the haloalkyl or hydrocarbon group represented by R 4, R 5, R 6, R 7, R 8, and R 9 is replaced with -O-, -CO-, -S-, or -SO 2-, the number of carbons before substitution is set as the total number of carbons in the haloalkyl or hydrocarbon group. Furthermore, the number of substitutions can be one or more. Examples of alkyl and hydrocarbon groups in which the -CH 2- group is replaced with -O-, -CO-, -S-, or -SO 2- include: hydroxyl (a group in a methyl group where the -CH 2- is replaced with -O-), carboxyl (a group in an ethyl group where the -CH 2-CH 2- is replaced with -O-CO-), thiol (a group in a methyl group where the -CH 2- is replaced with -S-), alkoxy (a group in an alkyl group where the -CH 2- is replaced with -O-), alkoxycarbonyl (a group in an alkyl group where the -CH 2-CH 2- is replaced with -O-CO-), alkylcarbonyl (a group in an alkyl group where the -CH 2- is replaced with -CO-), alkylcarbonyloxy (a group in an alkyl group where the -CH 2-CH 2- is replaced with -CO-O-), and alkylthio (a group in an alkyl group where the -CH 2- is replaced with -O-, -CO-, -S-, or -SO 2-). 2-substituted with -S-), alkylsulfonyl (the -CH 2- in the alkyl group is substituted with -SO 2-), oxy (the -CH 2- in the methylene group is substituted with -O-), carbonyl (the -CH 2- in the methylene group is substituted with -CO-), thio (the -CH 2- in the methylene group is substituted with -S-), sulfonyl (the -CH 2- in the methylene group is substituted with -SO 2-), alkadioxy (any position of -CH 2- in the alkadiyl group is substituted with -O-), alkadioxycarbonyl (any position of -CH 2-CH 2- in the alkadiyl group is substituted with -O-CO-), alkadicarbonyl (any position of -CH 2-CH 2- in the alkadiyl group is substituted with -CO-), alkadicarbonyloxy (any position of -CH 2-CH 2- in the alkadiyl group is substituted with -CO-). 2-substituted with -CO-O-, alkyldithio (any position of -CH2- in the alkyl group is substituted with -S-), alkyldisulfonyl (any position of -CH2- in the alkyl group is substituted with -SO2-), cycloalkoxy, cycloalkylalkoxy, alkoxycarbonyloxy, aromatic hydrocarbon-carbonyloxy, aromatic hydrocarbon-carbonyl, aromatic hydrocarbon-oxy, haloalkoxy (any position of -CH2- in the haloalkyl group is substituted with -O-), haloalkoxycarbonyl (any position of -CH2-CH2- in the haloalkyl group is substituted with -O-CO-), haloalkylcarbonyl (any position of -CH2- in the haloalkyl group is substituted with -CO-), haloalkylcarbonyloxy (any position of -CH2-CH2- in the haloalkyl group is substituted with -CO-). 2-substituted with -CO-O-, and groups formed by combining two or more of these groups. Alkoxy groups can be categorized by the number of carbon atoms from 1 to 17, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, etc. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl, alkylcarbonyl, and alkylcarbonyloxy groups represent groups formed by the bonding of a carbonyl or carbonyloxy group with the alkyl or alkoxy group. Examples of alkoxycarbonyl groups with 2 to 17 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. Examples of alkylcarbonyl groups with 2 to 18 carbon atoms include acetyl, propionic, and butionic. Examples of alkylcarbonyloxy groups with 2 to 17 carbon atoms include acetylated, propionic, and butionic. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylthio groups with 1 to 17 carbon atoms include: methylthio, ethylthio, propanethio, butanethio, pentanethio, hexanethio, octanethio, 2-ethylhexanethio, nonanethio, decanethio, undecanethio, etc. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyl sulfonyl groups with 1 to 17 carbon atoms include: methanesulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, nonylsulfonyl, decylsulfonyl, and undecylsulfonyl. The number of carbon atoms in the alkyl sulfonyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldioxy groups with 1 to 17 carbon atoms include methyleneoxy, ethyloxy, propanedioxy, butanedioxy, and pentanedioxy. Preferably, the number of carbon atoms in the alkyldioxy group is 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldioxycarbonyl groups with 2 to 17 carbon atoms include methyleneoxycarbonyl, ethyloxycarbonyl, propylenedioxycarbonyl, and succinylated carbonyl. Examples of alkyldioxycarbonyl groups with 2 to 17 carbon atoms include methylenecarbonyl, ethyloxycarbonyl, propylenedioxycarbonyl, succinylated carbonyl, and pentylcarbonyl. Examples of alkyldioxycarbonyl groups with 2 to 17 carbon atoms include methylenecarbonyloxy, ethyloxycarbonyloxy, propylenedioxycarbonyloxy, and succinylated carbonyloxy. The number of carbon atoms in the alkyldioxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkyldioxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkyldicarbonyloxy 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 alkyldithio groups with 1 to 17 carbon atoms include methylene thio, ethyl thio, and propyl thio. Preferably, the number of carbon atoms in the alkyldithio group is 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldisulfonyl groups with 1 to 18 carbon atoms include methylenesulfonyl, ethylsulfonyl, and propylsulfonyl. The number of carbon atoms in the alkyldisulfonyl group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of cycloalkoxy groups include those with 3 to 17 carbon atoms, such as cyclohexyloxy. Examples of cycloalkylalkoxy groups include those with 4 to 18 carbon atoms, such as cyclohexylmethoxy. Examples of alkoxycarbonyloxy groups include those with 2 to 16 carbon atoms, such as butoxycarbonyloxy. Examples of aromatic hydrocarbon-carbonyloxy groups include those with 7 to 18 carbon atoms, such as benzoyloxy. Examples of aromatic hydrocarbon-carbonyl groups include those with 7 to 18 carbon atoms, such as benzoyl. Examples of aromatic hydrocarbon-oxy groups include those with 6 to 16 carbon atoms, such as phenyloxy. Examples of haloalkoxy, haloalkoxycarbonyl, haloalkylcarbonyl, 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. Examples of groups formed by replacing one or more hydrogen atoms of the exemplified groups with halogen atoms are also included.

[0015] In addition, groups in alicyclic hydrocarbons where -CH 2- is replaced by -O-, -CO-, -S-, or -SO 2- can be listed below. The bonding site can be set at any position. Substituents that can be present in the hydrocarbon groups of R4, R5, R6, R7, R8 and R9 include halogen atoms and cyano groups. As halogen atoms, the same bases as those described can be listed. The hydrocarbon group may have one or more substituents.

[0016] The hydrocarbon groups in A1, A2 and A3 can be listed as straight-chain or branched chain hydrocarbon groups (e.g., alkyldiyl), monocyclic or polycyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or combinations of two or more of these groups. Examples of linear alkyl diyl groups include: methylene, ethyl, 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. Branched alkyl diyl groups include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. The chain hydrocarbon group preferably has 1 to 18 carbon atoms, 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. As an alicyclic hydrocarbon group, it can be either monocyclic or polycyclic, as exemplified by the groups shown below. The bonding site can be set at any position. Specifically, examples include: cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, etc., which are cycloalkyl diyl groups, i.e., monocyclic alicyclic hydrocarbon groups and... Cycloalkyl groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, spirocyclohexane-1,2'-cyclopentyl, and spiroadamantane-2,3'-cyclopentyl, as well as polycyclic alicyclic hydrocarbon groups having cycloalkyl groups bonded to norbornane or adamantane by spiro bonds, respectively. The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16, even more preferably 3 to 12, and even more preferably 3 to 10. Examples of aromatic hydrocarbon groups include: phenyl, naphthyl, anthraceneyl, biphenyl, phenanthryl, and aryl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, and even more preferably 6-10.

[0017] Examples of groups formed by combining two or more groups include: groups formed by combining an alicyclic hydrocarbon group with an alkyl group, groups formed by combining an aromatic hydrocarbon group with an alkyl group, and groups formed by combining an alicyclic hydrocarbon group with an aromatic hydrocarbon group. In these combinations, two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups can also be combined. Furthermore, any one of these groups can be bonded to a benzene ring. Examples of groups formed by combining alicyclic hydrocarbon groups with alkyldiyl groups include: -divalent alicyclic hydrocarbon group-alkyldiyl-, -alkyldiyl-divalent alicyclic hydrocarbon group-alkyldiyl-, -alkyldiyl-divalent alicyclic hydrocarbon group-, etc. Examples of groups formed by combining aromatic hydrocarbon groups with alkyl diyl groups include: -divalent aromatic hydrocarbon group-alkyl diyl-, -alkyl diyl-divalent aromatic hydrocarbon group-alkyl diyl-, -alkyl diyl-divalent aromatic hydrocarbon group-, etc. Examples of bases formed by combining alicyclic hydrocarbon groups and aromatic hydrocarbon groups include: -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, etc.

[0018] In A1, A2, and A3, where the -CH2- group in the hydrocarbon group is replaced by -O-, -CO-, -S-, or -SO2-, the number of carbons before the substitution is set as the total number of carbons in the hydrocarbon group. Furthermore, the number of such substitutions can be one or more, but preferably one to three. Examples of hydrocarbon groups where the -CH 2- group is replaced by -O-, -CO-, -S-, or -SO 2- include: hydroxyl (a group in a methyl group where the -CH 2- is replaced by -O-), carboxyl (a group in an ethyl group where the -CH 2-CH 2- is replaced by -O-CO-), thiol (a group in a methyl group where the -CH 2- is replaced by -S-), alkoxy (a group in an alkyl group where the -CH 2- is replaced by -O-), alkoxycarbonyl (a group in an alkyl group where the -CH 2-CH 2- is replaced by -O-CO-), alkylcarbonyl (a group in an alkyl group where the -CH 2- is replaced by -CO-), alkylcarbonyloxy (a group in an alkyl group where the -CH 2-CH 2- is replaced by -CO-O-), and alkylthio (a group in an alkyl group where the -CH 2- is replaced by -O-, -CO-, -S-, or -SO 2-). 2-substituted with -S-), alkylsulfonyl (any position of -CH 2- substituted with -SO 2- in the alkyl group), oxy (any position of -CH 2- substituted with -O- in the methylene group), carbonyl (any position of -CH 2- substituted with -CO- in the methylene group), thio (any position of -CH 2- substituted with -S- in the methylene group), sulfonyl (any position of -CH 2- substituted with -SO 2- in the methylene group), alkadioxy (any position of -CH 2- substituted with -O- in the alkadiyl group), alkadioxycarbonyl (any position of -CH 2-CH 2- substituted with -O-CO- in the alkadiyl group), alkadicarbonyl (any position of -CH 2-CH substituted with -CO- in the alkadiyl group), alkadicarbonyloxy (any position of -CH 2-CH substituted with -CO- in the alkadiyl group). 2-substituted with -CO-O-, alkyldisulfonyl (a group in which -CH 2- at any position in an alkyldiyl group is substituted with -SO 2-), alkyldithio (a group in which -CH 2- at any position in an alkyldiyl group is substituted with -S-), cycloalkoxy, cycloalkylalkoxy, alkoxycarbonyloxy, aromatic hydrocarbon-carbonyloxy, and groups formed by combining two or more of these groups. Examples of alkoxy groups with 1 to 20 carbon atoms include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, etc. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl, alkylcarbonyl, and alkylcarbonyloxy groups represent groups formed by the bonding of a carbonyl or carbonyloxy group with the alkyl or alkoxy group. Examples of alkoxycarbonyl groups with 2 to 20 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. Examples of alkylcarbonyl groups with 2 to 20 carbon atoms include acetyl, propionic, and butyryl. Examples of alkylcarbonyloxy groups with 2 to 20 carbon atoms include acetylated, propionic, and butyryl. Preferably, the alkoxycarbonyl group has 2 to 11 carbon atoms, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 or 3. Preferably, the alkylcarbonyl group has 2 to 12 carbon atoms, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 or 3. Preferably, the alkylcarbonyl group has 2 to 11 carbon atoms, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 or 3. Examples of alkylthio groups with 1 to 20 carbon atoms include methylthio, ethylthio, propanethio, and butylthio. The number of carbon atoms in the alkylthio group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyl sulfonyl groups with 1 to 20 carbon atoms include methyl sulfonyl, ethyl sulfonyl, and propyl sulfonyl. The number of carbon atoms in the alkyl sulfonyl group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldioxy groups with 1 to 20 carbon atoms include methyleneoxy, ethyloxy, propanedioxy, butanedioxy, and pentanedioxy. The number of carbon atoms in an alkyldioxy group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldioxycarbonyl groups with 2 to 20 carbon atoms include: methyleneoxycarbonyl, ethyloxycarbonyl, propylenedioxycarbonyl, butyloxycarbonyl, etc. Examples of alkyldioxycarbonyl groups with 2 to 20 carbon atoms include: methylenecarbonyl, ethyloxycarbonyl, propylenedioxycarbonyl, butyloxycarbonyl, pentylcarbonyl, etc. Examples of alkyldioxycarbonyl groups with 2 to 20 carbon atoms include: methylenecarbonyloxy, ethyloxycarbonyloxy, propylenedioxycarbonyloxy, butyloxycarbonyl, etc. The number of carbon atoms in the alkyldioxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkyldioxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkyldicarbonyloxy 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 alkyldisulfonyl groups with 1 to 20 carbon atoms include methylenesulfonyl, ethylsulfonyl, and propylsulfonyl. The number of carbon atoms in the alkyldisulfonyl group is preferably 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of alkyldithio groups with 1 to 20 carbon atoms include methylene thio, ethyl thio, and propyl thio. Preferably, the number of carbon atoms in the alkyldithio group is 1 to 11, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 to 3. Examples of cycloalkoxy groups include those with 3 to 20 carbon atoms, such as cyclohexyloxy. Examples of cycloalkylalkoxy groups include those with 4 to 17 carbon atoms, such as cyclohexylmethoxy. Examples of alkoxycarbonyloxy groups include those with 2 to 16 carbon atoms, such as butoxycarbonyloxy. Examples of aromatic hydrocarbon-carbonyloxy groups include those with 7 to 20 carbon atoms, such as benzoyloxy.

[0019] Furthermore, groups in alicyclic hydrocarbon groups where -CH 2- is replaced by -O-, -CO-, -S-, or -SO 2- can be listed below. Additionally, groups in which -O- is replaced by -S- and -CO- is replaced by -SO 2- can also be listed below. The bonding site can be set at any position. Substituents that may be present in the hydrocarbon groups of A1, A2 and A3 can be the same as those listed among the substituents that may be present in the hydrocarbon groups of R4 to R9.

[0020] A1, A2 and A3 are preferably each independently a hydrocarbon group having 1 to 20 carbon atoms (the hydrocarbon group may have substituents, and one of the -CH2- contained in the hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2-). Preferably, A1 is ***-L 011-X 01-L 012-, A2 is ***-L 021-X 02-L 022-, and A3 is ***-L 031-X 03-L 032- (X 01, X 02, and X 03 independently represent -O-, -CO-, -S-, or -SO 2-, respectively. L 011, L 012, L 021, L 022, L 031, and L 032 independently represent single bonds or hydrocarbon groups with 1 to 18 carbon atoms. Specifically, the combined carbon number of L 011 and L 012 is 0 to 18, the combined carbon number of L 021 and L 022 is 0 to 18, and the combined carbon number of L 031 and L 032 is 0 to 18. *** indicates a combination with S... +The bonding site of the benzene ring to which it is bonded), preferably A1 is ***-X 01-L 01- or ***-L 01-X 01-, A2 is ***-X 02-L 02- or ***-L 02-X 02-, A3 is ***-X 03-L 03- or ***-L 03-X 03- (X 01, X 02, and X 03 independently represent -O-, -CO-, -S-, or -SO 2- respectively. L 01, L 02, and L 03 independently represent single bonds or hydrocarbon groups with 1 to 18 carbon atoms respectively. *** indicates the bonding site of the benzene ring to which S+ is bonded). A1, A2, and A3 are preferably without substituents other than those using -O-, -CO-, -S-, or -SO 2- substitution. As a hydrocarbon group with 1 to 18 carbons in L 011, L 012, L 021, L 022, L 031, L 032, L 01, L 02 and L 03 (this hydrocarbon group may have substituents, and the -CH 2- contained in this hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO 2-), groups with 1 to 18 carbons and the same as the groups listed in A 1, A 2 and A 3 can be listed. X01, X02 and X03 are preferably -O- or -S-, respectively, and more preferably -O-. L011, L012, L021, L022, L031, L032, L01, L02, and L03 are preferably single-bonded hydrocarbon groups with 1 to 12 carbon atoms (the -CH2- contained in the hydrocarbon group can be replaced by -O-, -CO-, -S-, or -SO2-), more preferably single-bonded chain hydrocarbon groups with 1 to 9 carbon atoms (the -CH2- contained in the chain hydrocarbon group can be replaced by -O-, -CO-, -S-, or -SO2-), further preferably single-bonded alkyldiyl groups with 1 to 6 carbon atoms (the -CH2- contained in the alkyldiyl group can be replaced by -O- or -CO-), and even more preferably single-bonded alkyldiyl groups with 1 to 4 carbon atoms (the -CH2- contained in the alkyldiyl group can be replaced by -O- or -CO-). 2- (which can be replaced by -O- or -CO-), and more preferably a single bond, an alkyl diel with 1 to 3 carbon atoms (the -CH 2- contained in this alkyl diel can be replaced by -O- or -CO-). Preferably, it is a single bond, methylene, ethane-1,1-diyl, propane-1,1-diyl, propane-2,2-diyl, carbonyl, carbonyloxy, carbonyloxymethylene, ethyloxy, methylene carbonyloxymethylene, ethyloxycarbonyl, and more preferably a single bond, methylene, or carbonyl. The bonding positions of A1, A2, and A3 on the benzene ring bonded to S+ can be any of ortho, meta, or para relative to the bonding position of S+. Preferably, they are bonded at the para or meta position relative to the bonding position of S+. More specifically, when m1, m2, and m3 are 1, A1, A2, and A3 are preferably bonded independently at the para or meta position relative to the bonding position of S+, more preferably at the para position. When m1, m2, and m3 are 2, A1, A2, and A3 are preferably bonded independently at the bonding positions of S+, one at the ortho or meta position, one at the ortho or meta position, more preferably both at the meta position. When m1, m2, and m3 are 3, A1, A2, and A3 are preferably independently positioned relative to S+, with two bonds in adjacent or intermediate positions and one bond in opposite or intermediate positions; more preferably, two bonds are in intermediate positions and one bond is in opposite positions. When m1, m2, and m3 are 4, A1, A2, and A3 are preferably independently positioned relative to S+, with two bonds in adjacent or intermediate positions and two bonds in opposite or intermediate positions; more preferably, two bonds are in adjacent positions and two bonds are in intermediate positions. 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 or 1, 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 or 1, 2, and even more preferably 0 or 1. The m4 value is preferably 0, 1, 2, 3 or 5, and even more preferably 0, 1, 2 or 5. m5 is preferably 0 or 1, and even better is 0. m6 is preferably 0 or 1, and even better is 0. m7 is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and even better if it is 0. 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, when m1 is 2 or more, or when m2 and m3 are 1 or more, the bases within the parentheses can be the same or different. That is, when there are multiple X1 to X3, or multiple R4 to R6, these bases can be the same or different. R4, R5 and R6 are preferably independently halogen atoms, fluorinated alkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 6 carbon atoms (where -CH2- can be substituted by -O- or -CO-), more preferably halogen atoms, fluorinated alkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 4 carbon atoms (where -CH2- can be substituted by -O- or -CO-), further preferably fluorine atoms, iodine atoms, perfluoroalkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 4 carbon atoms (where -CH2- can be substituted by -O- or -CO-), and even more preferably fluorine atoms, iodine atoms or trifluoromethyl groups. The bonding positions of R4, R5, and R6 on the benzene ring are independently relative to the bonding positions of A1, A2, and A3, and can be any of the ortho, meta, or para positions. When m4, m5, and m6 are 1, R4, R5, and R6 are preferably independently bonded to the para or meta positions, more preferably to the para position. When m4, m5, and m6 are 2, R4, R5, and R6 are preferably independently bonded to the meta positions, one to the ortho or meta position and one to the para or meta position, more preferably both to the meta position. When m4, m5, and m6 are 3, R4, R5, and R6 are preferably independently positioned relative to the bond nodes of A1, A2, and A3, respectively, with two bonds in adjacent or intermediate positions and one bond node in opposite or intermediate positions; more preferably, two bonds are in intermediate positions and one bond node is in opposite positions. When m4, m5, and m6 are 4, R4, R5, and R6 are preferably independently positioned relative to the bond nodes of A1, A2, and A3, respectively, with two bonds in adjacent or intermediate positions and two bonds in opposite or intermediate positions; more preferably, two bonds are in intermediate positions, one bond node is adjacent, and one bond node is in opposite positions. R7, R8 and R9 are preferably independently halogen atoms, fluorinated alkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 6 carbon atoms (where -CH2- can be substituted by -O- or -CO-), more preferably halogen atoms, fluorinated alkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 4 carbon atoms (where -CH2- can be substituted by -O- or -CO-), further preferably fluorine atoms, iodine atoms, perfluoroalkyl groups having 1 to 4 carbon atoms, or alkyl groups having 1 to 4 carbon atoms (where -CH2- can be substituted by -O- or -CO-), and even more preferably fluorine atoms, iodine atoms or trifluoromethyl groups. The bonding positions of R7, R8, and R9 on the benzene ring are independently relative to the bonding position of S+, and can be any of ortho, meta, or para. When m7, m8, and m9 are 1, R7, R8, and R9 are preferably independently bonded relative to S+, at the para or meta position, more preferably at the para position. When m7, m8, and m9 are 2, R7, R8, and R9 are preferably independently bonded relative to S+, one at the ortho or meta position, one at the para or meta position, more preferably one at the meta position and one at the para position. When m7, m8, and m9 are 3, R7, R8, and R9 are preferably independently positioned relative to S+, with two bonds in adjacent or intermediate positions and one bond in opposite or intermediate positions; more preferably, two bonds are in intermediate positions and one bond is in opposite positions. When m7, m8, and m9 are 4, R7, R8, and R9 are preferably independently positioned relative to S+, with two bonds in adjacent or intermediate positions and two bonds in opposite or intermediate positions; more preferably, two bonds are in intermediate positions, one bond is in adjacent positions, and one bond is in opposite positions.

[0021] As the cation (I) represented by formula (IC), cations represented by formula (IC-1) can be listed (hereinafter sometimes referred to as "cation (IC-1)"). In formula (IC-1), The symbols R4, R5, R6, R7, R8, R9, m1, m2, m3, m4, m5, m6, m7, m8, m9, L01, L02, L03, X01, X02, and X03 represent the same meaning as described above.

[0022] X 01, X 02 and X 03 are preferably -O-. The bonding positions of X01, X02, and X03 on the benzene ring are the same as the bonding positions of A1, A2, and A3 on the benzene ring, respectively.

[0023] The cations that can be used as salts (I) include those represented by formulas (Ic-1) to (Ic-44).

[0024]

[0025]

[0026]

[0027]

[0028]

[0029] [Anion (I)] The anion (I) of the salt represented by formula (I) is the same as the anion represented by formula (IA). [In equation (IA), all symbols have the same meaning as in equation (I)]

[0030] In formula (IA), the hydrocarbon group represented by X0 can include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyldiyl, alkenyl, and alkynyl, as well as alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups formed by combining these. The -CH2- contained in the aliphatic hydrocarbon group can be replaced by -O-, -S-, -CO-, or -SO2-. Examples of straight-chain alkyldiyl groups include: methylene, ethyl, 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. Branched alkyl diyl groups include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. Examples of alkened diyl groups include: ethylene diyl, propylene diyl, isopropylene diyl, butene diyl, isobutene diyl, tributene diyl, pentene diyl, hexene diyl, hepten diyl, octyne diyl, isooctyn diyl, and nonene diyl. Examples of alkynyl groups include: acetylenic diyl, propynic diyl, isopropynic diyl, butynic diyl, isobutynic diyl, tributynic diyl, pentylenic diyl, hexynic diyl, octylenic diyl, nonynic diyl, etc. Examples of chain hydrocarbon groups in which -CH 2- is replaced with -O-, -S-, -CO-, or -SO 2- include: hydroxyl (a group in methyl groups in which -CH 2- is replaced with -O-), carboxyl (a group in ethyl groups in which -CH 2-CH 2- is replaced with -O-CO-), thiol (a group in methyl groups in which -CH 2- is replaced with -S-), alkoxy (a group in alkyl groups in which -CH 2- is replaced with -O-), alkoxycarbonyl (a group in alkyl groups in which -CH 2-CH 2- is replaced with -O-CO-), alkylcarbonyl (a group in alkyl groups in which -CH 2- is replaced with -CO-), alkylcarbonyloxy (a group in alkyl groups in which -CH 2-CH 2- is replaced with -CO-O-), and alkylthio (a group in alkyl groups in which -CH 2- is replaced with -S-). Examples of groups identical to those described above include alkoxy, alkoxycarbonyl, thioether, alkylcarbonyl, alkylcarbonyloxy, and alkylthio. Furthermore, regarding the substitution in the alkenyl and ynyl groups, it is sufficient that, in the examples of substitution in the alkyl group, a carbon-carbon double bond or a carbon-carbon triple bond is contained at any position.

[0031] As an alicyclic hydrocarbon group, it can be any of monocyclic, polycyclic, or spirocyclic. As a divalent alicyclic hydrocarbon group, examples include the groups shown below. The bonding site can be set at any position. Specifically, examples of monocyclic divalent alicyclic hydrocarbon groups include: cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclohexene-3,6-diyl, and cyclooctane-1,5-diyl. Examples of polycyclic divalent alicyclic hydrocarbon groups include: 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. As a group in an alicyclic hydrocarbon group or in which -CH 2- is replaced by -O-, -S-, -CO-, or -SO 2-, it can form ether rings, ketone rings, lactone rings, sulfonyl lactone rings, acetal rings, etc. Specifically, the following groups can be listed. The bonding site can be set at any position. The -CH 2- group contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO. The basis of 2- is preferably the basis represented by equations (y1) to (y71), more preferably the basis represented by any one of equations (y1) to (y20), (y26), (y27), (y30), (y31), (y39) to (y71), and even more preferably the basis represented by equations (y3), (y4), (y9), (y11), (y14), (y15), (y16), (y20), (y26), (y27), (y30), (y31), (y39), (y40), (y42), (y43), (y49) to (y58), (y62) to (y71). The alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24, even more preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12.

[0032] Examples of aromatic hydrocarbon groups include: pentylenyl, pentylenyl, pentylenyl anthraceneyl, pentylenyl biphenyl, and pentylenyl phenanthrene. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, and even more preferably 6-10. Examples of hydrocarbon groups formed by combining two or more hydrocarbon groups include those formed by combining an alkyl diene with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, such as: -alicyclic hydrocarbon group-alkyl diene-, -alkyl diene-alicyclic hydrocarbon group-, -alkyl diene-alicyclic hydrocarbon group-alkyl diene-, -alkyl diene-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkyl diene-, etc. When the -CH 2- in the hydrocarbon group represented by X 0 is replaced with -O-, -S-, -CO-, or -SO 2-, the number of carbons before the substitution is set as the total number of carbons in the hydrocarbon group. Additionally, when a substituent is bonded to the hydrocarbon group represented by X 0, the number of carbons before the substitution is set as the total number of carbons in the hydrocarbon group.

[0033] The hydrocarbon group represented by X 0 may have one or more substituents. Examples of substituents include: hydroxyl groups, halogen atoms, cyano groups, alkyl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, alkoxy carbonyl groups with 2 to 13 carbon atoms, alkyl carbonyl groups with 2 to 13 carbon atoms, alkyl carbonyloxy groups with 2 to 13 carbon atoms, alicyclic hydrocarbon groups with 3 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 10 carbon atoms, or groups formed by combining these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups having 1 to 12 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, hexyl, octyl, nonyl, etc. Examples of alkoxy groups with 1 to 12 carbon atoms include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc. Alkoxycarbonyl with 2 to 13 carbon atoms, alkylcarbonyl with 2 to 13 carbon atoms, and alkylcarbonyloxy with 2 to 13 carbon atoms represent groups formed by the bonding of a carbonyl group or carbonyloxy group with the alkyl or alkoxy group. Examples of alkoxy carbonyl groups with 2 to 13 carbon atoms include: methoxy carbonyl, ethoxy carbonyl, butoxy carbonyl, etc. Examples of alkyl carbonyl groups with 2 to 13 carbon atoms include: acetyl, propionic, and butoxy, etc. Examples of alkyl carbonyl groups with 2 to 13 carbon atoms include: acetyoxy, propionic, butoxy, etc. Examples of alicyclic hydrocarbon groups with 3 to 12 carbon atoms are shown below. ** indicates the bonding position with X0. Aryl groups that are 6 to 10 carbon atoms can be exemplified by phenyl, naphthyl, and other aryl groups. Examples of groups formed by combination include: groups formed by combining a hydroxyl group with an alkyl group having 1 to 12 carbon atoms, groups formed by combining an alkyl group having 1 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms, and groups formed by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of radicals formed by combining a hydroxyl group with an alkyl group having 1 to 12 carbon atoms include hydroxymethyl, hydroxyethyl, and other hydroxyalkyl groups having 1 to 12 carbon atoms. Examples of groups formed by combining an alkyl group having 1 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as benzyl, and alkylaryl groups having 7 to 22 carbon atoms such as tolyl and xylyl. Examples of groups formed by combining an alicyclic hydrocarbon group with 3 to 12 carbon atoms with an aromatic hydrocarbon group with 6 to 10 carbon atoms include cyclohexylphenyl.

[0034] The hydrocarbon group represented by X0 is preferably an aliphatic hydrocarbon group with 1 to 72 carbon atoms that may have substituents (the -CH2- in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group with 6 to 36 carbon atoms that may have substituents. More preferably, it is a group composed of an alicyclic hydrocarbon group having 3 to 36 carbon atoms that may have substituents (wherein -CH 2- in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2-), a group composed of an alicyclic hydrocarbon group having 3 to 36 carbon atoms that may have substituents and a chain hydrocarbon group having 1 to 18 carbon atoms that may have substituents (where -CH 2- in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO 2-, and -CH 2- in the chain hydrocarbon group may be replaced by -O- or -CO-), an aromatic hydrocarbon group having 6 to 36 carbon atoms that may have substituents, or a group composed of an aromatic hydrocarbon group having 6 to 36 carbon atoms that may have substituents and a chain hydrocarbon group having 1 to 18 carbon atoms that may have substituents. Preferably, it is an alicyclic hydrocarbon group (where -CH 2- can be replaced by -O-, -S-, -CO-, or -SO 2-, and the alicyclic hydrocarbon group may have a hydroxyl or fluorine atom. * indicates the bonding position with the carbon atom of -COO-), an alicyclic hydrocarbon group-chain hydrocarbon group (where -CH 2- can be replaced by -O-, -S-, -CO-, or -SO 2-, and the -CH 2- can be replaced by -O- or -CO-, and both the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine or hydroxyl atom. * indicates the bonding position with the carbon atom of -COO-), an alicyclic hydrocarbon group-alicyclic hydrocarbon group (where -CH 2- can be replaced by -O- or -CO-, and the -CH 2- can be replaced by -O-, -S-, -CO-, or -SO 2-). 2-, The chain hydrocarbon group and the alicyclic hydrocarbon group may have fluorine atoms or hydroxyl groups. * indicates the bonding position with the carbon atom of -COO-), *-Aromatic hydrocarbon group (the aromatic hydrocarbon group may have fluorine atoms or hydroxyl groups. * indicates the bonding position with the carbon atom of -COO-), *-Chain hydrocarbon group-aromatic hydrocarbon group (the -CH 2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, the chain hydrocarbon group and the aromatic hydrocarbon group may have fluorine atoms or hydroxyl groups. * indicates the bonding position with the carbon atom of -COO-), More preferably, it is a monocyclic alicyclic hydrocarbon group (the -CH 2- contained in the alicyclic hydrocarbon group can be replaced with -O-, -S-, -CO- or -SO 2-), a polycyclic alicyclic hydrocarbon group (the -CH 2- contained in the polycyclic alicyclic hydrocarbon group can be replaced with -O-, -S-, -CO- or -SO 2-, the polycyclic alicyclic hydrocarbon group can also be spirocyclic, and the polycyclic alicyclic hydrocarbon group can have hydroxyl or fluorine atoms. * indicates the bonding position with the carbon atom of -COO-), a polycyclic alicyclic hydrocarbon group-chain hydrocarbon group (the -CH 2- contained in the polycyclic alicyclic hydrocarbon group can be replaced with -O-, -S-, -CO- or -SO 2-, the -CH 2- contained in the chain hydrocarbon group... 2- can be replaced with -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group can have fluorine atoms or hydroxyl groups. * indicates the bonding position with the carbon atom of -COO-), *-chain hydrocarbon group-polycyclic alicyclic hydrocarbon group (the -CH 2- contained in the chain hydrocarbon group can be replaced with -O- or -CO-, the -CH 2- contained in the polycyclic alicyclic hydrocarbon group can be replaced with -O-, -S-, -CO- or -SO 2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group can have fluorine atoms or hydroxyl groups. * indicates the bonding position with the carbon atom of -COO-) or an aromatic hydrocarbon group that can have fluorine atoms or hydroxyl groups, In the aforementioned group, the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24, further preferably 3 to 18, even more preferably 3 to 16, and even more preferably 3 to 12. The chain hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12, even more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. The aromatic hydrocarbon group preferably has 6 to 36 carbon atoms, more preferably 6 to 24, even more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. In the aforementioned base, the number of carbon atoms in the chain hydrocarbon group is preferably 1 to 6. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkanediyl group with 5 or 6 carbon atoms (the -CH 2- contained in the cycloalkanediyl group can be replaced by -O- or -CO-, and the cycloalkanediyl group can also be an acetal ring). The polycyclic alicyclic hydrocarbon group is preferably adamantyl or norbornenediyl, adamantyl and a cycloalkanediyl group with 5 or 6 carbon atoms bonded to the adamantyl by a helical bond (the -CH 2- contained in the adamantyl, norbornenediyl and cycloalkanediyl can be replaced by -O- or -CO-, the -CH 2-CH 2- contained in the adamantyl and norbornenediyl can be replaced by -O-CO-, and the cycloalkanediyl group can also be an acetal ring). The aromatic hydrocarbon group is preferably phenyl. In the aforementioned base, the chain hydrocarbon group preferably has a fluorine atom. X0 is preferably a group consisting of an alkyldiyl group having 1 to 6 carbon atoms, a cycloalkyldiyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group, a phenyl group, an alkyldiyl group having 1 to 6 carbon atoms bonded to COO-, and a cycloalkyldiyl group having 5 or 6 carbon atoms bonded to the alkyldiyl group, an adamantanediyl group, a norbornanediyl group, or a phenyl group, or a cycloalkyldiyl group having 5 or 6 carbon atoms bonded to the adamantanediyl group by a helical bond. The -CH2- group contained in the alkyldiyl group, the cycloalkyldiyl group, the adamantanediyl group, and the norbornanediyl group may be substituted with -O- or -CO-. The -CH2-CH group contained in the alkyldiyl group, the adamantanediyl group, and the norbornanediyl group may be substituted with -O- or -CO-. 2- can be replaced with -O-CO- or -CO-O-, and one or more hydrogen atoms contained in the alkyldiyl, cycloalkyldiyl, adamantanediyl, norbornenediyl, or phenyl can be replaced with fluorine atoms, perfluoroalkyl groups having 1 to 4 carbon atoms, hydroxyl groups, or methylhydroxyl groups. As X0, preferably it is an adamantanediyl, hydroxyadamantanediyl, a group consisting of an alkyldiyl group with 1 to 6 carbon atoms bonded to COO- and an adamantanediyl group (the -CH2- contained in the alkyldiyl group can be replaced with -O- or -CO-), an enylphenyl group, or an enylphenyl group having a hydroxyl group.

[0035] The halogen atoms in R bb1 may be the same as those listed in R 4 to R 9. Provided the upper limit on the number of carbon atoms allows, the alkyl groups in R bb1 that may have halogen atoms may be the same as those listed in the examples of R 4 to R 9, including both alkyl and haloalkyl groups. R bb1 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. When X 10 is a basis represented by *-Ax-Ph-Ay-**, it is preferred to be a linking basis represented by the following formula (X10). In formula (X10), Ax represents the type of bond that the carbon atom bonded to R10 is selected from the group consisting of single bond, ether bond, ester bond and carbonate bond. Ay represents the type of bond that is bonded to L 10, and is selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. If either Ax or Ay is a single bond, the other is preferably selected from the group consisting of ether bonds, ester bonds and carbonate bonds. Rx represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Preferably, it is a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, or an ethyl group. mx represents any integer from 0 to 4, preferably 0, 1, or 2. When mx is an integer greater than 2, multiple Rx values ​​can be the same or different. Compared to Ax, the bonding position of Ay in the phenyl group is preferably meta or para, and more preferably para. As for X 10, examples include the bases represented by the following formulas (X 1-1), (X 1-2') to (X 1-7'), and (X 1-8). * indicates the bonding site of the carbon atom bonded to -R 10. ** indicates the bonding site of L 10. As specific examples of the bases represented by equations (X 1-2') to (X 1-7'), the following bases can be listed. Wherein, X10 is preferably a basis represented by equations (X1-1) to (X1-7), more preferably a basis represented by equations (X1-1), (X1-3), (X1-4) or (X1-5), and even more preferably a basis represented by equation (X1-1), equation (X1-4) or equation (X1-5).

[0036] Examples of divalent hydrocarbon groups with 1 to 36 carbon atoms in L 10 include: divalent aliphatic hydrocarbon groups (alkyl, alkenyl, alkynyl, etc., divalent chain hydrocarbon groups and divalent alicyclic hydrocarbon groups), divalent aromatic hydrocarbon groups, etc., or divalent hydrocarbon groups formed by combining two or more of these groups.

[0037] Examples of straight-chain alkyldiyl groups include: methylene, ethyl, 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. Branched alkyl diyl groups include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. Examples of alkened diyl groups include: ethylene diyl, propylene diyl, isopropylene diyl, butene diyl, isobutene diyl, tributene diyl, pentene diyl, hexene diyl, hepten diyl, octyne diyl, isooctyn diyl, and nonene diyl. Examples of alkynyl groups include: acetylenic diyl, propynic diyl, isopropynic diyl, butynic diyl, isobutynic diyl, tributynic diyl, pentylenic diyl, hexynic diyl, octylenic diyl, nonynic diyl, etc. The chain hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 9, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. As a divalent alicyclic hydrocarbon group, it can be any of monocyclic, polycyclic, or spirocyclic. Examples of divalent alicyclic hydrocarbon groups include those represented below. The bonding site can be set at any position. Specifically, examples of monocyclic divalent alicyclic hydrocarbon groups include: cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclohexene-3,6-diyl, and cyclooctane-1,5-diyl. Examples of polycyclic divalent alicyclic hydrocarbon groups include: 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: pentanylphenyl, pentanylnaphthyl, pentanylanthryl, pentanylbiphenyl, and pentanylphenanthryl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, and even more preferably 6-10. Examples of hydrocarbon groups formed by combining two or more hydrocarbon groups include those formed by combining an alkyl diene with an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, such as: -alicyclic hydrocarbon group-alkyl diene-, -alkyl diene-alicyclic hydrocarbon group-, -alkyl diene-alicyclic hydrocarbon group-alkyl diene-, -alkyl diene-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkyl diene-, etc.

[0038] In L 10, the -CH 2- in the hydrocarbon groups with carbon numbers 1 to 36 can be substituted with -O-, -S-, -CO-, or -SO 2-. In the case where the hydrocarbon group with carbon number 1 to 36 in L 10 has a substituent or where the -CH 2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO 2-, the carbon number before the substitution is set as the carbon number of the hydrocarbon group. Examples of hydrocarbon groups where the -CH 2- group is replaced by -O-, -S-, -SO 2-, or -CO- include: hydroxyl (a group in a methyl group where the -CH 2- is replaced by -O-), carboxyl (a group in an ethyl group where the -CH 2-CH 2- is replaced by -O-CO-), thiol (a group in a methyl group where the -CH 2- is replaced by -S-), alkoxy (a group in an alkyl group where the -CH 2- is replaced by -O-), alkoxycarbonyl (a group in an alkyl group where the -CH 2-CH 2- is replaced by -O-CO-), alkylcarbonyl (a group in an alkyl group where the -CH 2- is replaced by -CO-), alkylcarbonyloxy (a group in an alkyl group where the -CH 2-CH 2- is replaced by -CO-O-), and alkyldioxy (a group in an alkyldi group where the -CH 2- is replaced by -O-, -S-, -SO 2-, or -CO-). 2-substituted with -O-, alkadioxycarbonyl (any position of -CH2-CH2- in the alkadiyl group is substituted with -O-CO-), alkadioxycarbonyl (any position of -CH2- in the alkadiyl group is substituted with -CO-), alkadioxycarbonyl (any position of -CH2-CH2- in the alkadiyl group is substituted with -CO-O-), alkathio (any position of -CH2- in the alkyl group is substituted with -S-), alkylsulfonyl (any position of -CH2- in the alkyl group is substituted with -SO2-), cycloalkoxy, cycloalkylalkoxy, alkoxycarbonyloxy, aromatic hydrocarbon-carbonyloxy, and groups formed by combining two or more of these groups. Examples of alkoxy groups with 1 to 17 carbon atoms include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, etc. 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, alkylcarbonyl, and alkylcarbonyloxy groups represent groups formed by the bonding of a carbonyl or carbonyloxy group with the alkyl or alkoxy group. Examples of alkoxycarbonyl groups with 2 to 17 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl. Examples of alkylcarbonyl groups with 2 to 18 carbon atoms include acetyl, propionic, and butyryl. Examples of alkylcarbonyloxy groups with 2 to 17 carbon atoms include acetylated, propionic, and butyryl. The number of carbon atoms in the alkoxycarbonyl, alkylcarbonyl, and alkylcarbonyloxy groups is preferably 2 to 11, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2 to 3. Alkyloxy groups can be listed as having 1 to 17 carbon atoms, such as methyleneoxy, ethyloxy, propyleneoxy, styryloxy, pentyloxy, etc. Examples of alkyldioxycarbonyl groups with 2 to 17 carbon atoms include methyleneoxycarbonyl, ethyloxycarbonyl, propanedioxycarbonyl, and butanedioxycarbonyl. Examples of alkyldioxycarbonyl groups with 2 to 18 carbon atoms include methylenecarbonyl, propanedioxycarbonyl, propanedioxycarbonyl, butanedioxycarbonyl, and pentanedioxycarbonyl. Examples of alkyldioxycarbonyl groups with 2 to 17 carbon atoms include methylenecarbonyloxy, propanedioxycarbonyloxy, propanedioxycarbonyloxy, and butanedioxycarbonyloxy. The carbon number of the alkyldioxycarbonyl, alkyldioxy, and alkyldioxycarbonyl groups 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 with 1 to 17 carbon atoms include methylthio, ethylthio, and propylthio. 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 alkyl sulfonyl groups with 1 to 17 carbon atoms include methyl sulfonyl, ethyl sulfonyl, and propyl sulfonyl. The number of carbon atoms in the alkyl sulfonyl 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 those with 3 to 17 carbon atoms, such as cyclohexyloxy. Examples of cycloalkylalkoxy groups include those with 4 to 17 carbon atoms, such as cyclohexylmethoxy. Examples of alkoxycarbonyloxy groups include those with 2 to 16 carbon atoms, such as butoxycarbonyloxy. The carbon atoms of cycloalkoxy and cycloalkylalkoxy groups are preferably 3 to 11, more preferably 3 to 6. The carbon atoms of alkoxycarbonyloxy groups are preferably 2 to 11, more preferably 2 to 6, further preferably 2 to 4, and further preferably 2 to 3. Examples of aromatic hydrocarbon-carbonyloxy groups are those with 7 to 17 carbon atoms, such as benzoyloxy. Furthermore, groups in alicyclic hydrocarbon groups where the -CH 2- group is replaced by -O-, -S-, -CO-, or -SO 2- can be listed below. The -O- or -CO- positions in the groups listed below can also be replaced by -S- or -SO 2-, respectively. The bonding site can be set at any position.

[0039] Substituents that can exist in the hydrocarbon group of L 10 include halogen atoms, cyano groups, etc. By substituting the -CH 2- group in the hydrocarbon group of L 10 with a -O- or -CO- group, L 10 can substantially have substituents such as hydroxyl, carboxyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, and alkylcarbonyloxy. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The divalent hydrocarbon groups with carbon numbers 1 to 36 in L 10 may have one or more substituents.

[0040] L10 is preferably a single bond, an alkyldiyl group with 1 to 4 carbons (wherein the -CH2- contained in the alkyldiyl group can be replaced with -O- or -CO-), an alicyclic hydrocarbon group with 3 to 18 carbons (wherein the -CH2- contained in the alicyclic hydrocarbon group can be replaced with -O-, -S-, -SO2- or -CO-), an aromatic hydrocarbon group with 6 to 18 carbons that may have substituents, a group composed of an alkyldiyl group with 1 to 4 carbons and an alicyclic hydrocarbon group with 3 to 18 carbons (wherein the -CH2- contained in the alkyldiyl group can be replaced with -O- or -CO-, and the -CH2- contained in the alicyclic hydrocarbon group can be replaced with -O-, -S-, -SO2- or -CO-), or a group composed of an alkyldiyl group with 1 to 4 carbons and an aromatic hydrocarbon group with 6 to 18 carbons that may have substituents (wherein the -CH2- contained in the alkyldiyl group can be replaced with -O-, -S-, -SO2- or -CO-). 2- (which may be replaced by -O- or -CO-), preferably a single bond, an alkyldiyl group having 1 to 4 carbons (wherein the -CH 2- contained in the alkyldiyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbons (wherein the -CH 2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), a phenyl group having substituents, a group composed of an alkyldiyl group having 1 to 4 carbons and an alicyclic hydrocarbon group having 3 to 18 carbons (wherein the -CH 2- contained in the alkyldiyl group may be replaced by -O- or -CO-, and the -CH 2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group composed of an alkyldiyl group having 1 to 4 carbons and a phenyl group having substituents (wherein the -CH 2- contained in the alkyldiyl group may be replaced by -O- or -CO-), or a group composed of an alkyldiyl group having 1 to 4 carbons and a phenyl group having substituents (wherein the -CH 2- contained in the alkyldiyl group may be replaced by -O- or -CO-). 2- can be replaced with -O- or -CO-), and preferably a single bond or an alkyl diester with 1 to 4 carbon atoms (wherein the -CH 2- contained in the alkyl diester can be replaced with -O- or -CO-).

[0041] Examples of anions (I) include the following.

[0042] Specific examples of carboxylate (I) can be listed as salts formed by any combination of the cation and anion. Specific examples of salt (I) are shown in the table below. In the table below, each symbol represents a symbol accompanying the structure representing the anion and cation, and "~" indicates that salt (I) corresponds to anion (I). For example, carboxylate (I-1) represents a salt containing the anion represented by formula (Ia-1) and the cation represented by formula (Ic-1), salt (I-2) represents a salt containing the anion represented by formula (Ia-2) and the cation represented by formula (Ic-1), and salt (I-28) represents a salt containing the anion represented by formula (Ia-1) and the cation represented by formula (Ic-2). [Table 1] Carboxylate (I) Anion (I) Cation (I) (I-1)~(I-27) (Ia-1)~(Ia-27) (Ic-1) (I-28)~(I-54) (Ia-1)~(Ia-27) (Ic-2) (I-55)~(I-81) (Ia-1)~(Ia-27) (Ic-3) (I-82)~(I-108) (Ia-1)~(Ia-27) (Ic-4) (I-109)~(I-135) (Ia-1)~(Ia-27) (Ic-5) (I-136)~(I-162) (Ia-1)~(Ia-27) (Ic-6) (I-163)~(I-189) (Ia-1)~(Ia-27) (Ic-7) (I-190)~(I-216) (Ia-1)~(Ia-27) (Ic-8) (I-217)~(I-243) (I-a-1)~(I-a-27) (I-c-9) (I-244)~(I-270) (I-a-1)~(I-a-27) (I-c-10) (I-271)~(I-297) (I-a-1)~(I-a-27) (I-c-11) (I-298)~(I-324) (I-a-1)~(I-a-27) (I-c-12) (I-325)~(I-351) (I-a-1)~(I-a-27) (I-c-13) (I-352)~(I-378) (I-a-1)~(I-a-27) (I-c-14) (I-379)~(I-405) (I-a-1)~(I-a-27) (I-c-15) (I-406)~(I-432) (I-a-1)~(I-a-27) (I-c-16) (I-433)~(I-459) (I-a-1)~(I-a-27) (I-c-17) (I-460)~(I-486) (I-a-1)~(I-a-27) (I-c-18) (I-487)~(I-513) (I-a-1)~(I-a-27) (I-c-19) (I-514)~(I-540) (I-a-1)~(I-a-27) (I-c-20) (I-541)~(I-567) (I-a-1)~(I-a-27) (I-c-21) (I-568)~(I-594) (I-a-1)~(I-a-27) (I-c-22) (I-595)~(I-621) (I-a-1)~(I-a-27) (I-c-23) (I-622)~(I-648) (I-a-1)~(I-a-27) (I-c-24) (I-649)~(I-675) (I-a-1)~(I-a-27) (I-c-25) (I-676)~(I-702) (I-a-1)~(I-a-27) (I-c-26) (I-703)~(I-729) (I-a-1)~(I-a-27) (I-c-27) (I-730)~(I-756) (I-a-1)~(I-a-27) (I-c-28) (I-757)~(I-783) (I-a-1)~(I-a-27) (I-c-29) (I-784)~(I-810) (I-a-1)~(I-a-27) (I-c-30) (I-811)~(I-837) (I-a-1)~(I-a-27) (I-c-31) (I-838)~(I-864) (I-a-1)~(I-a-27) (I-c-32) (I-865)~(I-891) (I-a-1)~(I-a-27) (I-c-33) (I-892)~(I-918) (I-a-1)~(I-a-27) (I-c-34) (I-919)~(I-945) (I-a-1)~(I-a-27) (I-c-35) (I-946)~(I-972) (I-a-1)~(I-a-27) (I-c-36) (I-973)~(I-999) (I-a-1)~(I-a-27) (I-c-37) (I-1000)~(I-1026) (I-a-1)~(I-a-27) (I-c-38) (I-1027)~(I-1053) (I-a-1)~(I-a-27) (I-c-39) (I-1054)~(I-1080) (I-a-1)~(I-a-27) (I-c-40) (I-1081)~(I-1107) (I-a-1)~(I-a-27) (I-c-41) (I-1108)~(I-1134) (I-a-1)~(I-a-27) (I-c-42) (I-1135)~(I-1161) (I-a-1)~(I-a-27) (I-c-43) (I-1162)~(I-1188) (I-a-1)~(I-a-27) (I-c-44) (I-1189)~(I-1215) (I-a-1)~(I-a-27) (I-c-45) (I-1216)~(I-1242) (I-a-1)~(I-a-27) (I-c-46) (I-1243)~(I-1269) (I-a-1)~(I-a-27) (I-c-47) (I-1270)~(I-1296) (I-a-1)~(I-a-27) (I-c-48) (I-1297)~(I-1323) (I-a-1)~(I-a-27) (I-c-49) (I-1324)~(I-1350) (I-a-1)~(I-a-27) (I-c-50) (I-1351)~(I-1377) (I-a-1)~(I-a-27) (I-c-51) (I-1378)~(I-1404) (I-a-1)~(I-a-27) (I-c-52) (I-1405)~(I-1431) (I-a-1)~(I-a-27) (I-c-53) (I-1432)~(I-1458) (I-a-1)~(I-a-27) (I-c-54) (I-1459)~(I-1485) (I-a-1)~(I-a-27) (I-c-55) (I-1486)~(I-1512) (I-a-1)~(I-a-27) (I-c-56) (I-1513)~(I-1539) (I-a-1)~(I-a-27) (I-c-57) (I-1540)~(I-1566) (I-a-1)~(I-a-27) (I-c-58) (I-1567)~(I-1593) (I-a-1)~(I-a-27) (I-c-59) (I-1594)~(I-1620) (I-a-1)~(I-a-27) (I-c-60) (I-1621)~(I-1647) (I-a-1)~(I-a-27) (I-c-61) (I-1648)~(I-1674) (I-a-1)~(I-a-27) (I-c-62) (I-1675)~(I-1701) (I-a-1)~(I-a-27) (I-c-63) (I-1702)~(I-1728) (I-a-1)~(I-a-27) (I-c-64) (I-1729)~(I-1755) (I-a-1)~(I-a-27) (I-c-65) (I-1756)~(I-1782) (I-a-1)~(I-a-27) (I-c-66) (I-1783)~(I-1809) (I-a-1)~(I-a-27) (I-c-67) (I-1810)~(I-1836) (I-a-1)~(I-a-27) (I-c-68) (I-1837)~(I-1863) (I-a-1)~(I-a-27) (I-c-69) (I-1864)~(I-1890) (I-a-1)~(I-a-27) (I-c-70) (I-1891)~(I-1917) (I-a-1)~(I-a-27) (I-c-71) (I-1918)~(I-1944) (I-a-1)~(I-a-27) (I-c-72) (I-1945)~(I-1971) (I-a-1)~(I-a-27) (I-c-73) (I-1972)~(I-1998) (I-a-1)~(I-a-27) (I-c-74) (I-1999)~(I-2025) (I-a-1)~(I-a-27) (I-c-75) (I-2026)~(I-2052) (I-a-1)~(I-a-27) (I-c-76) (I-2053)~(I-2079) (I-a-1)~(I-a-27) (I-c-77) (I-2080)~(I-2106) (I-a-1)~(I-a-27) (I-c-78) (I-2107)~(I-2133) (I-a-1)~(I-a-27) (I-c-79) (I-2134)~(I-2160) (I-a-1)~(I-a-27) (I-c-80) (I-2161)~(I-2187) (I-a-1)~(I-a-27) (I-c-81) (I-2188)~(I-2214) (I-a-1)~(I-a-27) (I-c-82) (I-2215)~(I-2241) (I-a-1)~(I-a-27) (I-c-83) (I-2242)~(I-2268) (I-a-1)~(I-a-27) (I-c-84) (I-2269)~(I-2295) (I-a-1)~(I-a-27) (I-c-85) (I-2296)~(I-2322) (I-a-1)~(I-a-27) (I-c-86) (I-2323)~(I-2349) (I-a-1)~(I-a-27) (I-c-87) (I-2350)~(I-2376) (I-a-1)~(I-a-27) (I-c-88) (I-2377)~(I-2403) (I-a-1)~(I-a-27) (I-c-89) (I-2404)~(I-2430) (I-a-1)~(I-a-27) (I-c-90) (I-2431)~(I-2457) (I-a-1)~(I-a-27) (I-c-91) (I-2458)~(I-2484) (I-a-1)~(I-a-27) (I-c-92) (I-2485)~(I-2511) (I-a-1)~(I-a-27) (I-c-93) (I-2512)~(I-2538) (I-a-1)~(I-a-27) (I-c-94) (I-2539)~(I-2565) (I-a-1)~(I-a-27) (I-c-95) (I-2566)~(I-2592) (I-a-1)~(I-a-27) (I-c-96) (I-2593)~(I-2619) (I-a-1)~(I-a-27) (I-c-97) (I-2620)~(I-2646) (I-a-1)~(I-a-27) (I-c-98) (I-2647)~(I-2673) (I-a-1)~(I-a-27) (I-c-99) (I-2674)~(I-2700) (I-a-1)~(I-a-27) (I-c-100) (I-2701)~(I-2727) (I-a-1)~(I-a-27) (I-c-101) (I-2728)~(I-2754) (I-a-1)~(I-a-27) (I-c-102) (I-2755)~(I-2781) (I-a-1)~(I-a-27) (I-c-103) (I-2782)~(I-2808) (I-a-1)~(I-a-27) (I-c-104) (I-2809)~(I-2835) (I-a-1)~(I-a-27) (I-c-105) (I-2836)~(I-2862) (I-a-1)~(I-a-27) (I-c-106) (I-2863)~(I-2889) (I-a-1)~(I-a-27) (I-c-107) (I-2890)~(I-2916) (I-a-1)~(I-a-27) (I-c-108)

[0043] Among them, the carboxylates (I) are preferably carboxylates (I-1) to (I-12), (I-28) to (I-39), (I-55) to (I-66), (I-82) to (I-93), (I-109) to (I-120), (I-136) to (I-147), (I-163) to (I-174), (I-190) to (I-201), (I-217) to (I-228), (I-244) to (I-255), and (I-271) to (I-282). Carboxylates (I-298) ~ Carboxylates (I-309), Carboxylates (I-325) ~ Carboxylates (I-336), Carboxylates (I-352) ~ Carboxylates (I-363), Carboxylates (I-379) ~ Carboxylates (I-390), Carboxylates (I-406) ~ Carboxylates (I-417), Carboxylates (I-433) ~ Carboxylates (I-444), Carboxylates (I-460) ~ Carboxylates (I-471), Carboxylates (I-487) ~ Carboxylates (I-498), Carboxylates (I-514) ~ Carboxylates (I-525), Carboxylates (I-541) ~ Carboxylates (I-552), Carboxylates (I-568) ~ Carboxylates (I-579), Carboxylates ( I-595) ~ Carboxylate (I-606), Carboxylate (I-622) ~ Carboxylate (I-633), Carboxylate (I-649) ~ Carboxylate (I-660), Carboxylate (I-676) ~ Carboxylate (I-687), Carboxylate (I-703) ~ Carboxylate (I-714), Carboxylate (I-730) ~ Carboxylate (I-741), Carboxylate (I-757) ~ Carboxylate (I-768), Carboxylate (I-784) ~ Carboxylate (I-795), Carboxylate (I-811) ~ Carboxylate (I-822), Carboxylate (I-838) ~ Carboxylate (I-849), Carboxylate (I-865) ~ Carboxylate (I-876), Carboxylate (I-892) Carboxylates (I-903), (I-919) ~ Carboxylates (I-930), (I-946) ~ Carboxylates (I-957), (I-973) ~ Carboxylates (I-984), (I-1000) ~ Carboxylates (I-1011), (I-1027) ~ Carboxylates (I-1038), (I-1054) ~ Carboxylates (I-1065), (I-1081) ~ Carboxylates (I-1092), (I-1108) ~ Carboxylates (I-1119), (I-1135) ~ Carboxylates (I-1146), (I-1162) ~ Carboxylates (I-1173)Salt (I-1189)~Salt (I-1200), Salt (I-1216)~Salt (I-1227), Salt (I-1243)~Salt (I-1254), Salt (I-1270)~Salt (I-1281), Salt (I-1297)~Salt (I-1308), Salt (I-1324)~Salt (I-1335), Salt (I-1 351) ~ Salt (I-1362), Salt (I-1378) ~ Salt (I-1389), Salt (I-1405) ~ Salt (I-1416), Salt (I-1432) ~ Salt (I-1443), Salt (I-1459) ~ Salt (I-1470), Salt (I-1486) ~ Salt (I-1497), Salt (I-1513) ~ Salt (I-1524), Salt (I-1540)~Salt (I-1551), Salt (I-1567)~Salt (I-1578), Salt (I-1594)~Salt (I-1605), Salt (I-1621)~Salt (I-1632), Salt (I-1648)~Salt (I-1659), Salt (I-1675)~Salt (I-1 686), Salt (I-1702)~Salt (I-1713), Salt (I-1729)~Salt (I-1740), Salt (I-1756)~Salt (I-1767), Salt (I-1783)~Salt (I-1794), Salt (I-1810)~Salt (I-1821), Salt (I-1837)~Salt (I-1848), Salt (I-1864)~Salt (I-1875), Salt (I-1891)~Salt (I-1902), Salt (I-1918)~Salt (I-1929), Salt (I-1945)~Salt (I-1956), Salt (I-1972)~Salt (I-1983), Salt (I-1999)~Salt (I-2010), Salt (I-2 026)~Salt (I-2037), Salt (I-2053)~Salt (I-2064), Salt (I-2080)~Salt (I-2091), Salt (I-2107)~Salt (I-2118), Salt (I-2134)~Salt (I-2145), Salt (I-2161)~Salt (I-2172), Salt (I-2188)~ Salt (I-2199), Salt (I-2215)~Salt (I-2226), Salt (I-2242)~Salt (I-2253), Salt (I-2269)~Salt (I-2280), Salt (I-2296)~Salt (I-2307), Salt (I-2323)~Salt (I-2334), Salt (I-2350)~Salt (I-2 361), Salt (I-2377)~Salt (I-2388), Salt (I-2404)~Salt (I-2415), Salt (I-2431)~Salt (I-2442), Salt (I-2458)~Salt (I-2469), Salt (I-2485)~Salt (I-2496), Salt (I-2512)~Salt (I-2523),Salt (I-2539) ~ Salt (I-2550), Salt (I-2566) ~ Salt (I-2577), Salt (I-2593) ~ Salt (I-2604), Salt (I-2620) ~ Salt (I-2631), Salt (I-2647) ~ Salt (I-2658), Salt (I-2674) ~ Salt (I-2685), Salt (I-2701) ~ Salt (I-2712), Salt (I-2728)~Salt (I-2739), Salt (I-2755)~Salt (I-2766), Salt (I-2782)~Salt (I-2793), Salt (I-2809)~Salt (I-2820), Salt (I-2836)~Salt (I-2847), Salt (I-2863)~Salt (I-2874), Salt (I-2890)~Salt (I-2901).

[0044] <Method for manufacturing carboxylate (I)> Carboxylate (I) can be produced by reacting the salt represented by formula (Ia) with the salt represented by formula (Ib) in a solvent. [In the formula, the symbols R4, R5, R6, R7, R8, R9, Rbb1, m1, m2, m3, m4, m5, m6, m7, m8, m9, A1, A2, A3, X0, X10, and L10 respectively represent the same meaning as described above.] Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. The reaction temperature is usually 15℃~80℃, and the reaction time is usually 0.5 hours~24 hours.

[0045] As the salt represented by formula (Ia), salts represented by the following formulas can be listed. These salts can be easily manufactured by the same method as that described in Japanese Patent Application Publication No. 2020-15713, or by known manufacturing methods.

[0046] The salt represented by formula (Ib) can be produced by reacting the compound represented by formula (Ic) with silver oxide in a solvent. [In the formula, all symbols represent the same meaning as described above.] Examples of solvents used in this reaction include chloroform and acetonitrile. The reaction temperature is usually 15℃~80℃, and the reaction time is usually 0.5 hours~24 hours.

[0047] Compounds represented by formula (Ic) can be listed as those represented by the following formulas. These compounds are readily available from the market or can be easily manufactured by known methods.

[0048] [Derived from the structural unit of salt represented by formula (I)] The structural unit of the salt represented by formula (I) is the structural unit represented by formula (IP) (hereinafter sometimes referred to as "structural unit (IP)"). This structural unit (IP), like the salt (I), also functions as an acid-generating agent and as a structural unit constituting a compound or resin. [A resin containing structural units derived from the carboxylate represented by formula (I)] The resin of the present invention is a resin comprising a structural unit (IP) derived from a carboxylate represented by formula (I) (hereinafter sometimes referred to as "resin (Ap)"). [In the formula, the symbols R4, R5, R6, R7, R8, R9, Rbb1, m1, m2, m3, m4, m5, m6, m7, m8, m9, A1, A2, A3, X0, X10, and L10 respectively represent the same meaning as described above.] The structural unit (IP) represents the state of double bond cleavage in CH 2=CR bb1 contained in salt (I). The resin (Ap) can be a homopolymer containing one structural unit (IP) or a copolymer containing two or more structural units (IP). In addition, the resin (Ap) may also contain structural units other than structural units (IP). As structural units other than structural units (IP), examples include structural units having acid-instable groups (hereinafter sometimes referred to as "structural unit (a1)"), structural units without acid-instable 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. Here, "acid-instable group" refers to a group that has a detaching group, and through contact with an acid, the detaching group is detached, and the constituent unit is transformed into a constituent unit having a hydrophilic group (e.g., hydroxyl or carboxyl group). The content of structural units (IP) relative to the total amount of resin (Ap) is typically 0.1 mol% to 100 mol%, preferably 0.5 mol% to 50 mol%, more preferably 0.8 mol% to 30 mol%, and even more preferably 1 mol% to 10 mol.

[0049] In particular, when the resin (Ap) is used in a resist composition, as described later, it is preferable to include structural units (a1) in addition to structural units (IP). Furthermore, as described later, when resin (Ap) is used in resist compositions, it can be used in combination with resins containing structural units (a1) (hereinafter sometimes referred to as "resin (A)") and / or resins other than resin (A), regardless of whether it contains structural units (a1). Hereinafter, resin (Ap) and / or resin (A) are sometimes referred to as "resin (A) etc." Resin (Ap) and resin (A) are preferably structural units that include structural units other than structural unit (a1). Other structural units besides 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 field.

[0050] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer (hereinafter sometimes referred to as "monomer (a1)") that has an acid-instable group. The acid-instable groups contained in resin (A) and the like are preferably groups represented by formula (1) (hereinafter also referred to as group (1)) and / or groups represented by formula (2) (hereinafter also referred to as group (2)). In formula (1), Ra1, Ra2 and Ra3 independently represent alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 2 to 8 carbon atoms, alicyclic hydrocarbon groups with 3 to 20 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or groups formed by combining these, or Ra1 and Ra2 are bonded to each other and together with the bonded carbon atoms to form a non-aromatic hydrocarbon ring with 3 to 20 carbon atoms. ma and na independently represent 0 or 1, and at least one of ma and na represents 1. * indicates the bonding location] In formula (2), Ra1' and Ra2' independently represent hydrogen atoms or hydrocarbon groups with 1 to 12 carbon atoms, and Ra3' represents hydrocarbon groups with 1 to 20 carbon atoms. Alternatively, Ra2' and Ra3' may be bonded to each other and together with the bonded carbon atoms and X to form a heterocycle with 3 to 20 carbon atoms. The hydrocarbon group and the -CH2- contained in the heterocycle may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * indicates the bonding location]

[0051] Examples of alkyl groups in Ra1, Ra2, and Ra3 include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Examples of alkenyl groups in Ra1, Ra2, and Ra3 include: vinyl, propenyl, isopropenyl, butenyl, isobutenyl, tributenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl. The alicyclic hydrocarbon groups in Ra1, Ra2, and Ra3 can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl cycloalkyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). The alicyclic hydrocarbon groups in Ra1, Ra2, and Ra3 preferably have 3 to 16 carbon atoms. Aromatic hydrocarbon groups that make up Ra1, Ra2, and Ra3 include: phenyl, naphthyl, anthracene, biphenyl, phenanthrene, and other aryl groups. Examples of groups that can be combined include: groups formed by combining the alkyl group with an alicyclic hydrocarbon group (e.g., methylcyclohexyl, dimethylcyclohexyl, methylnorbornel, cyclohexylmethyl, adamantylmethyl, adamantyldimethyl, norbornelethyl, etc., alkylcycloalkyl or cycloalkylalkyl), benzyl and other arylalkyl groups, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, cumenel, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl, p-adamantylphenyl, etc.), phenylcyclohexyl and other aryl-cycloalkyl groups, etc. Ideally, ma should be 0 and na should be 1. When Ra1 and Ra2 are bonded together to form a non-aromatic hydrocarbon ring, the following rings can be listed. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * indicates the bonding site with -O-.

[0052] Examples of hydrocarbon groups in Ra1', Ra2', and Ra3' include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Alkyl, alicyclic hydrocarbon, aromatic hydrocarbon, and groups formed by combining these can be listed as the same as those listed in Ra1, Ra2, and Ra3. When Ra2' and Ra3' are bonded to each other and form a heterocycle together with the bonded carbon atoms and X, the following rings can be listed as -C(Ra1')(Ra2')-XRa3'. * indicates the bonding site. Of Ra1' and Ra2', at least one is preferably a hydrogen atom. na' is preferably 0.

[0053] As a basis (1), the following basis can be listed. In formula (1), Ra1, Ra2, and Ra3 are alkyl groups, ma=0, na=1. Preferably, the group is a third butoxycarbonyl group. In formula (1), Ra1 and Ra2 together with the bonded carbon atoms form adamantyl groups, Ra3 is an alkyl group, ma=0, and na=1. In formula (1), Ra1 and Ra2 are alkyl groups, Ra3 is adamantyl alkyl group, ma=0, and na=1. As a base (1), the following bases can be specifically listed. * indicates a bonding site.

[0054] As specific examples of base (2), the following bases can be listed. * indicates the bonding site.

[0055] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylene unsaturated bond, and more preferably a (meth)acrylic acid monomer having an acid-labile group.

[0056] Among (meth)acrylic acid monomers having acid-instable groups, those having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are preferred. If a resin (A) or the like having the following structural unit, derived from a monomer (a1) having a large-volume structure like an alicyclic hydrocarbon group, is used in the resist composition, the resolution of the resist pattern can be improved.

[0057] As structural units derived from (meth)acrylic acid monomers having a group (1), examples 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, at least one structural unit is selected from the group consisting of structural units (a1-0), structural units (a1-1), and structural units (a1-2), and more preferably, at least one structural unit is selected from the group consisting of structural units (a1-1) and structural units (a1-2). These can be used alone or in combination of two or more. In equations (a1-0), (a1-1), and (a1-2), La01, La1, and La2 independently represent -O- or *-O-(CH2) k1-CO-O-, where k1 represents any integer from 1 to 7, and * represents the bonding site with -CO-. Ra01, Ra4, and Ra5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Ra02, Ra03, and Ra04 each independently represent 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 composed of these. Ra6 and Ra7 respectively represent alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 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. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. [n1' represents any integer from 0 to 3]

[0058] Ra01, Ra4, and Ra5 are preferably hydrogen atoms or methyl groups, and more preferably methyl groups. La01, La1 and La2 are preferably oxygen atoms or *-O-(CH2)k01-CO-O- (wherein, k01 is preferably any integer from 1 to 4, more preferably 1), and are even more preferably oxygen atoms. As alkyl, alicyclic hydrocarbon, aromatic hydrocarbon, and groups formed by combining these in Ra02, Ra03, and Ra04, the same groups as those listed in Ra1, Ra2, and Ra3 of formula (1) can be listed. As alkyl, alkenyl, alicyclic hydrocarbon, aromatic hydrocarbon, and groups formed by combining these in Ra6 and Ra7, the same groups as those listed in Ra1, Ra2 and Ra3 of formula (1) can be listed. The alkyl groups in RaO2, RaO3, and RaO4 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl. The alkyl groups in Ra6 and Ra7 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl, ethyl, isopropyl or tributyl, and even more preferably ethyl, isopropyl or tributyl. The alkenyl groups in Ra6 and Ra7 are preferably alkenyl groups with 2 to 6 carbon atoms, and more preferably vinyl, propenyl, isopropenyl or butenyl. The alicyclic hydrocarbon groups in Ra02, Ra03, Ra04, Ra6 and Ra7 preferably have 5 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms. The aromatic hydrocarbon groups in Ra02, Ra03, Ra04, Ra6 and Ra7 preferably have 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. Regarding groups formed by combining alkyl groups with alicyclic hydrocarbon groups, the total number of carbon atoms in the combination of these alkyl and alicyclic hydrocarbon groups is preferably 18 or less. Regarding groups formed by combining alkyl groups and aromatic hydrocarbon groups, the total number of carbon atoms in the combination of these alkyl groups and aromatic hydrocarbon groups is preferably 18 or less. RaO2 and RaO3 are preferably alkyl groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 12 carbon atoms, and more preferably methyl, ethyl, phenyl or naphthyl. RaO4 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 methyl, ethyl, cyclohexyl or adamantyl. Ra6 and Ra7 are each preferably, independently and independently, alkyl, alkenyl, or aromatic hydrocarbon groups having 1 to 6 carbon atoms, more preferably methyl, ethyl, isopropyl, tributyl, vinyl, phenyl, or naphthyl, and even more preferably ethyl, isopropyl, tributyl, vinyl, or phenyl. m1 is preferably any integer from 0 to 3, and more preferably 0 or 1. n1 is preferably any integer from 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0059] As a structural unit (a1-0), for example, structural units represented by any of formulas (a1-0-1) to (a1-0-18) and structural units in which the methyl group corresponding to Ra01 in structural unit (a1-0) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl group are preferred, and structural units represented by any of formulas (a1-0-1) to (a1-0-10), (a1-0-13) and (a1-0-14) are preferred.

[0060] As structural unit (a1-1), examples include structural units derived from the monomer described in Japanese Patent Application Publication No. 2010-204646. Among them, structural units represented by any of formulas (a1-1-1) to (a1-1-7) and structural units in which the methyl group corresponding to Ra4 in structural unit (a1-1) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl group are more preferred.

[0061] As structural unit (a1-2), structural units represented by any of formulas (a1-2-1) to (a1-2-14) and structural units in which the methyl group corresponding to Ra5 ​​in structural unit (a1-2) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl group are listed. Preferred structural units are those represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6) and (a1-2-10) to (a1-2-14).

[0062] When the resin (A) and the like contains structural units (a1-0) and / or structural units (a1-1) and / or structural units (a1-2), the total content of these structural units relative to all structural units in the resin (A) and the like can be listed as 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. Alternatively, it can be listed as 95 mol% or less, preferably 90 mol% or less, even more preferably 85 mol% or less, and even more preferably 70 mol% or less. Specifically, it can be listed as 10 mol% to 95 mol%, preferably 15 mol% to 90 mol%, more preferably 20 mol% to 85 mol%, even more preferably 25 mol% to 70 mol%, and even more preferably 30 mol% to 70 mol%. When the resin (A) or the like contains structural units (a1-0), the content of these structural units relative to all structural units in the resin (A) or the like can be listed as 5 mol% or more, preferably 10 mol% or more. Alternatively, it can be listed as 80 mol% or less, preferably 75 mol% or less, and even more preferably 70 mol% or less. Specifically, it is 5 mol% to 80 mol%, preferably 5 mol% to 75 mol%, and even more preferably 10 mol% to 70 mol%. When resin (A) and the like contains structural units (a1-1) and / or structural units (a1-2), the total content of these structural units relative to all structural units in resin (A) and the like can be listed as 10 mol% or more, preferably 15 mol% or more, and more preferably 20 mol% or more. Alternatively, it can be listed as 90 mol% or less, preferably 85 mol% or less, more preferably 80 mol% or less, further preferably 75 mol% or less, and even more preferably 70 mol% or less. Specifically, it is 10 mol% to 90 mol%, preferably 15 mol% to 85 mol%, more preferably 20 mol% to 80 mol%, further preferably 20 mol% to 75 mol%, and even more preferably 20 mol% to 70 mol%.

[0063] As a structural unit with basis (2) in structural unit (a1), the structural unit represented by formula (a1-4) can be enumerated (hereinafter, sometimes referred to as "structural unit (a1-4)"). In formula (a1-4), Ra32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Ra33 represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkoxyalkyl group with 2 to 12 carbon atoms, alkoxyalkoxy group with 2 to 12 carbon atoms, alkyl carbonyl group with 2 to 4 carbon atoms, alkyl carbonyloxy group with 2 to 4 carbon atoms, acryloxy group or methacryloxy group. A a30 represents a single bond or *-X a31-(A a32-X a32) nc-, * represents the bonding site of the carbon atom bonded to -R a32. A a32 indicates an alkyldiyl group with 1 to 6 carbon atoms. X a31 and X a32 independently represent -O-, -CO-O-, or -O-CO-, respectively. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer greater than 2, multiple Ra33 can be the same or different. Ra34 and Ra35 independently represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and Ra36 represents hydrocarbon groups having 1 to 20 carbon atoms. Alternatively, Ra35 and Ra36 may be bonded together with the bonded -CO- to form divalent hydrocarbon groups having 2 to 20 carbon atoms. The hydrocarbon group and the -CH2- contained in the divalent hydrocarbon group may be substituted by -O- or -S-.

[0064] Halogen atoms in Ra32 and Ra33 include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 6 carbon atoms in Ra32 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. Ra32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Examples of alkyl groups in Ra33 include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, and hexyl. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl. Examples of alkoxy groups in Ra33 include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, dibutoxy, terbutoxy, pentyloxy, and hexyloxy. The alkoxy group is preferably an alkoxy group with 1 to 4 carbon atoms, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. Examples of alkoxyalkyl groups in Ra33 include: methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, dibutoxymethyl, and tertiary butoxymethyl. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably methoxymethyl or ethoxyethyl, and even more preferably methoxymethyl. Examples of alkoxyalkoxy groups in Ra33 include: methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, dibutoxymethoxy, and terbutoxymethoxy. Preferably, the alkoxyalkoxy group has 2 to 8 carbon atoms, and more preferably, it is methoxyethoxy or ethoxyethoxy. Examples of alkyl carbonyl groups in Ra33 include acetyl, propionic, and butyryl. The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 to 3 carbon atoms, and more preferably acetyl. Examples of alkyl carbonyl groups in Ra33 include acetylated carbonyl groups, propionic carbonyl groups, and butylated carbonyl groups. Preferably, the alkyl carbonyl group is an alkyl carbonyl group with 2 to 3 carbon atoms, and more preferably, it is an acetylated carbonyl group. Ra33 is preferably a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, 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.

[0065] As *-X a31-(A a32-X a32) nc-, examples include: *-O-, *-CO-O-, *-O-CO-, *-CO-OA a32-CO-O-, *-O-CO-A a32-O-, *-OA a32-CO-O-, *-CO-OA a32-O-CO-, and *-O-CO-A a32-O-CO-. Among these, *-CO-O-, *-CO-OA a32-CO-O-, or *-OA a32-CO-O- are preferred.

[0066] Examples of alkyldiyl groups include: methylene, ethyl, 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. A a32 is preferably methylene or ethyl.

[0067] A a30 is preferably a single bond, *-CO-O- or *-CO-OA a32-CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH 2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0068] la is preferably 0, 1, or 2, more preferably 0 or 1, and even better if it is 0. Examples of hydrocarbon groups in Ra34, Ra35 and Ra36 include: alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Alicyclic hydrocarbon groups can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl cycloalkyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). Examples of aromatic hydrocarbon groups include: phenyl, naphthyl, anthracene, biphenyl, phenanthrene, and other aryl groups. Examples of groups that can be combined include: groups formed by combining the alkyl group with an alicyclic hydrocarbon group (e.g., methylcyclohexyl, dimethylcyclohexyl, methylnorbornel, cyclohexylmethyl, adamantylmethyl, adamantyldimethyl, norbornelethyl, etc., alkylcycloalkyl or cycloalkylalkyl groups), aralkyl groups such as benzyl, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, cumenel, mesitylene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl, p-adamantylphenyl, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl. In particular, examples of Ra36 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.

[0069] Ra34 is preferably composed of hydrogen atoms. Ra35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl or ethyl group. The hydrocarbon group in Ra36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl and alicyclic hydrocarbon groups in Ra36 are preferably unsubstituted. The aromatic hydrocarbon groups in Ra36 are preferably aromatic rings having an aryloxy group having 6 to 10 carbon atoms.

[0070] In structural unit (a1-4), -OC(Ra34)(Ra35)-OR a36 comes into contact with an acid (e.g., p-toluenesulfonic acid) and detaches to form a hydroxyl group. -OC(Ra34)(Ra35)-OR a36 is preferably bonded to the meta- or para-position of the benzene ring.

[0071] As structural units (a1-4), examples include structural units derived from the monomers described in Japanese Patent Application Publication No. 2010-204646. Preferably, structural units represented by formulas (a1-4-1) to (a1-4-24) and structural units in which the hydrogen atom corresponding to Ra32 in structural unit (a1-4) is replaced by a halogen atom, a haloalkyl group, or an alkyl group can be listed. 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) can be listed.

[0072] When the resin (A) and the like contain structural units (a1-4), the content of the structural units is preferably 3 mol% to 80 mol% relative to the total of all structural units in the resin (A), more preferably 5 mol% to 75 mol%, even more preferably 7 mol% to 70 mol%, even more preferably 7 mol% to 65 mol%, and particularly preferably 10 mol% to 60 mol%.

[0073] As a structural unit derived from (meth)acrylic acid monomers having a group (2), structural units represented by formulas (a1-5) can also be listed (hereinafter sometimes referred to as "structural unit (a1-5)"). In equation (a1-5), Ra8 represents an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that may have halogen atoms. Za1 represents a single bond or *-(CH2)h3-CO-L54-, where h3 represents any integer from 1 to 4, and * represents the bond site with L51. L51, L52, L53 and L54 each independently represent -O- or -S-. s1 represents any integer from 1 to 3. s1' represents any integer from 0 to 3.

[0074] As halogen atoms, fluorine atoms and chlorine atoms can be listed, with fluorine atoms being preferred. Examples of alkyl groups having 1 to 6 carbon atoms that may contain halogen atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl, and trifluoromethyl. In formula (a1-5), Ra8 is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. L 51 is preferably an oxygen atom. Of L 52 and L 53, one is preferred to be -O- and the other is preferred to be -S-. s1 is preferably 1. s1' is preferably any integer from 0 to 2. Za1 is preferably a single bond or *-CH2-CO-O-.

[0075] As structural units (a1-5), examples include structural units derived from the single unit described in Japanese Patent Application Publication No. 2010-61117. Among them, structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and structural units represented by formulas (a1-5-1) or (a1-5-2) are even more preferred.

[0076] When the resin (A) and the like contain structural units (a1-5), the content of the structural units is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 45 mol%, and even more preferably 5 mol% to 40 mol%, and even more preferably 5 mol% to 30 mol% relative to all structural units in the resin (A).

[0077] In addition, the following structural units can also be listed as structural units (a1).

[0078] When resin (A) and the like contain structural units such as (a1-3-1) to (a1-3-7), the content of all structural units in resin (A) and the like is preferably 10 mol% to 95 mol%, more preferably 15 mol% to 90 mol%, even more preferably 20 mol% to 85 mol%, even more preferably 20 mol% to 70 mol%, and particularly preferably 20 mol% to 60 mol.

[0079] In addition, the following structural units can also be listed as structural units (a1). When resin (A) and the like contain structural units such as (a1-6-1) to (a1-6-3), the content of all structural units in resin (A) and the like is preferably 10 mol% to 60 mol%, more preferably 15 mol% to 55 mol%, even more preferably 20 mol% to 50 mol%, even more preferably 20 mol% to 45 mol%, and particularly preferably 20 mol% to 40 mol.

[0080] <Structural Unit(s)> The structural unit(s) is derived from a monomer (hereinafter sometimes referred to as "monomer(s)") that does not have an acid-labile group. The monomer from which the structural unit(s) is derived can be a monomer that does not have an acid-labile group and is known in the field of resists. As structural unit (s), it is preferred to have a hydroxyl group or a lactone ring. If a resin containing a structural unit having a hydroxyl group but not an acid-instable group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring but not an acid-instable 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.

[0081] <Structural Unit (a2)> The hydroxyl group in the structural unit (a2) can be either an alcoholic hydroxyl group or a phenolic hydroxyl group. When manufacturing resist patterns from the resist composition of the present invention, when using high-energy rays such as KrF excimer laser (248 nm), electron beam, or EUV (ultra-ultraviolet light) as the exposure light source, the structural unit (a2) is preferably a structural unit (a2) having phenolic hydroxyl groups, and more preferably a structural unit (a2-A) described later. Furthermore, when using ArF excimer laser (193 nm) or the like, the structural unit (a2) is preferably a structural unit (a2) having alcoholic hydroxyl groups, and more preferably a structural unit (a2-1) described later. The structural unit (a2) may consist of one type or two or more types.

[0082] As a structural unit with phenolic hydroxyl groups in structural unit (a2), the structural unit represented by formula (a2-A) can be listed (hereinafter sometimes referred to as "structural unit (a2-A)"). In formula (a2-A), Ra50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Ra51 represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkoxyalkyl group with 2 to 12 carbon atoms, alkoxyalkoxy group with 2 to 12 carbon atoms, alkyl carbonyl group with 2 to 4 carbon atoms, alkyl carbonyloxy group with 2 to 4 carbon atoms, acryloxy group or methacryloxy group. A a50 represents a single bond or *-X a51-(A a52-X a52) nb-, where * represents the bond position of the carbon atom bonded to -R a50. A a52 represents an alkyldiyl group with 1 to 6 carbon atoms. X a51 and X a52 independently represent -O-, -CO-O-, or -O-CO-, respectively. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer greater than 2, multiple Ra51 values ​​can be the same or different.

[0083] Halogen atoms in Ra50 and Ra51 can be listed as fluorine atoms, chlorine atoms, and bromine atoms, etc. Examples of alkyl groups having 1 to 6 carbon atoms in Ra50 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. Ra50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Examples of alkyl groups in Ra51 include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, and hexyl. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl. Examples of alkoxy groups in Ra51 include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, dibutoxy, and terbutoxy. The alkoxy group is preferably an alkoxy group with 1 to 4 carbon atoms, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. Examples of alkoxyalkyl groups in Ra51 include: methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, dibutoxymethyl, and terbutoxymethyl. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably methoxymethyl or ethoxyethyl, and even more preferably methoxymethyl. Examples of alkoxyalkoxy groups in Ra51 include: methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, dibutoxymethoxy, and terbutoxymethoxy. Preferably, the alkoxyalkoxy group has 2 to 8 carbon atoms, and more preferably, it is methoxyethoxy or ethoxyethoxy. Examples of alkyl carbonyl groups in Ra51 include acetyl, propionic, and butyryl. The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 to 3 carbon atoms, and more preferably acetyl. Examples of alkyl carbonyl groups in Ra51 include acetylated carbonyl groups, propionic carbonyl groups, and butylated carbonyl groups. The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 to 3 carbon atoms, and more preferably an acetylated carbonyl group. Ra51 is preferably a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, 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.

[0084] Examples of *-X a51-(A a52-X a52) nb- include: *-O-, *-CO-O-, *-O-CO-, *-CO-OA a52-CO-O-, *-O-CO-A a52-O-, *-OA a52-CO-O-, *-CO-OA a52-O-CO-, *-O-CO-A a52-O-CO-. Among them, *-CO-O-, *-CO-OA a52-CO-O-, or *-OA a52-CO-O- are preferred.

[0085] Examples of alkyldiyl groups include: methylene, ethyl, 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. A a52 is preferably methylene or ethyl.

[0086] A a50 is preferably a single bond, *-CO-O- or *-CO-OA a52-CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH 2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0087] mb is preferably 0, 1 or 2, even better is 0 or 1, and even better is 0. The hydroxyl group is preferably bonded to the meta- or para-position of the benzene ring. When more than two hydroxyl groups are present, it is preferable that the two hydroxyl groups are bonded to the meta- and para-positions, respectively.

[0088] As structural units (a2-A), examples can be found in the structural units of the single unit described in Japanese Patent Application Publication No. 2010-204634 and Japanese Patent Application Publication No. 2012-12577. As structural unit (a2-A), the structural units represented by formulas (a2-2-1) to (a2-2-24) and structural units represented by formulas (a2-2-1) to (a2-2-24) in which the methyl group equivalent to Ra50 in structural unit (a2-A) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or other alkyl group can be listed. The structural unit (a2-A) is preferably the structural unit represented by equation (a2-2-1) to equation (a2-2-4), the structural unit represented by equation (a2-2-6), the structural unit represented by equation (a2-2-8), the structural units represented by equations (a2-2-12) to (a2-2-18), and the structural unit represented by equation (a2-2-1) to equation (a2-2-4), the structural unit represented by equation (a2-2-6), the structural unit represented by equation (a2-2-8), and the structural unit represented by equations (a2-2-12) to (a2-2-18), which is equivalent to R in structural unit (a2-A). The structural unit in a50 where the methyl group is replaced by a hydrogen atom is more preferably the structural unit represented by formula (a2-2-3), formula (a2-2-4), formula (a2-2-8), formulas (a2-2-12) to (a2-2-14), formula (a2-2-18), and the structural unit represented by formula (a2-2-3), formula (a2-2-4), formula (a2-2-8), formulas (a2-2-12) to (a2-2-14), and formula (a2-2-18), where the R is equivalent to that in structural unit (a2-A). The structural unit in which the methyl group of a50 is replaced by a hydrogen atom is preferably the structural unit represented by formula (a2-2-3), formula (a2-2-4), formula (a2-2-8), and the structural unit in which the methyl group of Ra in structural unit (a2-A) is replaced by a hydrogen atom.

[0089] Relative to all structural units, the content of structural unit (a2-A) in resin (A) and the like is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and even more preferably 20 mol% or more. Additionally, 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 mol% to 80 mol%, more preferably 10 mol% to 70 mol%, further preferably 15 mol% to 65 mol%, and even more preferably 20 mol% to 65 mol%. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, by polymerizing the structural unit (a1-4) and then treating it with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into the resin (A) by polymerizing the acetoxystyrene and the like and then treating it with an alkali such as tetramethylammonium hydroxide.

[0090] As a structural unit with an alcoholic hydroxyl group in structural unit (a2), the structural unit represented by formula (a2-1) can be listed (hereinafter sometimes referred to as "structural unit (a2-1)"). In equation (a2-1), L a3 represents -O- or *-O-(CH 2) k2-CO-O-, k2 represents any integer from 1 to 7. * represents the bond bit with -CO-. Ra14 represents a hydrogen atom or a methyl group. Ra15 and Ra16 independently represent a hydrogen atom, a methyl group, or a hydroxyl group, respectively. o1 represents any integer from 0 to 10.

[0091] In formula (a2-1), L a3 is preferably -O-, -O-(CH 2) f1-CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. Ra14 is preferably methyl. Ra15 is preferably composed of hydrogen atoms. Ra16 is preferably composed of hydrogen atoms or hydroxyl groups. o1 is preferably any integer from 0 to 3, and more preferably 0 or 1.

[0092] As a structural unit (a2-1), for example, structural units derived from the single unit described in Japanese Patent Application Publication No. 2010-204646 can be listed. Preferably, it is a structural unit represented by any of formulas (a2-1-1) to (a2-1-6), more preferably, it is a structural unit represented by any of formulas (a2-1-1) to (a2-1-4), and even more preferably, it is a structural unit represented by formula (a2-1-1) or (a2-1-3).

[0093] When the resin (A) or the like contains structural unit (a2-1), its content relative to all structural units of the resin (A) or the like can be listed as 1 mol% or more, preferably 2 mol% or more. Alternatively, it can be listed as 45 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, further preferably 20 mol% or less, and even more preferably 10 mol% or less. Specifically, it is 1 mol% to 45 mol%, preferably 1 mol% to 40 mol%, more preferably 1 mol% to 35 mol%, further preferably 1 mol% to 20 mol%, and even more preferably 1 mol% to 10 mol%.

[0094] <Structural Unit (a3)> The lactone ring in structural unit (a3) ​​can be a monocyclic ring, such as a β-propiolactone ring, a γ-butyrolactone ring, or a fused ring of a monocyclic lactone ring and other rings. Preferably, it is a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (e.g., the structural unit represented by formula (a3-2) below).

[0095] The structural unit (a3) ​​is preferably the structural unit represented by equation (a3-1), equation (a3-2), equation (a3-3), or equation (a3-4). It may contain only one of these equations, or it may contain two or more of them. In equations (a3-1), (a3-2), (a3-3), and (a3-4), La4, La5, and La6 independently represent the base represented by -O- or *-O-(CH2)k3-CO-O- (k3 represents any integer from 1 to 7). L a7 represents -O-, *-OL a8-O-, *-OL a8-CO-O-, *-OL a8-CO-OL a9-CO-O-, or *-OL a8-O-CO-L a9-O-. La8 and La9 independently represent alkyldiyl groups with 1 to 6 carbon atoms, respectively. * indicates the bond site with the carbonyl group. Ra18, Ra19, and Ra20 each independently represent a hydrogen atom or a methyl group. Ra24 indicates an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that may have halogen atoms. X a3 represents -CH 2- or an oxygen atom. Ra21 represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. Ra22, Ra23, and Ra25 represent carboxyl, cyano, or aliphatic hydrocarbon groups with 1 to 4 carbon atoms, respectively. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple Ra21, Ra22, Ra23 and / or Ra25 may be the same or different.

[0096] Examples of aliphatic hydrocarbon groups in Ra21, Ra22, Ra23, and Ra25 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, dibutyl, and tributyl. Halogen atoms in Ra24 can be listed as: fluorine, chlorine, bromine, and iodine. Alkyl groups in Ra24 can be exemplified by: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, and hexyl, etc., preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl or ethyl. Examples of alkyl groups containing halogen atoms in Ra24 include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorodibutyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, triiodomethyl, etc.

[0097] Examples of alkyl diesters in La8 and La9 include: methylene, ethyl, 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.

[0098] In equations (a3-1) to (a3-3), L a4 to L a6 are preferably independently -O- or *-O-(CH 2) k3-CO-O-, where k3 is any integer from 1 to 4, more preferably -O- and *-O-CH 2-CO-O-, and even more preferably oxygen atoms. Ra18~Ra21 are preferably methyl. Ra22 and Ra23 are each preferably independently carboxyl, cyano, or methyl. p1, q1, and r1 are each preferably any integer from 0 to 2, and more preferably 0 or 1.

[0099] In formula (a3-4), Ra24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Ra25 is preferably carboxyl, cyano, or methyl. La7 is preferably -O- or *-OL a8-CO-O-, and even more preferably -O-, -O-CH 2-CO-O- or -OC 2H 4-CO-O-. w1 is preferably any integer from 0 to 2, and more preferably 0 or 1. In particular, equation (a3-4) is better than equation (a3-4)'. (In the formula, Ra24 and La7 represent the same meaning as described above)

[0100] As structural unit (a3), examples include the monomers described in Japanese Patent Application Publication No. 2010-204646, Japanese Patent Application Publication No. 2000-122294, and Japanese Patent Application Publication No. 2012-41274. Preferably, structural unit (a3) ​​is a structural unit represented by any one of formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and (a3-4-1) to (a3-4-12), and a structural unit in which the methyl groups corresponding to Ra18, Ra19, Ra20, and Ra24 in formulas (a3-1) to (a3-4) are replaced with hydrogen atoms.

[0101]

[0102] When the resin (A) and the like contain structural unit (a3), the total content of all structural units in the resin (A) and the like can be listed as 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Alternatively, it can be listed as 70 mol% or less, preferably 65 mol% or less, and even more preferably 60 mol% or less. Specifically, it is 1 mol% to 70 mol%, preferably 3 mol% to 65 mol%, and even more preferably 5 mol% to 60 mol%. Furthermore, relative to all structural units of resin (A), 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. Additionally, it is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less. Specifically, it is preferably 1 mol% to 60 mol%, more preferably 3 mol% to 50 mol%, and even more preferably 5 mol% to 50 mol%.

[0103] <Structural Unit (a4)> As structural unit (a4), the following structural units can be listed. In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group containing halogen atoms with 1 to 24 carbon atoms, wherein the -CH 2- in the saturated hydrocarbon group can be replaced with -O- or -CO-. The saturated hydrocarbon groups represented by R 42 can include chain saturated hydrocarbon groups, monocyclic or polycyclic alicyclic saturated hydrocarbon groups, and groups formed by combining these.

[0104] Examples of chain-type saturated hydrocarbon groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups; decahydronaphthyl, adamantyl, norbornyl, and polycyclic alicyclic saturated hydrocarbon groups (* indicates the bonding site). As a group formed by combination, examples include groups formed by combining one or more alkyl groups or one or more alkyldiyl groups with one or more alicyclic saturated hydrocarbon groups, such as: -alkyldiyl-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkyldiyl-alicyclic saturated hydrocarbon group-alkyl group, etc.

[0105] As a structural unit (a4), the structural units represented by equation (a4-0), equation (a4-1), and equation (a4-4) can be listed. In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkyl diyl group with 1 to 4 carbon atoms. L 3a represents a perfluoroalkyl dieryl with 1 to 8 carbon atoms or a perfluorocycloalkyl dieryl with 3 to 12 carbon atoms. R 64 represents a hydrogen atom or a fluorine atom.

[0106] Examples of alkyl dienes in L 4a include: straight-chain alkyl dienes such as methylene, ethyl, propane-1,3-diyl, and butane-1,4-diyl; and branched alkyl dienes such as ethane-1,1-diyl, propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, and 2-methylpropane-1,2-diyl.

[0107] Examples of perfluoroalkyl dimethyl groups in L 3a include: difluoromethylene, perfluoroethyl, 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-diyl. 3-Diyl, perfluorohexane-1,6-diyl, perfluorohexane-2,2-diyl, perfluorohexane-3,3-diyl, perfluoroheptane-1,7-diyl, perfluoroheptane-2,2-diyl, perfluoroheptane-3,4-diyl, perfluoroheptane-4,4-diyl, perfluorooctane-1,8-diyl, perfluorooctane-2,2-diyl, perfluorooctane-3,3-diyl, perfluorooctane-4,4-diyl, etc. Examples of perfluorocycloalkyl dimethyl groups in L3a include: perfluorocyclohexanediyl, perfluorocyclopentanediyl, perfluorocycloheptanediyl, and perfluoroadamantanediyl.

[0108] L 4a is preferably a single bond, methylene or ethyl group, and more preferably a single bond or methylene group. L 3a is preferably a perfluoroalkyl diester with 1 to 6 carbons, and more preferably a perfluoroalkyl diester with 1 to 3 carbons.

[0109] As a structural unit (a4-0), the following structural units and structural units in which the methyl group equivalent to R 54 in structural unit (a4-0) is replaced with a hydrogen atom can be listed.

[0110] As a structural unit (a4), the structural units represented by formula (a4-1) can be enumerated. In formula (a4-1), Ra41 represents a hydrogen atom or a methyl group. Ra42 represents a saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, wherein the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. A a41 represents an alkyldiyl group having 1 to 6 carbon atoms or a group represented by formula (a-g1) that may have substituents. At least one of A a41 and Ra a42 has a halogen atom (preferably a fluorine atom) as a substituent. In formula (a-g1), s represents 0 or 1. A a42 and A a44 independently represent divalent saturated hydrocarbon groups with 1 to 5 carbon atoms that can have substituents. A a43 represents a single bond or a divalent saturated hydrocarbon group with 1 to 5 carbon atoms that may have substituents. X a41 and X a42 independently represent -O-, -CO-, -CO-O-, or -O-CO-, respectively. Among them, the total number of carbons of A a42, A a43, A a44, X a41, and X a42 is 7 or less. * indicates the bonding site; the * on the right indicates the bonding site with -O-CO-RA42.

[0111] Examples of saturated hydrocarbon groups in Ra42 include chain hydrocarbon groups, monocyclic or polycyclic saturated alicyclic hydrocarbon groups, and groups formed by combining these.

[0112] Examples of chain hydrocarbon groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl. Examples of monocyclic or polycyclic saturated alicyclic hydrocarbon groups include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups; decahydronaphthyl, adamantyl, norbornyl, and polycyclic alicyclic hydrocarbon groups (* indicates the bonding site). As a group formed by combination, examples include groups formed by combining one or more alkyl groups or one or more alkyldiyl groups with one or more saturated alicyclic hydrocarbon groups, such as: -alkyldiyl-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl group, -alkyldiyl-saturated alicyclic hydrocarbon group-alkyl group, etc.

[0113] Substituents for Ra42 can be selected from at least one group consisting of halogen atoms and groups represented by formula (a-g3). Halogen atoms can be fluorine, chlorine, bromine, and iodine, with fluorine being preferred. In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 represents a saturated hydrocarbon group with 1 to 17 carbon atoms that can have halogen atoms. * indicates the bonding site with Ra42. In Ra42-Xa43-Aa45, where Ra42 does not have a halogen atom, Aa45 represents a saturated hydrocarbon group with 1 to 17 carbon atoms having at least one halogen atom.

[0114] Examples of saturated hydrocarbon groups in A a45 include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl alkyl groups. Monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). As a group formed by combination, examples include groups formed by combining one or more alkyl groups or one or more alkyldiyl groups with one or more alicyclic hydrocarbon groups, such as: -alkyldiyl-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkyldiyl-alicyclic hydrocarbon group-alkyl group, etc.

[0115] Ra42 is preferably a saturated hydrocarbon group that may have halogen atoms, more preferably an alkyl group having halogen atoms and / or a saturated hydrocarbon group having a group represented by formula (a-g3). When Ra42 is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl or perfluorocycloalkyl group, and even more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups include: perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, and perfluorooctyl. Examples of perfluorocycloalkyl groups include perfluorocyclohexyl. When Ra42 is a saturated hydrocarbon group having the group represented by formula (a-g3), the total number of carbons in Ra42, including the number of carbons contained in the group represented by formula (a-g3), is preferably 15 or less, more preferably 12 or less. When the group represented by formula (a-g3) is a substituent, the number of such substituents is preferably one.

[0116] When Ra42 is a saturated hydrocarbon group having the group represented by formula (a-g3), Ra42 is preferably a group represented by formula (a-g2). In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group with 1 to 17 carbon atoms that can have halogen atoms. X a44 represents **-O-CO- or **-CO-O- (** indicates the bonding site with A a46). A a47 represents a saturated hydrocarbon group with 1 to 17 carbon atoms that can have halogen atoms. Among them, the total number of carbon atoms in A a46, A a47 and X a44 is less than 18, and at least one of A a46 and A a47 has at least one halogen atom. * indicates the bonding site with the carbonyl group.

[0117] The saturated hydrocarbon group in A a46 preferably has 1 to 6 carbons, and more preferably 1 to 3 carbons. The saturated hydrocarbon group in A a47 preferably has 4 to 15 carbon atoms, more preferably 5 to 12, and A a47 is further preferably cyclohexyl or adamantyl.

[0118] The preferred structure of the group represented by formula (a-g2) is as follows (* indicates the bonding site with the carbonyl group).

[0119] Examples of alkyl dienes in A a41 include: straight-chain alkyl dienes such as methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and branched alkyl dienes such as propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. Examples of substituents in alkyl diesters represented by A a41 include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. A a41 is preferably an alkyldiyl group having 1 to 4 carbons, more preferably an alkyldiyl group having 2 to 4 carbons, and even more preferably an ethyl group.

[0120] The divalent saturated hydrocarbon groups represented by A a42, A a43, and A a44 in formula (a-g1) can include straight-chain or branched alkyldiyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and divalent saturated hydrocarbon groups formed by combining alkyldiyl groups and divalent alicyclic saturated hydrocarbon groups. Specifically, examples include: methylene, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, etc. Substituents for divalent saturated hydrocarbon groups represented by A a42, A a43, and A a44 include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. The optimal value for s is 0.

[0121] Among the bases represented by equation (a-g1), the following bases can be listed as bases where X a42 is -O-, -CO-, -CO-O-, or -O-CO-. In the following examples, * and ** represent bonding sites, and ** represents the bonding site with -O-CO-Ra42.

[0122] As structural units represented by formula (a4-1), the following structural units and structural units in which the methyl group of Ra41 in the structural unit represented by formula (a4-1) is replaced with a hydrogen atom can be listed.

[0123]

[0124] As a structural unit (a4), the structural units represented by equation (a4-2) and equation (a4-3) can be listed. In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkyldiyl group with 1 to 6 carbon atoms, in which the -CH 2- group can be substituted with -O- or -CO-. R f6 represents a saturated hydrocarbon group with fluorine atoms that has 1 to 20 carbon atoms. Among them, the upper limit of the combined carbon number of L 44 and R f6 is 21.

[0125] Alkadiyl groups with carbon numbers 1 to 6 in L 44 can be listed as the same groups exemplified in A a41. The saturated hydrocarbon groups in Rf6 can be the same as those exemplified in Ra42. The alkyl dienyllium in L 44 is preferably an alkyl dienyllium with 2 to 4 carbon atoms, and more preferably an ethyl alkyl ...

[0126] As structural units represented by formula (a4-2), examples of structural units represented by formulas (a4-1-1) to (a4-1-11) can be listed. Structural units that replace the methyl group of Rf5 in structural unit (a4-2) with hydrogen atoms can also be listed as structural units represented by formula (a4-2).

[0127] In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L5 indicates an alkyldiyl group with 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms that may have fluorine atoms. X f12 represents *-O-CO- or *-CO-O- (* indicates the bonding site with A f13). A f14 represents a saturated hydrocarbon group with 1 to 17 carbon atoms that may have fluorine atoms. Among them, at least one of Af13 and Af14 has fluorine atoms, and the maximum total number of carbon atoms in L5, Af13 and Af14 is 20.

[0128] As alkyl diesters in L 5, the same groups as those exemplified in alkyl diesters of A a41 can be listed.

[0129] As a divalent saturated hydrocarbon group that may have fluorine atoms in A f13, it is preferably a divalent chain saturated hydrocarbon group that may have fluorine atoms or a divalent alicyclic saturated hydrocarbon group that may have fluorine atoms, and more preferably a perfluoroalkyl dimethyl group. Examples of divalent chain saturated hydrocarbon groups that can have fluorine atoms include: alkyl dimethyl groups such as methylene, perfluoroethyl, propylene, butyl, and pentyl; and perfluoroalkyl dimethyl groups such as difluoromethylene, perfluoroethyl, perfluoropropylene, perfluorobutyl, and perfluoropentyl. Divalent alicyclic saturated hydrocarbon groups containing fluorine atoms can be either monocyclic or polycyclic. Examples of monocyclic groups include cyclohexanediol and perfluorocyclohexanediol. Examples of polycyclic groups include adamantanediol, norbornenediol, and perfluoroadamantanediol.

[0130] The saturated hydrocarbon groups in A f14 and the saturated hydrocarbon groups that may have fluorine atoms are examples of the same groups exemplified in Ra42. Among them, the preferred ones are: 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, perfluorohexyl, heptyl, perfluoroheptyl, octyl and perfluorooctyl fluorinated alkyl groups, cyclopropylmethyl, cyclopropyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, perfluorocyclohexyl, adamantyl, adamantylmethyl, adamantyl dimethyl, norbornyl, norbornylmethyl, perfluoroadamantyl, perfluoroadamantyl, etc.

[0131] In formula (a4-3), L5 is preferably ethylenyl. The divalent saturated hydrocarbon group in A f13 is preferably a group comprising a divalent chain saturated hydrocarbon group having 1 to 6 carbons and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbons, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbons. The saturated hydrocarbon group in A f14 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. A f14 is preferably a group comprising an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably cyclopropylmethyl, cyclopentyl, cyclohexyl, norbornyl, and adamantylalkyl.

[0132] As structural units represented by formula (a4-3), examples of structural units represented by formulas (a4-1'-1) to (a4-1'-11) can be listed. Structural units that replace the methyl group of Rf7 in structural unit (a4-3) with hydrogen atoms can also be listed as structural units represented by formula (a4-3).

[0133] As a structural unit (a4), structural units represented by formula (a4-4) can also be listed. In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH 2) j1-, -(CH 2) j2-O-(CH 2) j3-, or -(CH 2) j4-CO-O-(CH 2) j5-. j1~j5 each independently represent any integer from 1 to 6. R f22 represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing fluorine atoms.

[0134] The saturated hydrocarbon group in Rf22 may be the same as that represented by Ra42. Rf22 is preferably an alkyl group with 1 to 10 carbon atoms having fluorine atoms or an alicyclic saturated hydrocarbon group with 1 to 10 carbon atoms having fluorine atoms, more preferably an alkyl group with 1 to 10 carbon atoms having fluorine atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms having fluorine atoms.

[0135] In formula (a4-4), A f21 is preferably -(CH 2) j1-, more preferably ethyl or methylene, and even more preferably methylene.

[0136] As a structural unit represented by formula (a4-4), for example, the following structural units and structural units represented by the following formulas, in which the methyl group equivalent to R f21 in structural unit (a4-4) is replaced with a hydrogen atom.

[0137] When the resin (A) and the like have structural unit (a4), the content of the structural unit (a4) is preferably 1 mol% to 20 mol% relative to all structural units of the resin (A) and the like, more preferably 2 mol% to 15 mol%, and even more preferably 3 mol% to 10 mol%.

[0138] <Structural Unit (a5)> As a non-detached hydrocarbon group in the structural unit (a5), examples include groups having straight-chain, branched, or cyclic hydrocarbon groups. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. As a structural unit (a5), for example, the structural unit represented by the enumerable formula (a5-1). In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group with 3 to 18 carbon atoms, in which the hydrogen atoms can be replaced by aliphatic hydrocarbon groups with 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, wherein the -CH 2- in the saturated hydrocarbon group can be replaced with -O- or -CO-.

[0139] The alicyclic hydrocarbon group in R 52 can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl. Examples of aliphatic hydrocarbon groups with 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, octyl, and 2-ethylhexyl alkyl groups. Examples of alicyclic hydrocarbon groups with substituents include 3-methyladamantyl. R 52 is preferably an unsubstituted alicyclic hydrocarbon group with 3 to 18 carbon atoms, and more preferably adamantyl, norbornyl or cyclohexyl.

[0140] As for the divalent saturated hydrocarbon group in L 55, divalent chain saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups can be listed, with divalent chain saturated hydrocarbon groups being preferred. Examples of divalent chain saturated hydrocarbon groups include: methylene, ethyl, propylene, butyl, and pentyl alkyl diols. Divalent alicyclic saturated hydrocarbon groups can be either monocyclic or polycyclic. Examples of monocyclic alicyclic saturated hydrocarbon groups include cyclopentadiyl and cyclohexanediyl. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include adamantanediyl and norbornanediyl.

[0141] As a divalent saturated hydrocarbon group represented by L 55, the group in which -CH 2- is replaced by -O- or -CO- can be represented, for example, by the groups represented by formulas (L1-1) to (L1-4). In the following formulas, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. In equation (L1-1), X x1 represents *-O-CO- or *-CO-O- (* indicates the bonding site with L x1). L x1 represents a divalent aliphatic saturated hydrocarbon group with 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. Among them, the combined carbon number of L x1 and L x2 is less than 16. In equation (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 16 carbon atoms. Among them, the combined carbon number of L x3 and L x4 is less than 17. In equation (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 independently represent single bonds or divalent aliphatic saturated hydrocarbon groups with 1 to 14 carbon atoms. Among them, the total carbon number of L x5, L x6 and L x7 is less than 15. In equation (L1-4), L x8 and L x9 represent single bonds or divalent aliphatic saturated hydrocarbon groups with 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. Among them, the total number of carbon atoms in L x8, L x9 and W x1 is less than 15.

[0142] L x1 is preferably a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a methylene or ethyl group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a methylene or ethyl group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a methylene or ethyl group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group with 1 to 8 carbon atoms, and more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group with 3 to 10 carbon atoms, and more preferably cyclohexadiyl or adamantanediyl.

[0143] As a base represented by equation (L1-1), for example, the following divalent bases can be listed.

[0144] As a base represented by equation (L1-2), for example, the following divalent bases can be listed.

[0145] As a base represented by equation (L1-3), for example, the following divalent bases can be listed.

[0146] As a base represented by equation (L1-4), for example, the following divalent bases can be listed.

[0147] L 55 is preferably a single bond or a base represented by formula (L1-1).

[0148] As structural unit (a5-1), the following structural units and structural units in which the methyl group equivalent to R 51 in structural unit (a5-1) is replaced with a hydrogen atom can be listed. When the resin (A) and the like have structural unit (a5), the content of the structural unit (a5) is preferably 1 mol% to 30 mol% relative to all structural units of the resin (A) and the like, more preferably 2 mol% to 20 mol%, and even more preferably 3 mol% to 15 mol%.

[0149] <Structural Unit (a6)> The structural unit (a6) is a structural unit with a -SO 2- group, preferably with a -SO 2- group in the side chain. The structural unit having the -SO 2- group may contain a linear structure having the -SO 2- group, a branched structure having the -SO 2- group, or a cyclic structure having the -SO 2- group (monocyclic and polycyclic structures). Preferably, the structural unit contains a cyclic structure having the -SO 2- group, and more preferably, the structural unit contains a cyclic structure (sulfonyl lactone ring) including -SO 2-O-.

[0150] Examples of sulfonyl lactone rings include those represented by formulas (T1-1), (T1-2), (T1-3), and (T1-4). The bonding site can be any position. Sulfonyl lactone rings can be monocyclic, but polycyclic is preferred. Polycyclic sulfonyl lactone rings refer to bridging rings containing -SO₂O₻ as a constituent group, and examples include those represented by formulas (T1-1) and (T1-2). Like the ring represented by formula (T1-2), the constituent groups of the sulfonyl lactone ring may include heteroatoms in addition to -SO₂O₻. Examples of heteroatoms include oxygen, sulfur, or nitrogen atoms, with oxygen being preferred.

[0151] The sulfonyl lactone ring may have substituents. Examples of substituents include: alkyl groups with 1 to 12 carbon atoms, halogen atoms, hydroxyl groups, cyano groups, alkoxy groups with 1 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, aralkyl groups with 7 to 12 carbon atoms, glycidoxy groups, alkoxy carbonyl groups with 2 to 12 carbon atoms, and alkyl carbonyl groups with 2 to 4 carbon atoms.

[0152] Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl, with alkyl groups having 1 to 6 carbon atoms being more preferred, and methyl being even more preferred. Examples of alkyl groups having halogen atoms include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorodibutyl, perfluoroterbutyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl, with trifluoromethyl being a preferred example. Examples of alkyl groups containing hydroxyl groups include hydroxymethyl and 2-hydroxyethyl alkyl groups. Examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, decoxy, and dodecyloxy. Examples of aryl groups include: phenyl, naphthyl, anthraceneyl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl. Examples of aralkyl groups include: benzyl, phenethyl, phenylpropyl, naphthylmethyl, and naphthylethyl. As an alkoxycarbonyl group, examples include methoxycarbonyl, ethoxycarbonyl, etc., which are groups formed by bonding an alkoxy group to a carbonyl group. Preferably, an alkoxycarbonyl group with 6 or fewer carbon atoms is included, and more preferably, a methoxycarbonyl group is included. Examples of alkyl carbonyl groups include acetyl, propionic, and butyryl.

[0153] From the viewpoint that monomers that readily produce the derived structural unit (a6) are readily available, sulfonyl lactone rings without substituents are preferred. The sulfonyl lactone ring is preferably represented by the following formula (T1'). 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, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidoxy group, an alkoxy carbonyl group having 2 to 12 carbon atoms, or an alkyl carbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or higher, multiple R 41 values ​​can be the same or different. [The bonding location can be any position] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. As R 41, examples include those with the same substituents as the sulfonyl lactone ring, preferably alkyl groups having 1 to 12 carbon atoms that may have halogen atoms or hydroxyl groups. ma is preferably 0 or 1, and even better is 0.

[0154] The following rings can be listed as examples of the rings represented by equation (T1'). The bonding location is arbitrary.

[0155] The structural unit having a sulfonyl lactone ring preferably has the following groups. * in the following groups indicates a bonding site.

[0156] The structural unit having the -SO₂- group is preferably a group derived from a polymerizable group. Examples of polymerizable groups include: vinyl, acrylonitrile, methacrylonitrile, acrylonitrileoxy, methacrylonitrileoxy, acrylonitrileamine, methacrylonitrileamine, acrylonitrilethio, methacrylonitrilethio, etc. Among them, the monomer of the derived structural unit (a6) is preferably a monomer with an ethylene unsaturated bond, and more preferably a (meth)acrylic acid monomer.

[0157] The structural unit (a6) is preferably the structural unit represented by equation (Ix). In formula (Ix), Rx represents an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that may have halogen atoms. A xx represents an oxygen atom, -N(R c)-, or a sulfur atom. Ax represents a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, in which the -CH 2- can be replaced by -O-, -CO- or -N(R d)-. X 11, R 41, and ma represent the same meanings as described above. Rc and Rd independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.

[0158] Halogen atoms in Rx can be listed as: fluorine, chlorine, bromine, and iodine. Alkyl groups in Rx can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, n-pentyl, and n-hexyl, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl or ethyl. Examples of alkyl groups containing halogen atoms in Rx include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorodibutyl, perfluoroterbutyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.

[0159] Examples of divalent saturated hydrocarbon groups in Ax include: straight-chain alkyl dimethyl groups, branched alkyl dimethyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups. Specifically, examples include: methylene, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, and propane-2,2-diyl, etc., all straight-chain alkyl diyl groups. Branched alkyldiyl groups include butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. Cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, and other cycloalkyl diyl groups are monocyclic divalent alicyclic saturated hydrocarbon groups; Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups.

[0160] As a structural unit (a6), the following structural units can be listed.

[0161] The preferred structural units are those represented by equations (a6-1), (a6-2), (a6-6), (a6-7), (a6-8), and (a6-12), and even more preferably are those represented by equations (a6-1), (a6-2), (a6-7), and (a6-8). When resin (A) has structural unit (a6), its content relative to all structural units of resin (A) is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 40 mol%, and even more preferably 3 mol% to 30 mol.

[0162] <Structural Unit (II)> Resin (A) may further contain structural units (hereinafter sometimes referred to as "structural units (II)") that decompose upon exposure and generate acid. Specifically, structural units (II) can be listed in Japanese Patent Application Publication No. 2016-79235, and are preferably structural units with sulfonate or carboxylic acid ester groups and organic cations on the side chain or structural units with strontium groups and organic anions on the side chain.

[0163] The structural unit with a side chain having a sulfonate group or a carboxylic acid ester group and an organic cation is preferably the structural unit represented by formula (II-2-A'). In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. The -CH 2- in the saturated hydrocarbon group can be replaced by -O-, -S- or -CO-. The hydrogen atom in the saturated hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 6 carbon atoms, or a hydroxyl group. A x1 represents an alkyl diel with 1 to 8 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a perfluoroalkyl group with 1 to 6 carbon atoms. RA - indicates sulfonate group or carboxylic ester group. R III3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. ZA+ indicates an organic cation.

[0164] Examples of halogen atoms represented by R III3 include fluorine, chlorine, bromine, and iodine atoms. As an alkyl group represented by R III3 that has 1 to 6 carbon atoms and may have halogen atoms, examples can be listed that are the same as those represented by Ra8 that have 1 to 6 carbon atoms and may have halogen atoms. Examples of alkyldiyl groups with 1 to 8 carbon atoms represented by Ax1 include: methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. Examples of perfluoroalkyl groups having 1 to 6 carbon atoms that can be substituted in A x1 include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorodibutyl, perfluoroterbutyl, perfluoropentyl, perfluorohexyl, etc. As represented by X III3, divalent saturated hydrocarbon groups with 1 to 18 carbon atoms can be listed as straight-chain or branched alkyl diols, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, or combinations thereof. Specifically, examples include: methylene, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, and other straight-chain alkyl diyl groups; butane-1,3-diyl, 2-methylpropane-1,3-diyl, etc. - Diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl and other branched alkyl diyl groups; cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl and other cycloalkyl diyl groups; norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl and other divalent polycyclic alicyclic saturated hydrocarbon groups, etc. As a divalent group represented by formulas (X1) to (X53), the -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbons in the -CH2- group before being replaced by -O-, -S-, or -CO- is 17 or less. In the following formulas, * and ** denote bonding sites, and * denotes the bond with Ax1.

[0165] X 3 represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0166] The ZA+ in formula (II-2-A') can be listed as the same as the Z1+ cation in the salt represented by formula (B1).

[0167] The structural unit represented by equation (II-2-A') is preferably the structural unit represented by equation (II-2-A). In formula (II-2-A), R III3, X III3, and ZA + represent the same meanings as described above. z2A represents any integer from 0 to 6. R III2 and R III4 independently represent hydrogen atoms, fluorine atoms, or perfluoroalkyl groups having 1 to 6 carbon atoms. When z2A is 2 or more, multiple R III2 and R III4 may be the same or different. Qa and Qb independently represent fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. As perfluoroalkyl groups with 1 to 6 carbon atoms represented by R III2, R III4, Q a and Q b, examples can be listed that are the same as the perfluoroalkyl groups with 1 to 6 carbon atoms represented by Q b1.

[0168] The structural unit represented by equation (II-2-A) is preferably the structural unit represented by equation (II-2-A-1). In formula (II-2-A-1), R III2, R III3, R III4, Q a, Q b, and ZA + represent the same meanings as described above. R III5 represents a saturated hydrocarbon group with 1 to 12 carbon atoms. z2A1 represents any integer from 0 to 6. X I2 represents a divalent saturated hydrocarbon group with 1 to 11 carbon atoms. The -CH 2- in this saturated hydrocarbon group can be replaced with -O-, -S-, or -CO-, and the hydrogen atom in this saturated hydrocarbon group can be replaced with a halogen atom or a hydroxyl group. Examples of saturated hydrocarbon groups with 1 to 12 carbon atoms represented by R III5 include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, as well as straight-chain or branched alkyl groups. As for the divalent saturated hydrocarbon group represented by X I2, examples can be listed that are the same as the divalent saturated hydrocarbon group represented by X III3.

[0169] As the structural unit represented by equation (II-2-A-1), it is more preferably the structural unit represented by equation (II-2-A-2). In formula (II-2-A-2), R III3, R III5, and ZA + represent the same meanings as described above. m and nA represent 1 or 2 independently.

[0170] As structural units represented by formula (II-2-A'), examples include structural units in which a methyl group corresponding to R III3 is replaced by a hydrogen atom, a halogen atom (e.g., a fluorine atom), or an alkyl group having 1 to 6 carbon atoms (e.g., trifluoromethyl, etc.) and structural units described in International Publication No. 2012 / 050015. ZA+ represents an organic cation.

[0171] The structural unit with strontium group and organic anion in the side chain is preferably the structural unit represented by formula (II-1-1). In formula (II-1-1), A II1 represents a single bond or a divalent linker. R II1 represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 independently represent hydrocarbon groups with 1 to 18 carbon atoms. R II2 and R II3 can bond to each other and form a ring together with the bonded sulfur atoms. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. A - indicates an organic anion. Examples of divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms represented by R II1 include phenyl and naphthyl groups. Examples of hydrocarbon groups represented by R II2 and R II3 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Halogen atoms represented by R II4 can include: fluorine, chlorine, bromine, and iodine atoms. As alkyl groups represented by R II4 that have 1 to 6 carbon atoms and can have halogen atoms, examples can be listed that are the same as alkyl groups represented by Ra8 that have 1 to 6 carbon atoms and can have halogen atoms. As represented by A II1, divalent linking groups can be, for example, divalent saturated hydrocarbon groups with 1 to 18 carbon atoms, wherein the -CH 2- group can be replaced by -O-, -S-, or -CO-. Specifically, those identical to divalent saturated hydrocarbon groups with 1 to 18 carbon atoms represented by X III3 can be listed.

[0172] As structural units containing cations in formula (II-1-1), the following structural units and structural units in which the methyl group equivalent to R II4 is replaced with hydrogen atoms, fluorine atoms, trifluoromethyl groups, etc. can be listed.

[0173] Examples of organic anions represented by A- include: sulfonate anion, sulfonylimid anion, sulfonylimidate anion, and carboxylate anion. Preferably, the organic anion represented by A- is a sulfonate anion, and more preferably, it is an anion contained in the salt represented by formula (B1) described later. The following are examples of sulfonylimid anions. The following are examples of sulfonylmethane anions. The following can be listed as carboxylate anions.

[0174] As structural units represented by equation (II-1-1), the following structural units can be listed.

[0175] In resin (A) and the like, the content of structural unit (II) when it contains structural unit (II) is preferably 1 mol% to 20 mol%, more preferably 2 mol% to 15 mol%, and even more preferably 3 mol% to 10 mol% when it contains structural unit (II) and all structural units of resin (A).

[0176] Resin (A) is preferably a resin containing structural unit (a1). In particular, resin (Ap) is more preferably a resin containing structural unit (IP), structural unit (a1), and structural unit (s), i.e., a copolymer of salt (I), monomer (a1), and monomer (s). Resin (A) that does not contain structural unit (IP) is preferably a resin containing structural unit (a1) and structural unit (s). The structural unit (a1) is preferably selected from at least one of the group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably the structural unit having cyclohexyl or cyclopentyl groups), more preferably at least two, and even more preferably at least two of the group consisting of structural unit (a1-1) and structural unit (a1-2). Structural unit (s) is preferably selected from at least one of the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably structural unit (a2-1) or structural unit (a2-A). Structural unit (a3) ​​is preferably selected from at least one of the group consisting of the structural unit represented by formula (a3-1), the structural unit represented by formula (a3-2), and the structural unit represented by formula (a3-4).

[0177] The structural units constituting resin (A) and the like can be made using only one type or in combination of two or more types. They can be manufactured using monomers that derive these structural units by a known polymerization method (e.g., free radical polymerization). The content of each structural unit in resin (A) and the like can be adjusted by the amount of monomer used in the polymerization. The weight-average molecular weight of resin (A) and the like is preferably 2,000 or more (more preferably 2,500 or more, and even more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, and even more preferably 15,000 or less). In this specification, the weight-average molecular weight is a value obtained using gel permeation chromatography under the conditions described in the examples. Furthermore, the structural unit (IP) may also constitute a dimer, a trimer, or a compound with a weight-average molecular weight of less than 2,000.

[0178] [Carboxylic acid generating agent] The carboxylic acid generator of the present invention is a carboxylic acid generator containing a carboxylate (I) or a structural unit (IP). The structural unit (IP) may be contained as a compound or resin formed by polymerization of multiple components. The carboxylate (I) or structural unit (IP) of the present invention can function as a carboxylic acid generator in a resist composition. When a carboxylate (I) is used as a carboxylic acid generator in a resist composition, the carboxylic acid generator may contain only one or more carboxylate (I) components. Furthermore, when a structural unit (IP) is used as a carboxylic acid generator in a resist composition, a compound or resin containing a structural unit (IP) may be used alone, or two or more may be combined. The carboxylic acid generator of the present invention may contain both a carboxylate (I) and a structural unit (IP). As described below, the carboxylic acid generator of the present invention may also contain an acid generator (hereinafter sometimes referred to as "acid generator (B)") known in the field of resists other than carboxylate (I) and / or a carboxylate known in the field of resists other than carboxylate (I). Acid generator (B) may be used alone or in combination of two or more. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio (mass ratio; carboxylic acid (I): acid generator (B) or the like) of the content of carboxylate (I) to acid generator (B) or the like is generally 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, even more preferably 5:95 to 95:5, even more preferably 15:85 to 85:15, and particularly preferably 10:90 to 40:60.

[0179] [Resist composition] The resist composition of the present invention contains the carboxylic acid generator of the present invention. The carboxylic acid generator of the present invention may also be a resin (Ap) containing a structural unit (IP). The resist composition of the present invention is a composition containing at least one of a carboxylate (I) and a structural unit (IP), or a composition containing both. That is, the resist composition of the present invention only needs to contain a carboxylic acid generator containing either a structural unit (IP) or a carboxylate (I). 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 and / or a resin (Ap) and a carboxylate (I) as a carboxylic acid generator. The resist composition of the present invention is preferably a resin containing a structural unit (a1) having an acid-instable group. That is, more preferably: (a) Contains carboxylate (I) and resin (A), (b) A resin (Ap) comprising a structural unit (IP) and a structural unit (a1) having an acid-instable group. (c) Contains a resin (Ap) and a resin (A) containing a structural unit (IP). Preferably, it is the resist composition of (b). It may also contain two or more resins (A) and / or resins (Ap). The resist composition of the present invention preferably contains an acid generator (hereinafter sometimes referred to as "acid generator (B)"), a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)") known in the field of resists. <Carboxylic acid generating agents> Based on the solid content of the resist composition, the content of the carboxylate (I) of the present invention is preferably about 0.001% to 15% by mass, more preferably about 0.001% to 10% by mass, even more preferably about 0.001% to 8% by mass, and even more preferably about 0.005% to 7% by mass. The resin (Ap) content of the present invention is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition.

[0180] <Resins other than Resin (A)> The resist composition of the present invention may also be used in combination with resins other than resin (Ap) and resin (A). Examples of resins other than resin (Ap) and resin (A) include: resin (AX) having the same structural units as resin (A) except that it does not contain structural unit (a1); resin containing structural unit (a4) and / or structural unit (a5) (wherein, it does not contain structural unit (IP) and structural unit (a1). Hereinafter, it is sometimes referred to as "resin (X)"). As the resin (AX), resins containing structural unit (a2) can be listed, and resins containing structural unit (a2-A) are preferred. In the 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 number of structural units in the resin (AX). Furthermore, it is preferably 80 mol% or less, and more preferably 70 mol% or less. As structural units that resin (X) may have, examples include structural units (a2), structural units (a3), and structural units derived from other known monomers. Preferably, resin (X) is a resin containing only structural units (a4) and / or structural units (a5), and more preferably a resin containing only structural unit (a4). When resin (X) contains structural unit (a4), the content of structural unit (a4) relative to the total number of structural units in resin (X) can be 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more. Alternatively, it can be 100 mol% or less, 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 can be 20 mol% to 100 mol%, preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, even more preferably 40 mol% to 60 mol%, and even more preferably 45 mol% to 55 mol%. When resin (X) contains structural unit (a5), the content of structural unit (a5) relative to the total number of structural units in resin (X) can be 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more. Alternatively, it can be 100 mol% or less, 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 can be 20 mol% to 100 mol%, preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, even more preferably 40 mol% to 60 mol%, and even more preferably 45 mol% to 55 mol%. Furthermore, when the resin (X) comprises structural units (a4) and (a5), the total content of structural units (a4) and (a5) relative to the total of all structural units in the resin (X) can be 40 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. Furthermore, it can be 100 mol% or less. Specifically, it can be 40 mol% to 100 mol%, preferably 60 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, and even more preferably 80 mol% to 100 mol%. The structural units constituting resins (AX) and (X) may be used in combination or by using only one type of unit. They may be manufactured using monomers from which these structural units are derived, by a known polymerization method (e.g., free radical polymerization). The content of each structural unit in resins (AX) and (X) may be adjusted by the amount of monomer used in the polymerization. The weight-average molecular weight of resins (AX) and (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The method for determining the weight-average molecular weight of resins (AX) and (X) is the same as that for resin (A).

[0181] When the resist composition of the present invention includes resin (X), the content of resin (X) is preferably 1 part to 60 parts by mass relative to 100 parts by mass of resin (A), more preferably 1 part to 50 parts by mass, even more preferably 1 part to 40 parts by mass, even more preferably 1 part to 30 parts by mass, and particularly preferably 1 part to 8 parts by mass.

[0182] The content of resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition. Furthermore, when resins other than resin (A) are included, the total content of resin (A) and other resins relative to the solid content of the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less. The solid content of the resist composition and the content of resin relative to it can be determined by known analytical methods such as liquid chromatography or gas chromatography.

[0183] <Acid Generator (B)> Acid generating agent (B) can be either nonionic or ionic. Examples of nonionic acid generating agents include: sulfonates (e.g., 2-nitrobenzyl ester, aromatic sulfonates, oxime sulfonates, N-sulfonoxynimodiimides, sulfonoxy ketones, diazonoquinone 4-sulfonates), and ternaries (e.g., di-ternaries, ketone ternaries, sulfonyldiazomethane). Representative examples of ionic acid generating agents are ononium salts containing ononium cations (e.g., diazonium salts, phosphonium salts, strontium salts, monium salts). Examples of ononium salt anions include: sulfonate anions, sulfonylnimodiimide anions, sulfonylmethyl anions, etc.

[0184] As acid generating agent (B), compounds that generate acid by radiation as described in Japanese Patent Application Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, US Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3,914,407, and European Patent No. 126,712 may be used. Alternatively, compounds manufactured by known methods may also be used. Two or more acid generating agents (B) may be used in combination.

[0185] The acid generating agent (B) is preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generating agent (B1)"). In formula (B1), Qb1 and Qb2 independently represent hydrogen atoms, fluorine atoms, perfluoroalkyl groups having 1 to 6 carbon atoms, or alkyl groups having 1 to 6 carbon atoms, respectively. L b1 represents a divalent saturated hydrocarbon group with 1 to 24 carbon atoms. The -CH 2- in this divalent saturated hydrocarbon group can be replaced with -O- or -CO-, and the hydrogen atom in this divalent saturated hydrocarbon group can be replaced with a fluorine atom or a hydroxyl group. Y represents a methyl group that may have substituents or an alicyclic hydrocarbon group with 3 to 24 carbon atoms that may have substituents, wherein the -CH 2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO 2- or -CO-. Z+ indicates an organic cation.

[0186] Examples of perfluoroalkyl groups represented by Qb1 and Qb2 include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorodibutyl, perfluoroterbutyl, perfluoropentyl, and perfluorohexyl. Examples of alkyl groups represented by Qb1 and Qb2 include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, terbutyl, pentyl, hexyl, etc. The acid generating agent (B) is preferably a fluorinated acid generating agent, preferably either Qb1 or Qb2 is a fluorine atom or a perfluoroalkyl group, more preferably both Qb1 and Qb2 are fluorine atoms or trifluoromethyl groups, and even more preferably both are fluorine atoms.

[0187] Examples of divalent saturated hydrocarbon groups in Lb1 include: straight-chain alkyl dimethyl groups, branched alkyl dimethyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and groups formed by combining two or more of these groups. Specifically, examples include: methylene, ethyl, 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, etc., which are straight-chain alkyl diyl groups. Branched alkyldiyl groups include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. Cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, and other cycloalkyl diyl groups are monocyclic divalent alicyclic saturated hydrocarbon groups; Norbornene-1,4-diyl, norbornene-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, and other polycyclic divalent alicyclic saturated hydrocarbon groups.

[0188] As a divalent saturated hydrocarbon group represented by L b1, the group in which -CH 2- is replaced by -O- or -CO-, for example, the groups represented by any of formulas (b1-1) to (b1-3) can be listed. Furthermore, in the groups represented by formulas (b1-1) to (b1-3) and the groups represented by formulas (b1-4) to (b1-11) as specific examples of these, * and ** represent bonding sites, and * represents a bond with -Y.

[0189] In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group with 1 to 22 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom. Lb3 represents a single bond or a divalent saturated hydrocarbon group with 1 to 22 carbon atoms. The hydrogen atom in the saturated hydrocarbon group can be replaced by a fluorine atom or a hydroxyl group, and the -CH 2- in the saturated hydrocarbon group can be replaced by -O- or -CO-. Among them, the combined carbon number of Lb2 and Lb3 is less than 22. In equation (b1-2), Lb4 represents a single bond or a divalent saturated hydrocarbon group with 1 to 22 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom. Lb5 represents a single bond or a divalent saturated hydrocarbon group with 1 to 22 carbon atoms. The hydrogen atom in the saturated hydrocarbon group can be replaced by a fluorine atom or a hydroxyl group, and the -CH 2- in the saturated hydrocarbon group can be replaced by -O- or -CO-. Among them, the combined carbon number of Lb4 and Lb5 is less than 22. In equation (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group with 1 to 23 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. L b7 represents a single bond or a divalent saturated hydrocarbon group with 1 to 23 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group can be replaced by a fluorine atom or a hydroxyl group, and the -CH 2- contained in the saturated hydrocarbon group can be replaced by -O- or -CO-. Among them, the combined carbon number of Lb6 and Lb7 is less than 23.

[0190] Regarding the groups represented by formulas (b1-1) to (b1-3), when the -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbons before the substitution is set as the number of carbons of the saturated hydrocarbon group. As a divalent saturated hydrocarbon group, examples that are identical to the divalent saturated hydrocarbon group of L b1 can be listed.

[0191] Lb2 is preferably a single bond, methylene, -CH(CF3)-, or -C(CF3)2-. Lb3 is preferably a divalent saturated hydrocarbon group with 1 to 4 carbon atoms. Lb4 is preferably a divalent saturated hydrocarbon group with 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group can be replaced by a fluorine atom, preferably methylene, -CH(CF3)-, or -C(CF3)2-. Lb5 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb6 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group can be replaced by a fluorine atom. Lb7 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group can be replaced by a fluorine atom or a hydroxyl group, and the -CH 2- contained in the divalent saturated hydrocarbon group can be replaced by -O- or -CO-.

[0192] The group in which the -CH 2- is substituted by -O- or -CO- in the divalent saturated hydrocarbon group represented by L b1 is preferably the group represented by formula (b1-1) or formula (b1-3). As the basis represented by equation (b1-1), the bases represented by equations (b1-4) to (b1-8) can be listed respectively. In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group with 1 to 22 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. In equation (b1-5), L b9 represents a divalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the -CH 2- can be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group with 1 to 19 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. Among them, the combined carbon number of Lb9 and Lb10 is less than 20. In equation (b1-6), L b11 represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. Among them, the combined carbon number of Lb11 and Lb12 is less than 21. In equation (b1-7), L b13 represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, wherein the -CH 2- contained in the divalent saturated hydrocarbon group can be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. Among them, the total number of carbon atoms in Lb13 to Lb15 is less than 19. In equation (b1-8), L b16 represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, in which the -CH 2- can be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group with 1 to 17 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom or a hydroxyl group. Among them, the total carbon number of Lb16 to Lb18 is less than 19.

[0193] Lb8 is preferably a divalent saturated hydrocarbon group with 1 to 4 carbon atoms. Lb9 is preferably a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb10 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb11 is preferably a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb12 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb13 is preferably a divalent saturated hydrocarbon group with 1 to 12 carbon atoms. Lb14 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 6 carbon atoms. Lb15 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group with 1 to 8 carbon atoms. Lb16 is preferably a divalent saturated hydrocarbon group with 1 to 12 carbon atoms. Lb17 is preferably a divalent saturated hydrocarbon group with 1 to 6 carbon atoms. Lb18 is preferably a single bond or a divalent saturated hydrocarbon group with 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group with 1 to 4 carbon atoms.

[0194] As the basis represented by equation (b1-3), the bases represented by equations (b1-9) to (b1-11) can be listed respectively. In equation (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group with 1 to 23 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom. Lb20 represents a single bond or a divalent saturated hydrocarbon group with 1 to 23 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom, a hydroxyl group, or an alkyl carbonyl group. The -CH2- in the alkyl carbonyl group can be replaced by -O- or -CO-, and the hydrogen atom in the alkyl carbonyl group can be replaced by a hydroxyl group. Among them, the combined carbon number of Lb19 and Lb20 is less than 23. In equation (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group with 1 to 21 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. Lb23 represents a single bond or a divalent saturated hydrocarbon group with 1 to 21 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom, a hydroxyl group, or an alkyl carbonyl group. The -CH2- in the alkyl carbonyl group can be replaced by -O- or -CO-, and the hydrogen atom in the alkyl carbonyl group can be replaced by a hydroxyl group. Among them, the total number of carbon atoms in Lb21, Lb22 and Lb23 is less than 21. In equation (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom. L b25 represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. Lb26 represents a single bond or a divalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atom can be replaced by a fluorine atom, a hydroxyl group, or an alkyl carbonyl group. The -CH2- in the alkyl carbonyl group can be replaced by -O- or -CO-, and the hydrogen atom in the alkyl carbonyl group can be replaced by a hydroxyl group. Among them, Lb24, Lb25 and Lb26 have a total carbon number of less than 21.

[0195] Furthermore, regarding the groups represented by formulas (b1-9) to (b1-11), when the hydrogen atom contained in the saturated hydrocarbon group is replaced by an alkyl carbonyl group, the number of carbon atoms before the substitution is set as the number of carbon atoms of the saturated hydrocarbon group. Examples of alkyl carbonyl groups include: acetylated carbonyl group, propionic carbonyl group, butylated carbonyl group, cyclohexyl carbonyl group, adamantyl carbonyl group, etc.

[0196] The following can be listed as bases represented by equation (b1-4).

[0197] The following can be listed as bases represented by equation (b1-5).

[0198] The following can be listed as bases represented by equation (b1-6).

[0199] The following can be listed as bases represented by equation (b1-7).

[0200] The following can be listed as bases represented by equation (b1-8).

[0201] The following can be listed as bases represented by equation (b1-2).

[0202] The following can be listed as bases represented by equation (b1-9).

[0203] The following can be listed as bases represented by equation (b1-10).

[0204] The following can be listed as bases represented by equation (b1-11).

[0205] As for the alicyclic hydrocarbon group represented by Y, the groups represented by formulas (Y1) to (Y11) and (Y36) to (Y38) can be listed. When the -CH 2- group in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S-, -SO 2-, or -CO-, the number of such replacements can be one or more. Examples of such groups include those represented by formulas (Y12) to (Y35) and (Y39) to (Y43). The -O- or -CO- bond positions in the groups represented below can be replaced by -S- or -SO 2-.

[0206] The alicyclic hydrocarbon group represented by Y is preferably represented by any one of formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y43), more preferably by formulas (Y11), (Y15), (Y16), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42) or (Y43), and even more preferably by formulas (Y11), (Y15), (Y20), (Y26), (Y27), (Y30), (Y31), (Y39), (Y40), (Y42) or (Y43). When the alicyclic hydrocarbon group represented by Y is a spirocyclic ring containing an oxygen atom, such as formulas (Y28) to (Y35), (Y39), (Y40), (Y42), or (Y43), the alkyl diene between the two oxygen atoms preferably has one or more fluorine atoms. Furthermore, in the ketal structure, the methylene group adjacent to the oxygen atom in the alkyl diene preferably has an unsubstituted fluorine atom.

[0207] Examples of substituents for the methyl group represented by Y include: halogen atoms, hydroxyl groups, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, glycidyloxy groups, -(CH2)ja-CO-ORb1 groups or -(CH2)ja-O-CO-Rb1 groups (where Rb1 represents an alkyl group with 1 to 16 carbon atoms, an alicyclic hydrocarbon group with 3 to 16 carbon atoms, an aromatic hydrocarbon group with 6 to 18 carbon atoms, or a combination thereof; the -CH2- group 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 hydroxyl or fluorine atoms. ja represents any integer from 0 to 4). Examples of substituents for the alicyclic hydrocarbon group represented by Y include: halogen atoms, hydroxyl groups, alkyl groups of 1 to 16 carbons that can be substituted by hydroxyl groups (where -CH2- can be substituted by -O- or -CO-), alicyclic hydrocarbon groups of 3 to 16 carbons, aromatic hydrocarbon groups of 6 to 18 carbons, aralkyl groups of 7 to 21 carbons, glycidyl oxy groups, -(CH2)ja-CO-ORb1 group or -(CH2)ja-O-CO-Rb1 group (where Rb1 represents an alkyl group of 1 to 16 carbons, an alicyclic hydrocarbon group of 3 to 16 carbons, an aromatic hydrocarbon group of 6 to 18 carbons, or a combination thereof, wherein -CH2- in the alkyl group and the alicyclic hydrocarbon group can be substituted with -O- or -SO-). 2- or -CO-, where the hydrogen atom in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced with a hydroxyl or fluorine atom. (ja represents any integer from 0 to 4), etc.

[0208] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl. Alicyclic hydrocarbon groups can also have chain-like hydrocarbon groups, such as methylcyclohexyl and dimethylcyclohexyl. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 10. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, biphenyl, phenanthrene, and other aryl groups. The aromatic hydrocarbon group can be a chain hydrocarbon group or an alicyclic hydrocarbon group, preferably an aromatic hydrocarbon group with 1 to 18 carbon atoms (tolyl, xylyl, cumenel, mesitylene, p-methylphenyl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.) and an aromatic hydrocarbon group with 3 to 18 carbon atoms (p-adamantylphenyl, p-cyclohexylphenyl, etc.). The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkyl groups that are substituted with hydroxyl groups include hydroxymethyl, hydroxyethyl, and other hydroxyalkyl groups. Examples of aralkyl groups include: benzyl, phenylethyl, phenylpropyl, naphthylmethyl, and naphthylethyl. Examples of alkyl groups in which -CH 2- is replaced by -O-, -SO 2- or -CO- include: alkoxy, alkylsulfonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, or combinations thereof. Examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, decyloxy, and dodecyloxy. 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 alkyl sulfonyl groups include: methanesulfonyl, ethylsulfonyl, propylsulfonyl, etc. 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, ethoxycarbonyl, and butoxycarbonyl. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkyl carbonyl groups include acetyl, propionic, and butyryl. The number of carbon atoms in the alkyl carbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkyl carbonyloxy groups include acetylated carbonyloxy, propionic carbonyloxy, and butylated carbonyloxy. The number of carbon atoms in the alkyl carbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of groups that can be combined include: groups formed by combining alkoxy groups with alkyl groups, groups formed by combining alkoxy groups with alkoxy groups, groups formed by combining alkoxy groups with alkyl carbonyl groups, and groups formed by combining alkoxy groups with alkyl carbonyl groups. Examples of alkoxyalkyl groups formed by combining alkoxy groups and alkyl groups include methoxymethyl, methoxyethyl, ethoxyethyl, ethoxymethyl, and other alkoxyalkyl groups. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkoxy groups formed by combining alkoxy groups include: methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, etc. The number of carbon atoms in an alkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of groups formed by combining an alkoxy group and an alkyl carbonyl group include methoxyacetyl, methoxypropionic, ethoxyacetyl, ethoxypropionic, and other alkoxyalkyl carbonyl groups. The alkoxyalkyl carbonyl group preferably has 3 to 13 carbon atoms, more preferably 3 to 7, and even more preferably 3 to 5. Examples of groups formed by combining alkoxy and alkyl carbonyloxy groups include: methoxyacetyloxy, methoxypropyloxy, ethoxyacetyloxy, ethoxypropyloxy, and other alkoxyalkyl carbonyloxy groups. The number of carbon atoms in the alkoxyalkyl carbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. As a group in which -CH 2- is replaced by -O-, -SO 2- or -CO-, the groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43) can be listed.

[0209] Y is preferably an alicyclic hydrocarbon group with 3 to 24 carbon atoms that may have substituents, more preferably an alicyclic hydrocarbon group with 3 to 20 carbon atoms that may have substituents, further preferably an alicyclic hydrocarbon group with 3 to 18 carbon atoms that may have substituents, and even more preferably an adamantyl or norbornyl group that may have substituents. The -CH 2- constituting the alicyclic hydrocarbon group, adamantyl or norbornyl group may also be replaced with -CO-, -SO 2- or -CO-. Specifically, the following can be listed.

[0210] Wherein, Y is preferably adamantyl, hydroxydamantyl, oxodamantyl, norbornene lactone, or a group represented by formula (Y42), (Y100) to (Y114), (Y134) to (Y139).

[0211] The anion in the salt represented by formula (B1) is preferably an anion represented by formulas (B1-A-1) to (B1-A-65) (hereinafter, it is sometimes referred to as "anion (B1-A-1)" or the like corresponding to the formula number), and more preferably an anion represented by any one 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), and (B1-A-47) to (B1-A-65).

[0212]

[0213] Here, Ri2 to Ri7 are independently, for example, alkyl groups having 1 to 4 carbon atoms, preferably methyl or ethyl. Ri8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably methyl, ethyl, cyclohexyl, or adamantyl. LA41 is a single bond or an alkyl diel having 1 to 4 carbon atoms. Qb1 and Qb2 have the same meaning as described above. Specifically, the anions in the salt represented by formula (B1) can be listed in Japanese Patent Application Publication No. 2010-204646.

[0214] The anion in the salt represented by formula (B1) is preferably the anion represented by formulas (B1a-1) to (B1a-43).

[0215]

[0216] Preferably, the anion is represented by any one of formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), or (B1a-22) to (B1a-38). Sulfoimidin anions and sulfomethyl anions can be listed as being the same as those described above.

[0217] Examples of Z+ organic cations include: organonium cations, organostronium cations, organosmium cations, organammonium cations, benzothiazolium cations, and organophosphorus cations. Among these, organostronium cations and organosmium cations are preferred, and arylstromium cations are even more preferred. Specifically, cations represented by any of formulas (b2-1) to (b2-4) can be listed (hereinafter, sometimes referred to as "cation (b2-1)" etc., corresponding to the formula number). In equations (b2-1) to (b2-4), Rb4 to Rb6 independently represent a chain hydrocarbon group with 1 to 30 carbon atoms, an alicyclic hydrocarbon group with 3 to 36 carbon atoms, or an aromatic hydrocarbon group with 6 to 36 carbon atoms. The hydrogen atom in the chain hydrocarbon group can be replaced by a hydroxyl group, an alkoxy group with 1 to 12 carbon atoms, an alicyclic hydrocarbon group with 3 to 12 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms. The hydrogen atom in the alicyclic hydrocarbon group can be replaced by a halogen atom, an aliphatic hydrocarbon group with 1 to 18 carbon atoms, an alkyl carbonyl group with 2 to 4 carbon atoms, or a glycidoxy group. The hydrogen atom in the aromatic hydrocarbon group can be replaced by a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group with 1 to 18 carbon atoms, a fluorinated alkyl group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms. Rb4 and Rb5 can bond to each other and form a ring together with the bonded sulfur atoms. The -CH2- in the ring can be replaced by -O-, -S- or -CO-. Rb7 and Rb8 independently represent a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms, respectively. m2 and n2 each independently represent any integer from 0 to 5. When m2 is 2 or more, multiple R b7s can be the same or different; when n2 is 2 or more, multiple R b8s can be the same or different. Rb9 and Rb10 independently represent either a chain hydrocarbon group with 1 to 36 carbon atoms or an alicyclic hydrocarbon group with 3 to 36 carbon atoms. Rb9 and Rb10 can bond to each other and form a ring together with the bonded sulfur atoms. The -CH2- in the ring can be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, an alicyclic hydrocarbon group with 3 to 36 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group with 1 to 12 carbon atoms, an alicyclic hydrocarbon group with 3 to 18 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms. The hydrogen atoms contained in the chain hydrocarbon group can be replaced by an aromatic hydrocarbon group with 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group can be replaced by an alkoxy group with 1 to 12 carbon atoms or an alkyl carbonyloxy group with 1 to 12 carbon atoms. Rb11 and Rb12 can bond to each other and contain the bonded -CH-CO- to form a ring, in which the -CH2- can be replaced by -O-, -S- or -CO-. Rb13 to Rb18 represent, independently, a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group with 1 to 12 carbon atoms, a fluorinated alkyl group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different; when p2 is 2 or more, multiple R b14 are the same or different; when q2 is 2 or more, multiple R b15 are the same or different; when r2 is 2 or more, multiple R b16 are the same or different; when s2 is 2 or more, multiple R b17 are the same or different; when t2 is 2 or more, multiple R b18 are the same or different. The term aliphatic hydrocarbon groups refers to both chain hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include: methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tributyl, pentyl, hexyl, octyl, and 2-ethylhexyl alkyl groups. In particular, the chain hydrocarbon groups of Rb9 to Rb12 are preferably 1 to 12 carbon atoms. As an alicyclic hydrocarbon group, it can be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and other cycloalkyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups. In particular, the alicyclic hydrocarbon groups of Rb9 to Rb12 are preferably 3 to 18 carbons, and more preferably 4 to 12 carbons. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include: methylcyclohexyl, dimethylcyclohexyl, 2-methyladamantane-2-yl, 2-ethyladamantane-2-yl, 2-isopropyladamantane-2-yl, methylnorbornyl, isobornyl, etc. For alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The term "fluorinated alkyl" refers to an alkyl group having 1 to 12 carbon atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, and perfluorobutyl. The preferred number of carbon atoms in a fluorinated alkyl group is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthrene aryl groups. Aromatic hydrocarbon groups can be either chain-like or alicyclic. Examples include chain-like hydrocarbon groups with 1 to 18 carbon atoms (tolyl, xylyl, cumenel, mesitylene, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.) and alicyclic hydrocarbon groups with 3 to 18 carbon atoms (p-cyclohexylphenyl, p-adamantylphenyl, etc.). Furthermore, when the aromatic hydrocarbon group has either a chain-like or alicyclic hydrocarbon group, chain-like 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 hydrogen atoms are replaced by alkoxy groups include p-methoxyphenyl. Examples of chain hydrocarbon groups in which hydrogen atoms are replaced by aromatic hydrocarbon groups include: benzyl, phenylethyl, phenylpropyl, triphenylmethyl, naphthylmethyl, naphthylethyl, and other aryl groups. Examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, decoxy, and dodecyloxy. Examples of alkyl carbonyl groups include acetyl, propionic, and butyryl. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl carbonyloxy groups include: methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, dibutyl carbonyloxy, terbutyl carbonyloxy, pentyl carbonyloxy, hexyl carbonyloxy, octyl carbonyloxy, and 2-ethylhexyl carbonyloxy. The ring formed by the mutual bonding of Rb4 and Rb5 with the bonded sulfur atoms can be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of such rings include those with 3 to 18 carbon atoms, preferably 4 to 18. Furthermore, the ring containing sulfur atoms can be 3 to 12-membered, preferably 3 to 7-membered, for example, the following rings. * indicates the bonding site. The ring formed by Rb9 and Rb10 can be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of rings include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples include: thiocyclopentane-1-ring (tetrahydrothiophene ring), thiocyclohexane-1-ring, and 1,4-oxothiocyclohexane-4-ring. The ring formed by Rb11 and Rb12 can be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of rings include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples include oxo-heptane rings, oxo-cyclohexane rings, oxo-norbornene rings, and oxo-adamantane rings.

[0218] Among cations (b2-1) to (b2-4), cation (b2-1) is preferred. The following cations can be listed as cations (b2-1). The following cations can be listed as cations (b2-2). The following cations can be listed as cations (b2-3). The following cations can be listed as cations (b2-4).

[0219] The acid generator (B) is a combination of the said anion and the said organic cation, which can be combined arbitrarily. Preferably, the acid generator (B) is 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) with a cation (b2-1), cation (b2-2), cation (b2-3), or cation (b2-4).

[0220] As an acid generating agent (B), it is preferably represented by formulas (B1-1) to (B1-60). Among them, it is more preferably a aryl strontium cation, and even more preferably a cation 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).

[0221]

[0222]

[0223] In the resist composition of the present invention, the content of the acid generating agent relative to the solid component of the resist composition 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, further 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. When the resin (A) is included, the content of the acid generating agent relative to 100 parts by mass of the resin (A) 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.

[0224] Solvent (E) In the resist composition, the solvent (E) content is typically 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 solvent (E) content can be determined, for example, by known analytical methods such as liquid chromatography or gas chromatography.

[0225] Examples of solvents (E) include: glycol ether esters such as ethyl cellulose acetate, methyl cellulose 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; and cyclic esters such as γ-butyrolactone. One solvent (E) may be used alone, or two or more may be used.

[0226] <Quencher (C)> Examples of quenching agents (C) include salts of acids that produce acids weaker than those produced by the acid-generating agent (B), and basic nitrogen-containing organic compounds. Based on the solid content of the resist composition, the content of quenching agent (C) is preferably about 0.01% to 15% by mass, more preferably about 0.01% to 10% by mass, even more preferably about 0.1% to 8% by mass, and even more preferably about 0.1% to 7% by mass.

[0227] <Salts that produce acids weaker than those produced by the acid-producing agent> The acidity of the salt that generates an acid with a weaker acidity than the acid generated by the acid generator (B) is expressed by the acid dissociation constant (pKa). The salt that generates an acid with a weaker acidity than the acid generated by the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is generally -3 < pKa, preferably -1 < pKa < 7, more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a weaker acidity than the acid generated by the acid generator (B) include: the salt represented by the following formula, the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. As the salt that generates an acid with a weaker acidity than the acid generated by the acid generator (B), preferably a salt of a carboxylic acid (a salt having a carboxylate anion) that generates an acid with a weaker acidity than the acid generated by the acid generator (B), more preferably the weak acid inner salt (D).

[0228] As the weak acid inner salt (D), preferably a diphenylsulfonium salt having a sulfonium cation bonded to two phenyl groups and a carboxylate anion substituting at least one of the two phenyl groups bonded to the sulfonium cation, and examples of the salt include those represented by the following formulas. [In formula (D), R D1 and R D2 each independently represent 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 any integer from 0 to 4. When m' is 2 or more, the plurality of R D's may be the same or different, and when n' is 2 or more, the plurality of R D2's may be the same or different] Examples of the hydrocarbon group in R D1 and R D2 include: a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by a combination of these. Examples of the chain hydrocarbon group include: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and nonyl. As an alicyclic hydrocarbon group, it can be either monocyclic or polycyclic, and can be either saturated or unsaturated. Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, cyclododecyl and other cycloalkyl groups, norbornyl, adamantyl, etc. Examples of aromatic hydrocarbon groups include: phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, anthracene, p-adamantylphenyl, tolyl, xylyl, cumenel, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, and other aryl groups. Examples of groups formed by combining these groups include: alkyl-cycloalkyl, cycloalkyl-alkyl, aralkyl (e.g., phenylmethyl, 1-phenylethyl, 2-phenylethyl, 1-phenyl-1-propyl, 1-phenyl-2-propyl, 2-phenyl-2-propyl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, etc.). Examples of alkoxy groups include methoxy and ethoxy. Examples of acetylated groups include: acetylated, propionic, benzoyl, and cyclohexane carbonyl. Examples of acetylated groups include those with an oxygen group (-O-) bonded to the acetylated group. Examples of alkoxy carbonyl groups include those with a carbonyl (-CO-) bonded to the alkoxy group. Examples of halogen atoms include fluorine, chlorine, and bromine. R D1 and R D2 are preferably independently alkyl with 1 to 8 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, alkoxy with 1 to 6 carbon atoms, acetyl with 2 to 4 carbon atoms, acetyloxy with 2 to 4 carbon atoms, alkoxycarbonyl with 2 to 4 carbon atoms, nitro or halogen atom. m' and n' are preferably independent integers from 0 to 2, and more preferably 0. When m' is 2 or more, multiple R D1s can be the same or different. When n' is 2 or more, multiple R D2s can be the same or different. More specifically, the following salts can be listed.

[0229] As basic nitrogen-containing organic compounds, amines and ammonium salts can be listed. Aliphatic amines and aromatic amines can be listed. As aliphatic amines, primary amines, secondary amines, and tertiary amines can be listed. Examples of amines include: 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-methylaniline, 3-methylaniline or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, and trihexylamine. Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutylamine, Ethyldipentylamine, Ethyldihexylamine, Ethyldiheptylamine, Ethyldinonylamine, Ethyldidecylamine, Dicyclohexylmethylamine, Tri[2-(2-methoxyethoxy)ethyl]amine, Triisopropanolamine, Ethylenediamine, Tetramethylenediamine Amines, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisphenylamine, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl) Ethylene, 1,2-di(4-pyridyl)ethylene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)one, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dimethylpyridinylamine, bipyridine, etc., preferably aromatic amines such as diisopropylaniline, and more preferably 2,6-diisopropylaniline. Examples of ammonium salts include: tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

[0230] <Other Ingredients> The resist composition of the present invention may also contain other components besides those described herein (hereinafter sometimes referred to as "other components (F)"). Other components (F) are not particularly limited and may be additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc.

[0231] <Preparation of the resist composition> The resist composition of the present invention can be prepared by mixing a resin containing a carboxylate represented by formula (I) or a structural unit represented by formula (I-1), any 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 range from 10°C to 40°C, and an appropriate temperature can be selected based on the type of resin or the solubility of the resin in the solvent (E). The mixing time can be selected from 0.5 hours to 24 hours depending on the mixing temperature. Furthermore, the mixing method is not particularly limited, and stirring or mixing can be used. After mixing the components, it is preferable to use a filter with a pore size of about 0.003 μm to 0.2 μm for filtration.

[0232] <Method for Manufacturing Resist Patterns> The method for manufacturing the resist pattern of the present invention includes: (1) The step of coating the resist composition of the present invention onto a substrate; (2) The step of drying the coated composition to form a composition layer; (3) The step of exposing the constituent layers; (4) The step of heating the exposed constituent layer; and (5) The step of developing the heated composition layer. When coating the resist composition onto a substrate, it can be done using commonly used equipment such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers and organic substrates on which a resist film is formed. Before coating the resist composition, the substrate can be cleaned, and an anti-reflective film can be formed on the substrate. The solvent is removed by drying the coated composition, forming a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a heating plate (so-called pre-baking), or by using a depressurization device. The heating temperature is preferably 50°C to 200°C, and the heating time is preferably 10 seconds to 180 seconds. In addition, the pressure during depressurization drying is preferably about 1 Pa to 1.0 × 10⁵ Pa. The obtained constituent layers are typically exposed using an exposure machine. This exposure machine can be an immersion exposure machine. As the exposure light source, various sources can be used, including laser light emitting ultraviolet light such as KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm); high-harmonic laser light emitting far-ultraviolet or vacuum ultraviolet light by wavelength conversion of laser light from solid-state laser sources (such as YAG or semiconductor lasers); and electron beams or ultraviolet (EUV) light. Furthermore, in this specification, the irradiation of these radiation sources is sometimes collectively referred to as "exposure." During exposure, a mask corresponding to the desired pattern is usually used. When the exposure light source is an electron beam, exposure can also be performed by direct drawing without using a mask. To promote the deprotection reaction of acid-indestructible groups, the exposed composition layer is subjected to heat treatment (so-called post-exposure bake). The heating temperature is usually around 50°C to 200°C, preferably around 70°C to 150°C. Chemical treatment (silylation) can also be performed to adjust the hydrophilicity or hydrophobicity of the resin present on the surface of the heated composition. Furthermore, before development, the steps of coating, drying, exposing, and heating the resist composition can be repeatedly performed on the exposed composition layer. A developing apparatus is typically used, and a developing solution is employed to develop the heated resist layer. Examples of developing methods include: immersion, coating, spraying, and dynamic dispense. The preferred developing temperature is, for example, 5°C to 60°C, and the preferred developing time is, for example, 5 seconds to 300 seconds. By selecting the type of developing solution as follows, positive or negative resist patterns can be created. When manufacturing a positive resist pattern using 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. Examples include aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may also contain a surfactant. It is preferable to use ultrapure water to clean the resist pattern after development, and then remove the water remaining on the substrate and the pattern. When a negative resist pattern is manufactured 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. Organic solvents included in organic-based 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; acetamide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. In organic-based developers, the content of organic solvents is preferably 90% by mass or more and 100% by mass, more preferably 95% by mass or more and 100% by mass, and even more preferably is essentially only organic solvents. The organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass, more preferably 90% by mass or more and 100% by mass, and even more preferably substantially only butyl acetate and / or 2-heptanone. Organic-based developers may also contain surfactants. Additionally, organic-based developers may contain trace amounts of water. During development, development can also be stopped by replacing the solvent with a different type of organic developer. It is preferable to use a rinsing solution to clean the developed resist pattern. There are no particular limitations on the rinsing solution, as long as it does not dissolve the resist pattern; a solution containing a common organic solvent can be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove the residual rinsing solution from the substrate and pattern.

[0233] <use> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, ArF excimer laser exposure, electron beam (EB) exposure, or EUV exposure, especially for electron beam (EB) exposure or EUV exposure, and is useful in the microfabrication of semiconductors. [Example]

[0234] Examples are provided to illustrate the invention in more detail. In these examples, unless otherwise specified, "%" and "parts" indicating content or usage are mass standards. The weight-average molecular weight was determined by gel permeation chromatography. Furthermore, the analytical conditions for gel permeation chromatography are as follows. Column: TSK gel multipore H XL-M × 3 + guard column (manufactured by Tosoh Corporation) Dissolution solution: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by determining the molecular ion peak using mass spectrometry (LC 1100 manufactured by Agilent and MASS LC / MSD manufactured by Agilent). In the following examples, "MASS" is used to denote the value of the molecular ion peak.

[0235] Example 1: Synthesis of the salt represented by formula (I-1) 5.28 parts of the compound represented by formula (I-1-a), 30 parts of acetonitrile, and 2.32 parts of silver oxide were mixed, stirred at 23°C for 4 hours, and filtered. 20 parts of third butyl methyl ether were added to the obtained filtrate, stirred at 23°C for 30 minutes, and filtered to obtain 5.86 parts of the salt represented by formula (I-1-b). 3.91 parts of the salt represented by formula (I-1-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by liquid-liquid extraction to obtain the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by liquid-liquid extraction to obtain the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 5.82 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum): M +355.1 MASS(ESI(-)Spectrum): M -263.1

[0236] Example 2: Synthesis of the salt represented by formula (I-190) 5.16 parts of the salt represented by formula (I-190-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 7.01 parts of the salt represented by formula (I-190). MASS(ESI(+)Spectrum):M +481.0 MASS(ESI(-)Spectrum): M -263.1

[0237] Example 3: Synthesis of the salt represented by formula (I-192) 5.32 parts of the compound represented by formula (I-192-a), 30 parts of acetonitrile, and 2.32 parts of silver oxide were mixed, stirred at 23°C for 4 hours, and filtered. 20 parts of third butyl methyl ether were added to the obtained filtrate, stirred at 23°C for 30 minutes, and filtered to obtain 5.61 parts of the salt represented by formula (I-192-b). 5.16 parts of the salt represented by formula (I-190-c), 3.73 parts of the salt represented by formula (I-192-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by liquid-liquid extraction to obtain the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by liquid-liquid extraction to obtain the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 6.24 parts of the salt represented by formula (I-192). MASS(ESI(+)Spectrum):M +481.0 MASS(ESI(-)Spectrum): M -265.1

[0238] Example 4: Synthesis of the salt represented by formula (I-194) 4.12 parts of the compound represented by formula (I-194-a), 30 parts of acetonitrile, and 2.32 parts of silver oxide were mixed, stirred at 23°C for 4 hours, and filtered. 20 parts of third butyl methyl ether were added to the obtained filtrate, stirred at 23°C for 30 minutes, and filtered to obtain 4.31 parts of the salt represented by formula (I-194-b). 5.16 parts of the salt represented by formula (I-190-c), 3.13 parts of the salt represented by formula (I-194-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 5.08 parts of the salt represented by formula (I-194). MASS(ESI(+)Spectrum):M +481.0 MASS(ESI(-)Spectrum): M -205.1

[0239] Example 5: Synthesis of the salt represented by formula (I-946) 6.53 parts of the salt represented by formula (I-946-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 8.02 parts of the salt represented by formula (I-946). MASS(ESI(+)Spectrum): M +617.0 MASS(ESI(-)Spectrum): M -263.1

[0240] Example 6: Synthesis of the salt represented by formula (I-1000) 6.17 parts of the salt represented by formula (I-1000-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 7.43 parts of the salt represented by formula (I-1000). MASS(ESI(+)Spectrum): M +581.0 MASS(ESI(-)Spectrum): M -263.1

[0241] Example 7: Synthesis of the salt represented by formula (I-1189) 5.31 parts of the salt represented by formula (I-1189-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 6.06 parts of the salt represented by formula (I-1189). MASS(ESI(+)Spectrum): M +495.0 MASS(ESI(-)Spectrum): M -263.1

[0242] Example 8: Synthesis of the salt represented by formula (I-1405) 5.16 parts of the salt represented by formula (I-1405-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 7.68 parts of the salt represented by formula (I-1405). MASS(ESI(+)Spectrum): M +636.9 MASS(ESI(-)Spectrum): M -263.1

[0243] Example 9: Synthesis of the salt represented by formula (I-2482) 8.09 parts of the salt represented by formula (I-2482-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 8.81 parts of the salt represented by formula (I-2482). MASS(ESI(+)Spectrum): M +772.9 MASS(ESI(-)Spectrum): M -263.1

[0244] Example 10: Synthesis of the salt represented by formula (I-2509) 8.09 parts of the salt represented by formula (I-2509-c), 3.71 parts of the salt represented by formula (I-1-b), 20 parts of methanol, and 10 parts of deionized water were mixed and stirred at 23°C for 30 minutes. 0.44 parts of potassium carbonate were added to the obtained mixture, and the mixture was stirred at 23°C for 5 hours. 60 parts of chloroform and 10 parts of deionized water were added to the obtained reaction product, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. 30 parts of deionized water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to extract the organic layer. This washing operation was repeated seven times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and concentrated to obtain 8.44 parts of the salt represented by formula (I-2509). MASS(ESI(+)Spectrum): M +772.9 MASS(ESI(-)Spectrum): M -263.1

[0245] Resin Synthesis The following shows the compounds (monomers) used in the synthesis of resin (A). Hereinafter, these compounds will be referred to as "monomers (a1-1-3)" etc., according to their formula numbers.

[0246] Example 11 [Synthesis of Resin A1] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-1)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A1 with a weight average molecular weight of approximately 5.5 × 10³ in a yield of 64%. Resin A1 has the following structural units.

[0247] Example 12 [Synthesis of Resin A2] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-190) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-190)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A2 with a weight average molecular weight of approximately 5.4 × 10³ in a yield of 60%. Resin A2 has the following structural units.

[0248] Example 13 [Synthesis of Resin A3] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-192) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-192)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A3 with a weight average molecular weight of approximately 5.6 × 10³ in a yield of 62%. Resin A3 has the following structural units.

[0249] Example 14 [Synthesis of Resin A4] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-194) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-194)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A4 with a weight average molecular weight of approximately 5.2 × 10³ in a yield of 66%. Resin A4 has the following structural units.

[0250] Example 15 [Synthesis of Resin A5] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-190) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13): monomer (I-190)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid, in a mass ratio of 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A5 with a weight average molecular weight of approximately 5.4 × 10³ in a yield of 58%. Resin A5 has the following structural units.

[0251] Example 16 [Synthesis of Resin A6] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-190) were mixed in a molar ratio of 55:3:12:25:5. Then, 1.5 times the total mass of all monomers was added to this monomer mixture as initiators. To the resulting mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) were added as initiators, respectively, and the mixture was heated at 73°C for approximately 5 hours. Afterward, 2.0 times the total mass of all monomers was added to the polymerization reaction mixture as initiators, and the mixture was stirred for 12 hours before separation. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A6 with a weight average molecular weight of approximately 5.4 × 10³ in a yield of 78%. Resin A6 has the following structural units.

[0252] Example 17 [Synthesis of Resin A7] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-190) were mixed in a molar ratio of 55:3:12:25:5 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13): monomer (I-190)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A7 with a weight average molecular weight of approximately 5.4 × 10³ in 70% yield. Resin A7 has the following structural units.

[0253] Example 18 [Synthesis of Resin A8] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-19), and (I-190) were mixed in a molar ratio of 55:3:12:25:5 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-19): monomer (I-190)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A8 with a weight average molecular weight of approximately 5.3 × 10³ in a yield of 73%. Resin A8 has the following structural units.

[0254] Example 19 [Synthesis of Resin A9] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-20), and (I-190) were mixed in a molar ratio of 55:3:12:25:5 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-20): monomer (I-190)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A9 with a weight average molecular weight of approximately 5.5 × 10³ in a yield of 64%. Resin A9 has the following structural units.

[0255] Example 20 [Synthesis of Resin A10] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-946) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-946)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A10 with a weight average molecular weight of approximately 5.4 × 10³ in a yield of 63%. Resin A10 has the following structural units.

[0256] Example 21 [Synthesis of Resin A11] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1000) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-1000)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A11 with a weight average molecular weight of approximately 5.6 × 10³ in a yield of 61%. Resin A11 has the following structural units. Example 22 [Synthesis of Resin A12] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1189) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-1189)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), which is 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A12 with a weight average molecular weight of approximately 5.3 × 10³ in a yield of 66%. Resin A12 has the following structural units.

[0257] Example 23 [Synthesis of Resin A13] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1405) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-1405)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A13 with a weight average molecular weight of approximately 5.4 × 10³ in a yield of 62%. Resin A13 has the following structural units.

[0258] Example 24 [Synthesis of Resin A14] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-1189) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13): monomer (I-1189)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid, in a mass ratio of 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A14 with a weight average molecular weight of approximately 5.3 × 10³ in a yield of 61%. Resin A14 has the following structural units.

[0259] Example 25 [Synthesis of Resin A15] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-1189) were mixed in a molar ratio of 55:3:12:25:5. Then, 1.5 times the total mass of all monomers was added to this monomer mixture as initiators. To the resulting mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) were added as initiators, respectively, and the mixture was heated at 73°C for approximately 5 hours. Afterward, 2.0 times the total mass of all monomers was added to the polymerization reaction mixture as initiators, and the mixture was stirred for 12 hours before separation. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A15 with a weight average molecular weight of approximately 5.5 × 10³ in a yield of 84%. Resin A15 has the following structural units.

[0260] Example 26 [Synthesis of Resin A16] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-13), and (I-1189) were mixed in a molar ratio of 55:3:12:25:5 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13): monomer (I-1189)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A16 with a weight average molecular weight of approximately 5.3 × 10³ in 75% yield. Resin A16 has the following structural units.

[0261] Example 27 [Synthesis of Resin A17] As monomers, monomers (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-19), and (I-1189) were mixed in a molar ratio of 55:3:12:25:5 [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-19): monomer (I-1189)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A17 with a weight average molecular weight of approximately 5.3 × 10³ in a yield of 79%. Resin A17 has the following structural units.

[0262] Example 28 [Synthesis of Resin A18] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-2482) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-2482)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A18 with a weight average molecular weight of approximately 5.6 × 10³ in a yield of 65%. Resin A18 has the following structural units.

[0263] Example 29 [Synthesis of Resin A19] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (I-2509) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (I-2509)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin A19 with a weight average molecular weight of approximately 5.3 × 10³ in a yield of 62%. Resin A19 has the following structural units.

[0264] Synthesis Example 1 [Synthesis of Resin AX1] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), (a1-4-2), and (AX-1) were mixed in a molar ratio of 20:35:3:12:25:5 [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2): monomer (AX-1)]. Then, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, relative to the amount of each monomer, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin AX1 with a weight average molecular weight of approximately 5.5 × 10³ in a yield of 66%. This resin AX1 has the following structural units.

[0265] Synthesis Example 2 [Synthesis of Resin AA1] As monomers, monomers (a1-1-3), (a1-2-6), (a2-1-3), (a3-4-2), and (a1-4-2) were mixed in a molar ratio of 20:35:3:15:27. Then, methyl isobutyl ketone was added to this monomer mixture in 1.5 times its total mass relative to all monomers. To the obtained mixture, 1.2 mol% and 3.6 mol% of azobisisobutyronitrile and azobis(2,4-dimethylpentanonitrile) as initiators were added respectively, and the mixture was heated at 73°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%), 2.0 times the total mass of all monomers, was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was injected into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, thereby obtaining resin AA1 with a weight average molecular weight of approximately 5.5 × 10³ in a yield of 68%. Resin AA1 has the following structural units.

[0266] <Preparation of Anti-corrosion Composition> As shown in Table 2, the following components were mixed and filtered using a fluoropolymer filter with a pore size of 0.2 μm to prepare the resist composition. [Table 2] Anti-corrosion composition resin Acid generating agent (B) Carboxylate (I) Quenching agent (C) PB / PEB Composition 1 AA1 = 10 portions B1-25=2.5 portions I-190 = 0.4 parts --- 100℃ / 130℃ Composition 2 AA1 = 10 portions B1-25=2.5 portions I-1 = 0.4 parts --- 100℃ / 130℃ Composition 3 AA1 = 10 portions B1-25=2.5 portions I-192 = 0.4 parts --- 100℃ / 130℃ Composition 4 AA1 = 10 portions B1-25=2.5 portions I-194 = 0.4 copies --- 100℃ / 130℃ Composition 5 A2 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 6 A1 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 7 A2 = 10 portions B1-25=2.5 portions I-190 = 0.1 units --- 100℃ / 130℃ Composition 8 A1 = 10 portions B1-25=2.5 portions I-1 = 0.1 parts --- 100℃ / 130℃ Composition 9 A2 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 10 A1 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 11 A3 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 12 A4 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 13 A5 = 10 servings B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 14 A6 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 15 A7 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 16 A8 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 17 A9 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 18 AA1 = 10 portions B1-25=2.5 portions I-946 = 0.4 copies --- 100℃ / 130℃ Composition 19 A10 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 20 A10 = 10 portions B1-25=2.5 portions I-946 = 0.1 units --- 100℃ / 130℃ Composition 21 A10 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 22 AA1 = 10 portions B1-25=2.5 portions I-1000=0.4 parts --- 100℃ / 130℃ Composition 23 A11 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 24 A11 = 10 portions B1-25=2.5 portions I-1000=0.1 parts --- 100℃ / 130℃ Composition 25 A11 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 26 AA1 = 10 portions B1-25=2.5 portions I-1189 = 0.4 parts --- 100℃ / 130℃ Composition 27 AA1 = 10 portions B1-25=2.5 portions I-1405 = 0.4 parts --- 100℃ / 130℃ Composition 28 A12 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 29 A13 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 30 A12 = 10 portions B1-25=2.5 portions I-1189 = 0.1 units --- 100℃ / 130℃ Composition 31 A13 = 10 portions B1-25=2.5 portions I-1405 = 0.1 parts --- 100℃ / 130℃ Composition 32 A12 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 33 A13 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 34 A14 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 35 A15 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 36 A16 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 37 A17 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 38 AA1 = 10 portions B1-25=2.5 portions I-2482 = 0.4 parts --- 100℃ / 130℃ Composition 39 A18 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 40 A19 = 10 portions B1-25=2.5 portions I-2482 = 0.1 units --- 100℃ / 130℃ Composition 41 A18 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Composition 42 AA1 = 10 portions B1-25=2.5 portions I-2509 = 0.4 parts --- 100℃ / 130℃ Composition 43 A19 = 10 portions B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Composition 44 A19 = 10 portions B1-25=2.5 portions I-2509 = 0.1 units --- 100℃ / 130℃ Composition 45 A19 = 10 portions B1-25=2.5 portions --- --- 100℃ / 130℃ Comparative composition 1 AA1 = 10 portions B1-25=2.5 portions --- IX-1 = 0.4 parts 100℃ / 130℃ Comparative composition 2 AX1 = 10 copies B1-25=2.5 portions --- C1 = 0.1 parts 100℃ / 130℃ Comparative composition 3 AX1 = 10 copies B1-25=2.5 portions --- IX-1 = 0.1 units 100℃ / 130℃ Comparative composition 4 AX1 = 10 copies B1-25=2.5 portions --- --- 100℃ / 130℃

[0267] <Resin> A1~A19, AA1, AX1: Resin A1~Resin A19, Resin AA1, Resin AX1 <Acid Generator (B)> B1-25: The salt represented by formula (B1-25); synthesized using the method described in Japanese Patent Application Publication No. 2011-126869. <Carboxylate(I)> I-1: The salt represented by formula (I-1) I-190: The salt represented by formula (I-190) I-192: The salt represented by formula (I-192) I-194: The salt represented by formula (I-194) I-946: Salt represented by formula (I-946) I-1000: The salt represented by formula (I-1000) I-1189: The salt represented by formula (I-1189) I-1405: The salt represented by formula (I-1405) I-2482: The salt represented by formula (I-2482) I-2509: The salt represented by formula (I-2509) <Quencher (C)> C1: Synthesized using the method described in Japanese Patent Application Publication No. 2011-39502 IX-1: The salt represented by formula (IX-1) is synthesized using the method described in Japanese Patent Application Publication No. 2011-037834. Solvent 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0268] (Electron beam exposure evaluation of resist composition) For a 6-inch silicon wafer, hexamethyldisilazane was used for 60 seconds at 90°C on a direct-heat plate. The resist composition was spin-coated onto the silicon wafer with a composition layer thickness of 0.04 μm. Afterwards, the composition layer was pre-baked for 60 seconds on a direct-heat plate at the temperature shown in column "PB" of Table 2 to form the composition layer. The composition layer formed on the wafer was directly patterned after development using an electron beam tracing machine (Elionix (stock) "ELS-F125 125 keV"), with the exposure varying in stages, to form a line and space pattern (60 nm spacing / 30 nm linewidth). After exposure, the wafer is exposed to a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 2, followed by baking. Then, using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer, the composition layer on the silicon wafer is developed for 20 seconds at 23°C by dynamic partitioning method to obtain a resist pattern. The obtained resist patterns (line and space patterns) were observed using a scanning electron microscope. The effective sensitivity was set by setting the exposure ratio of the line width to the space width of the line and space patterns with a spacing of 60 nm to be 1:1.

[0269] Line edge roughness (LER) evaluation: The amplitude of the unevenness of the sidewall surface of the resist pattern manufactured with effective sensitivity was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 3. [Table 3] Anti-corrosion composition LER Example 30 Composition 1 3.69 Example 31 Composition 2 3.79 Example 32 Composition 3 3.67 Example 33 Composition 4 3.70 Example 34 Composition 5 3.51 Example 35 Composition 6 3.66 Example 36 Composition 7 3.57 Example 37 Composition 8 3.76 Example 38 Composition 9 3.68 Example 39 Composition 10 3.85 Example 40 Composition 11 3.50 Example 41 Composition 12 3.53 Example 42 Composition 13 3.40 Example 43 Composition 14 3.53 Example 44 Composition 15 3.42 Example 45 Composition 16 3.46 Example 46 Composition 17 3.60 Example 47 Composition 18 3.60 Example 48 Composition 19 3.41 Example 49 Composition 20 3.46 Example 50 Composition 21 3.62 Example 51 Composition 22 3.62 Example 52 Composition 23 3.44 Example 53 Composition 24 3.49 Example 54 Composition 25 3.65 Example 55 Composition 26 3.62 Example 56 Composition 27 3.53 Example 57 Composition 28 3.51 Example 58 Composition 29 3.40 Example 59 Composition 30 3.46 Example 60 Composition 31 3.35 Example 61 Composition 32 3.57 Example 62 Composition 33 3.48 Example 63 Composition 34 3.39 Example 64 Composition 35 3.52 Example 65 Composition 36 3.40 Example 66 Composition 37 3.45 Example 67 Composition 38 3.44 Example 68 Composition 39 3.33 Example 69 Composition 40 3.35 Example 70 Composition 41 3.39 Example 71 Composition 42 3.45 Example 72 Composition 43 3.34 Example 73 Composition 44 3.36 Example 74 Composition 45 3.40 Comparative Example 1 Comparative composition 1 3.98 Comparative Example 2 Comparative composition 2 3.86 Comparative Example 3 Comparative composition 3 3.93 Comparative Example 4 Comparative composition 4 4.02 Compared with comparative compositions 1 to 4, compositions 1 to 45 have good centerline edge roughness (LER). [Industrial Applicability]

[0270] Resist compositions containing the carboxylates of the present invention can obtain resist patterns with good line edge roughness (LER), thus being suitable for the microfabrication of semiconductors and extremely useful in industry.

[0271] none

Claims

1. A carboxylic acid generator comprising a carboxylate salt represented by formula (I) or a structural unit represented by formula (IP), wherein in formula (I) and formula (IP), R4, R5, R6, R7, R8 and R9 independently represent halogen atoms or hydrocarbon groups having 1 to 18 carbon atoms, the hydrocarbon groups may have substituents, and the -CH2- contained in the hydrocarbon groups may be replaced by -O-, -CO-, -S- or -SO2-; at least one of the more than one R4 is a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms; A1, A2 and A3 independently represent hydrocarbon groups having 1 to 20 carbon atoms, the hydrocarbon groups may have substituents, and the -CH2- contained in the hydrocarbon groups may be replaced by -O-, -CO-, -S- or -SO2-; m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within the parentheses may be the same or different from each other; m2 represents any integer from 0 to 5. When m2 is 2 or higher, the bases within the parentheses can be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 1 to 5. When m4 is 2 or higher, the bases within the parentheses can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, the bases within the parentheses can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, the bases within the parentheses can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, the bases within the parentheses can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, the bases within the parentheses can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, the bases within the parentheses can be the same or different. 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5; X0 represents a single bond, a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-; Rbb1 represents a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have halogen atoms; X10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**; Ph represents a phenyl group that may have substituents; Ax represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds; Ay represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to Rbb1, and ** indicates the bonding site with L10; L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.

2. The carboxylic acid generating agent as claimed in claim 1, wherein A1 is ***-X01-L01- or ***-L01-X01-, A2 is ***-X02-L02- or ***-L02-X02-, A3 is ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 independently represent -O-, -CO-, -S- or -SO2-, L01, L02 and L03 independently represent single bonds or hydrocarbon groups having 1 to 18 carbon atoms, and *** represents the bonding site of the benzene ring bonded to S+.

3. The carboxylic acid generating agent as claimed in claim 2, wherein X01, X02 and X03 are oxygen atoms.

4. The carboxylic acid generating agent as claimed in claim 1, wherein R4, R5 and R6 are each independently a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

5. The carboxylic acid generating agent as claimed in claim 1, wherein X0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms that may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) or an aromatic hydrocarbon group having 6 to 36 carbon atoms that may have substituents.

6. The carboxylic acid generating agent as claimed in claim 5, wherein X0 comprises an alicyclic hydrocarbon group having 3 to 36 carbons and a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), a group composed of an alicyclic hydrocarbon group having 3 to 36 carbons and a chain hydrocarbon group having 1 to 18 carbons (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-, the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, the alicyclic hydrocarbon group and the chain hydrocarbon group may have fluorine atoms and a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group), or an aromatic hydrocarbon group having 6 to 36 carbons and a perfluoroalkyl group having 1 to 4 carbons or a hydroxyl group.

7. The carboxylic acid generating agent as claimed in claim 5, wherein X0 comprises the alicyclic hydrocarbon group, the alicyclic hydrocarbon group being a 5- or 6-carbon cycloalkyldiyl group (the -CH2- contained in the cycloalkyldiyl group may be replaced by -O- or -CO-, and the cycloalkyldiyl group may also be an acetal ring), the polycyclic alicyclic hydrocarbon group comprising adamantyl or norbornanediyl, adamantyl and a 5- or 6-carbon cycloalkyldiyl group bonded to the adamantyl by a helical bond (the -CH2- contained in the adamantyl, norbornanediyl and cycloalkyldiyl group may be replaced by -O- or -CO-, the -CH2-CH2- contained in the adamantyl and norbornanediyl group may be replaced by -O- or -CO-, and the cycloalkyldiyl group may also be an acetal ring).

8. The carboxylic acid generating agent as claimed in claim 1, wherein X10 is a single bond or a group represented by any of formulas (X1-1), (X1-2') to (X1-7'), and (X1-8); in formulas (X1-1), (X1-2') to (X1-7'), and (X1-8), * and ** are bonding sites, and ** indicates a bonding site with L10; Rx represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; and mx represents any integer from 0 to 4.

9. The carboxylic acid generating agent as claimed in claim 8, wherein X10 is a single bond, a group represented by any one of formula (X1-1), formula (X1-4) and formula (X1-5), and in formula (X1-1), formula (X1-4) and formula (X1-5), * and ** are bonding sites, and ** indicates a bonding site with L10.

10. The carboxylic acid generating agent as claimed in claim 1, wherein L10 is a single bond or an alkyldiyl group having 1 to 4 carbon atoms (wherein, The -CH2- contained in the alkyl diel group can be replaced with -O- or -CO-.

11. The carboxylic acid generating agent as claimed in claim 6, wherein X0 is a phenyl group that may have substituents, L10 is a single bond, and X10 is a single bond or a group represented by formula (X1-1).

12. A resist composition comprising a carboxylic acid generating agent as described in any one of claims 1 to 11.

13. The resist composition as claimed in claim 12, comprising a carboxylate represented by formula (I) and a resin comprising a structural unit (a1) having an acid-instable group.

14. The resist composition as claimed in claim 12, comprising a resin containing a structural unit represented by formula (IP), wherein the resin containing the structural unit represented by formula (IP) further comprises a structural unit (a1) having an acid-indestabilized group.

15. The resist composition as claimed in claim 14 further comprises a carboxylate represented by formula (I).

16. The resist composition as claimed in claim 13 or claim 14, wherein the structural unit (a1) having an acid-instable group comprises at least one selected from the group consisting of structural units represented by formula (a1-0), structural units represented by formula (a1-1), and structural units represented by formula (a1-2), wherein in formulas (a1-0), (a1-1), and (a1-2), La01, La1, and La2 independently represent -O- or *-O-(CH2)k1-CO-O-, k1 represents any integer from 1 to 7, and * represents a bonding site with -CO-; Ra01, Ra4, and Ra5 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; and Ra02, Ra03, and Ra04 independently represent 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 composed of combinations thereof. Ra6 and Ra7 independently represent alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 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; m1 represents any integer from 0 to 14; n1 represents any integer from 0 to 10; n1' represents any integer from 0 to 3.

17. The resist composition as claimed in claim 12 further comprises a resin containing a structural unit represented by formula (a2-A), in which Ra50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; Ra51 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkyl carbonyl group having 2 to 4 carbon atoms, an alkyl carbonyloxy group having 2 to 4 carbon atoms, an acryloxy group, or amethystoxy; Aa50 represents a single bond or *-Xa51-(Aa52-Xa52)nb-, where * represents a bonded bond to the carbon atom bonded to -Ra50; Aa52 represents an alkyldiyl group having 1 to 6 carbon atoms; Xa51 and Xa52 independently represent -O-, -CO-O-, or -O-CO-, respectively; nb represents 0 or 1; mb represents any integer from 0 to 4; when mb is any integer greater than 2, multiple Ra51 values ​​can be the same or different.

18. The resist composition as claimed in claim 12 further comprises a salt represented by formula (B1), in which Qb1 and Qb2 independently represent 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, respectively; Lb1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein the -CH2- contained in the divalent saturated hydrocarbon group may be substituted 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 having a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms having a substituent, wherein the -CH2- contained in the alicyclic hydrocarbon group may be substituted with -O-, -S-, -SO2-, or -CO-; and Z+ represents an organic cation.

19. A method for manufacturing a resist pattern, comprising: (1) The step of coating the resist composition as described in claim 12 onto a substrate; (2) The step of drying the coated composition to form a composition layer; (3) The step of exposing the composition layer; (4) The step of heating the exposed composition layer; and (5) The step of developing the heated composition layer.

20. A carboxylate, represented by formula (I), wherein in formula (I), R4, R5, R6, R7, R8 and R9 each independently represent a halogen atom or 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 by -O-, -CO-, -S- or -SO2-; at least one of the more than one R4 is a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms; A1, A2 and A3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-; m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within the parentheses may be the same or different; m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups within the parentheses may be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 1 to 5. When m4 is 2 or higher, the bases within the parentheses can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, the bases within the parentheses can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, the bases within the parentheses can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, the bases within the parentheses can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, the bases within the parentheses can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, the bases within the parentheses can be the same or different. 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5; X0 represents a single bond or a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-; Rbb1 represents a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have halogen atoms; X10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**; Ph represents a phenyl group that may have substituents; Ax represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds; Ay represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to Rbb1, and ** indicates the bonding site with L10; L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.

21. The carboxylate as claimed in claim 20, wherein A1 is ***-X01-L01- or ***-L01-X01-, A2 is ***-X02-L02- or ***-L02-X02-, A3 is ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 independently represent -O-, -CO-, -S- or -SO2-, L01, L02 and L03 independently represent a single bond or a hydrocarbon group having 1 to 18 carbon atoms, and *** represents the bonding site of the benzene ring bonded to S+.

22. The carboxylate as claimed in claim 21, wherein X01, X02 and X03 are oxygen atoms.

23. The carboxylate as claimed in claim 20 or claim 21, wherein R4, R5 and R6 are each independently a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.

24. The carboxylate as claimed in claim 20 or claim 21, wherein X0 is a single bond or an aliphatic hydrocarbon group having 1 to 72 carbon atoms that may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) or an aromatic hydrocarbon group having 6 to 36 carbon atoms that may have substituents.

25. The carboxylate as claimed in claim 20 or claim 21, wherein X0 comprises a single bond, an alicyclic hydrocarbon group of 3 to 36 carbons having a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-), a group composed of an alicyclic hydrocarbon group of 3 to 36 carbons and a chain hydrocarbon group of 1 to 18 carbons (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-, the -CH2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group), or an aromatic hydrocarbon group of 6 to 36 carbons having a fluorine atom, a perfluoroalkyl group of 1 to 4 carbons or a hydroxyl group.

26. The carboxylate as claimed in claim 20 or claim 21, wherein X0 comprises the alicyclic hydrocarbon group, the alicyclic hydrocarbon group being a 5- or 6-carbon cycloalkyldiyl group (the -CH2- contained in the cycloalkyldiyl group may be replaced by -O- or -CO-, and the cycloalkyldiyl group may also be an acetal ring), the polycyclic alicyclic hydrocarbon group comprising adamantyl or norbornanediyl, adamantyl and a 5- or 6-carbon cycloalkyldiyl group bonded to the adamantyl by a helical bond (the -CH2- contained in the adamantyl, norbornanediyl and cycloalkyldiyl group may be replaced by -O- or -CO-, the -CH2-CH2- contained in the adamantyl and norbornanediyl group may be replaced by -O- or -CO-, and the cycloalkyldiyl group may also be an acetal ring).

27. The carboxylate as claimed in claim 20 or claim 21, wherein X10 is a single bond or a group represented by any of formulas (X1-1), (X1-2') to (X1-7'), and (X1-8); in formulas (X1-1), (X1-2') to (X1-7'), and (X1-8), * and ** are bonding sites, and ** indicates a bonding site with L10; Rx represents a halogen atom, a hydroxyl group, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; and mx represents any integer from 0 to 4.

28. The carboxylate as claimed in claim 27, wherein X10 is a single bond, a base represented by any of the formulas (X1-1), (X1-4), and (X1-5), and in formulas (X1-1), (X1-4), and (X1-5), * and ** are bonding sites, and ** indicates a bonding site with L10.

29. The carboxylate as claimed in claim 20 or claim 21, wherein L10 is a single bond or an alkyldiyl group having 1 to 4 carbon atoms (wherein, The -CH2- contained in the alkyl diel group can be replaced with -O- or -CO-.

30. A resin comprising the structural unit represented by formula (IP), wherein in formula (IP), R4, R5, R6, R7, R8, and R9 independently represent halogen atoms or hydrocarbon groups having 1 to 18 carbon atoms, the hydrocarbon groups may have substituents, and the -CH2- contained in the hydrocarbon groups may be replaced by -O-, -CO-, -S-, or -SO2-; at least one of the more than one R4 is a fluorine atom, an iodine atom, or a perfluoroalkyl group having 1 to 4 carbon atoms; A1, A2, and A3 independently represent hydrocarbon groups having 1 to 20 carbon atoms, the hydrocarbon groups may have substituents, and the -CH2- contained in the hydrocarbon groups may be replaced by -O-, -CO-, -S-, or -SO2-; m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within the parentheses may be the same or different; m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups within the parentheses may be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 1 to 5. When m4 is 2 or higher, the bases within the parentheses can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, the bases within the parentheses can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, the bases within the parentheses can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, the bases within the parentheses can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, the bases within the parentheses can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, the bases within the parentheses can be the same or different. 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5; X0 represents a single bond, a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-; Rbb1 represents a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have halogen atoms; X10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**; Ph represents a phenyl group that may have substituents; Ax represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds; Ay represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to Rbb1, and ** indicates the bonding site with L10; L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.

31. A carboxylic acid generator comprising a carboxylate salt represented by formula (I) or a structural unit represented by formula (IP), wherein in formula (I) and formula (IP), R4, R5, R6, R7, R8 and R9 independently represent a halogen atom or 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 substituted by -O-, -CO-, -S- or -SO2-; A1 is ***-X01-L01- or ***-L01-X01-, A2 is ***-X02-L02- or ***-L02-X02-, A3 is ***-X03-L03- or ***-L03-X03-, X01, X02 and X03 independently represent -O-, -CO-, -S- or -SO2-, and L01, L02 and L03 are independently alkyldiyl groups having 1 to 6 carbon atoms. m1 represents any integer from 1 to 5. When m1 is 2 or higher, the bases within the parentheses can be the same or different. m2 represents any integer from 0 to 5. When m2 is 2 or higher, the bases within the parentheses can be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 0 to 5. When m4 is 2 or higher, the bases within the parentheses can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, the bases within the parentheses can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, the bases within the parentheses can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, the bases within the parentheses can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, the bases within the parentheses can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, multiple R9 values ​​can be the same or different. 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5; X0 represents a single bond, a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-; Rbb1 represents a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have halogen atoms; X10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**; Ph represents a phenyl group that may have substituents; Ax represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds; Ay represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to Rbb1, and ** indicates the bonding site with L10; L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.

32. A carboxylate, represented by formula (I), wherein R4, R5, R6, R7, R8, and R9 independently represent halogen atoms or hydrocarbon groups having 1 to 18 carbon atoms, the hydrocarbon groups may have substituents, and the -CH2- contained in the hydrocarbon groups may be substituted by -O-, -CO-, -S-, or -SO2-; A1 is ***-X01-L01- or ***-L01-X01-, A2 is ***-X02-L02- or ***-L02-X02-, A3 is ***-X03-L03- or ***-L03-X03-, X01, X02, and X03 independently represent -O-, -CO-, -S-, or -SO2-, and L01, L02, and L03 are independently alkyldiyl groups having 1 to 6 carbon atoms. m1 represents any integer from 1 to 5. When m1 is 2 or higher, the bases within the parentheses can be the same or different. m2 represents any integer from 0 to 5. When m2 is 2 or higher, the bases within the parentheses can be the same or different. m3 represents any integer from 0 to 5. When m3 is 2 or higher, the bases within the parentheses can be the same or different. m4 represents any integer from 0 to 5. When m4 is 2 or higher, the bases within the parentheses can be the same or different. m5 represents any integer from 0 to 5. When m5 is 2 or higher, the bases within the parentheses can be the same or different. m6 represents any integer from 0 to 5. When m6 is 2 or higher, the bases within the parentheses can be the same or different. m7 represents any integer from 0 to 4. When m7 is 2 or higher, the bases within the parentheses can be the same or different. m8 represents any integer from 0 to 5. When m8 is 2 or higher, the bases within the parentheses can be the same or different. m9 represents any integer from 0 to 5. When m9 is 2 or higher, multiple R9 values ​​can be the same or different. 1≦m1+m7≦5, 0≦m2+m8≦5, 0≦m3+m9≦5; X0 represents a single bond or a hydrocarbon group with 1 to 72 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-; Rbb1 represents a hydrogen atom, a halogen atom, or an alkyl group with 1 to 6 carbon atoms that may have halogen atoms; X10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**; Ph represents a phenyl group that may have substituents; Ax represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds; Ay represents a bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate bonds. * indicates the bonding site of the carbon atom bonded to Rbb1, and ** indicates the bonding site with L10; L10 represents a single bond or a hydrocarbon group with 1 to 36 carbon atoms that may have substituents, wherein the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-.