Resist composition, method for producing resist pattern, salt, acid generator, and resin
The introduction of acid generators with specific salts and resin structures in resist compositions addresses the issue of CD uniformity in semiconductor manufacturing, improving pattern precision and consistency.
Patent Information
- Application Number
- JP2025004354
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-01-19
- Filing Date
- 2025-01-10
- Publication Date
- 2025-08-01
AI Technical Summary
Existing resist compositions fail to produce resist patterns with adequate CD uniformity (CDU), which is crucial for semiconductor microfabrication.
The use of a specific acid generator containing salts represented by formulas (I1) and (I2), or structural units derived from these salts, within a resist composition, along with a resin containing acid-labile groups, to enhance CD uniformity.
The proposed resist composition achieves improved CD uniformity in resist patterns, enhancing the precision and consistency of semiconductor manufacturing processes.
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Abstract
Description
Technical Field
[0001] The present invention relates to a salt for an acid generator used in semiconductor microfabrication, an acid generator containing the salt, a resin, a resist composition, and a method for producing a resist pattern.
Background Art
[0002] Patent Document 1 describes a resin containing a structural unit derived from a salt represented by the following formula and a resist composition containing the resin, respectively. TIFF2025113198000001.tif30110
Prior Art Documents
Patent Documents
[0003]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0004] The present invention provides a salt capable of producing a resist pattern with better CD uniformity (CDU) than a resist pattern formed from the above resist composition.
Means for Solving the Problems
[0005] The present invention includes the following inventions. [1] An acid generator containing a salt represented by formula (I1) or formula (I2) or a structural unit represented by formula (IP1) or formula (IP2). TIFF2025113198000002.tif98160[In formula (I1), formula (I2), formula (IP1), and formula (IP2), R 1represents a halogen atom, a cyano group, a nitro group, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group may have a substituent. -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO2-. R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m1 represents any integer from 0 to 4. When m1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * represents the bonding site to the benzene ring). L 1 represents a single bond or an aliphatic hydrocarbon group having 1 to 28 carbon atoms which may have a substituent. -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO2-. R 3 and R 4 each independently represents 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 a substituent. -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO2-. m3 represents any integer from 1 to 4. When m3 is 2 or more, the plurality of R 3 may be the same as or different from each other. m4 represents any integer from 0 to 4. When m4 is 2 or more, the plurality of R 4 may be the same as or different from each other. R 5 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZI + represents an organic cation.] [2]R 3and R 4 The acid generator according to [1], wherein R is a fluorine atom, an iodine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a perfluoroalkyl group having 1 to 3 carbon atoms. [3]X 1 The acid generator according to [1] or [2], wherein X is *-CO-O- or *-O-CO-. [4]L 1 The acid generator according to any one of [1] to [3], wherein L is a single bond or a linear alkanediyl group having 1 to 6 carbon atoms. [5]m3 and m4 are each independently 1 or 2, and the acid generator according to any one of [1] to [4]. [6]A resist composition containing the acid generator according to any one of [1] to [5]. [7]The acid generator is a salt represented by formula (I1) or formula (I2), The resist composition according to [6], further containing a resin containing a structural unit (a1) having an acid-labile group. [8]The acid generator is a resin containing a structural unit represented by formula (IP1) or formula (IP2), and the resin further contains a structural unit (a1) having an acid-labile group, and the resist composition according to [6]. [9]The resist composition according to [8], further containing a salt represented by formula (I1) or formula (I2).
[10] The resist composition according to any one of [7] to [9], wherein the structural unit (a1) having an acid-labile group includes at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a1-4), a structural unit represented by formula (a1-5), and a structural unit represented by formula (a1-6). TIFF2025113198000003.tif46153 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or *-O-(CH2) k1-CO-O- represents, k1 represents any integer from 1 to 7, and * represents the bonding site with -CO-. R a01 、R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 、R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. m1’ represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3. TIFF2025113198000004.tif31118[In formula (a1-4), R a1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a17 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a11represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -CO- or -NR a18 -. R a18 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a1 represents a single bond or a carbonyl group. R a34 and R a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. na1 represents any integer from 1 to 5. When na1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. na11 represents any integer from 0 to 4. When na11 is 2 or more, the plurality of R a17 may be the same as or different from each other. mc represents any integer from 0 to 2.] TIFF2025113198000005.tif4558[In formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents any integer from 1 to 4, and * represents the bonding site with L 51 L 51 、L 52 、L 53 and L 54 each independently represent -O- or -S-. s1 represents any integer from 1 to 3. s1’ represents any integer from 0 to 3. TIFF2025113198000006.tif3580[In formula (a1-6), R a61 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a62 , R a63 and R a64 each independently represent an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, or R a62 and R a63 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. X a61 represents a single bond, -CO-O-*, or -CO-NR a65 -, * represents the bonding site with Ar, and R a65 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a62 represents a single bond, *-O-L a61 -, or *-CO-O-L a62 -, * represents the bonding site with Ar, and L a61 and L a62 each independently represent an alkanediyl group having 1 to 4 carbon atoms. Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
[11] The resist composition according to any one of [7] to
[10] , wherein the resin containing the structural unit (a1) having an acid-labile group further contains a structural unit represented by formula (a2-A). TIFF2025113198000007.tif31128[In formula (a2-A), R a2 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a27represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -CO- or -NR a28 -. R a28 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a2 represents a single bond or a carbonyl group. nA2 represents any integer from 1 to 5, and when nA2 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. na21 represents any integer from 0 to 4, and when na21 is 2 or more, the plurality of R a27 may be the same as or different from each other. mc represents any integer from 0 to 2. The resist composition according to any one of [6] to
[11] , further containing a salt that generates an acid having a lower acidity than the acid generated from the
[12] acid generator.
[13] (1) A step of applying the resist composition according to any one of [6] to
[12] onto a substrate, (2) A step of drying the applied resist composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for producing a resist pattern including the above steps.
[14] The salt represented by the above formula (I1) or formula (I2).
[15] R 3 and R 4is the salt described in
[14] , which is a fluorine atom, an iodine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a perfluoroalkyl group having 1 to 3 carbon atoms.
[16] X 1 is the salt described in
[14] or
[15] , where *-CO-O- or *-O-CO-.
[17] L 1 is the salt described in any one of
[14] to
[16] , which is a single bond or a linear alkanediyl group having 1 to 6 carbon atoms.
[18] m3 and m4 are each independently 1 or 2, which is the salt described in any one of
[14] to
[17] .
[19] A resin containing a structural unit represented by the above formula (IP1) or formula (IP2).
Advantages of the Invention
[0006] By using the resist composition using the salt of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU).
Embodiments for Carrying Out the Invention
[0007] In this specification, the “(meth)acrylic monomer” means “at least one of an acrylic monomer and a methacrylic monomer”. Expressions such as “(meth)acrylate” and “(meth)acrylic acid” also represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either. -CH2- contained in a hydrocarbon group, etc. is -O-, -S-, -CO-, -SO-, -NR XWhen replaced by -(X is any sign) or -SO2-, the same examples apply to each group, and the number of carbon atoms before replacement is defined as the number of carbon atoms in the hydrocarbon group etc. The "combined group" means a group formed by bonding two or more of the exemplified groups, and the valences of these groups may be appropriately changed depending on the bonding form. "Derived from" or "induced from" means that the polymerizable C=C bond contained in the molecule becomes a -C-C- group (single bond) by polymerization. When stereoisomers exist, all stereoisomers are included. Depending on the number of substituents etc., any position and number of hydrogen atoms contained in the group may be replaced by a bond. The number of carbon atoms in the substituent is not included in the number of carbon atoms of the group to be substituted. In this specification, an "acid-labile group" means a group having a leaving group, which forms a hydrophilic group (e.g., a hydroxy group or a carboxy group etc.) when the leaving group is eliminated upon contact with an acid (e.g., trifluoromethanesulfonic acid etc.). A "base-labile group" means a group having a leaving group, which forms a hydrophilic group (e.g., a carboxy group or a hydroxy group etc.) when the leaving group is eliminated upon contact with a base (e.g., trimethylamine, tetramethylammonium hydroxide etc.). In this specification, the "solid content of the resist composition" means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.
[0008] [Salts represented by formula (I1) and formula (I2)] The present invention relates to a salt represented by formula (I1) (hereinafter sometimes referred to as "salt (I1)") and a salt represented by formula (I2) (hereinafter sometimes referred to as "salt (I2)"). The combination of salt (I1) and salt (I2) may be referred to as salt (I). Among salts (I), the side having a negative charge may be referred to as "anion (I)", and the side having a positive charge may be referred to as "cation (I)". TIFF2025113198000008.tif44144[wherein all the symbols have the same meanings as described above respectively.]
[0009] [Anion (I)] In formula (I), R 1Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. R 1 The C1-C12 haloalkyl group in R represents an alkyl group having 1 to 12 carbon atoms and having a halogen atom, and examples thereof include a C1-C12 fluoroalkyl group, a C1-C12 chloroalkyl group, a C1-C12 bromoalkyl group, and a C1-C12 iodoalkyl group. Examples of the haloalkyl group include a C1-C12 perfluoroalkyl group (such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc.), a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a difluoromethyl group, and the like. The number of carbon atoms of the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. R 1 Examples of the C1-C18 hydrocarbon group in R include chain hydrocarbon groups such as an alkyl group and an alkanediyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. The alkyl group is a linear or branched alkyl group, and examples thereof include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples of the alkanediyl group include linear or branched alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. The terminal of the branched alkanediyl group may be an alkyl group such as a methyl group. The number of carbon atoms in the chain hydrocarbon group is preferably from 1 to 12, more preferably from 1 to 9, still more preferably from 1 to 6, even more preferably from 1 to 4, and even more preferably from 1 to 3. Examples of the alicyclic hydrocarbon group include monocyclic or polycyclic groups such as those represented below. The bonding site can be at any position. JPEG2025113198000009.jpg46168Specifically, examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and cyclododecyl group. Examples of the polycyclic alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, and norbornyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 18, more preferably from 3 to 16, and still more preferably from 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Among the chain hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group, examples of the group formed by combining two or more kinds of groups include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, an aromatic hydrocarbon group-alkanediyl group-*, an alkyl group-aromatic hydrocarbon group-*, an alkyl group-aromatic hydrocarbon group-alkanediyl group-*, and -CH2- contained in the alkanediyl group and the alkyl group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2-. ), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, an alicyclic hydrocarbon group-alkanediyl group-*, an alkyl group-alicyclic hydrocarbon group-*, an alkyl group-alicyclic hydrocarbon group-alkanediyl group-*, and -CH2- contained in the alicyclic hydrocarbon group, the alkanediyl group, and the alkyl group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2-. ), a group formed by combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group-alicyclic hydrocarbon group-*, an alicyclic hydrocarbon group-aromatic hydrocarbon group-*, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2-. ). * represents a bonding site. R 7 Examples of the alkyl group of include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc. Examples of the aromatic hydrocarbon group-alkanediyl group-* include aralkyl groups such as a benzyl group and a phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group, a xylyl group, a cumenyl group, etc. Examples of the alicyclic hydrocarbon group-alkane diyl group-* include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl group, and the like. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group, and the like. Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group-* include phenylcyclohexyl group and the like. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include cyclohexylphenyl group and the like. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined with each other. Also, any of these groups may be bonded to a benzene ring.
[0010] R 1 When -CH2- contained in the haloalkyl group or hydrocarbon group represented by is replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2-, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the haloalkyl group or the hydrocarbon group. Also, the number may be one or two or more. Examples of the group in which -CH2- contained in the haloalkyl group and hydrocarbon group is replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2- include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an amino group (a group in which -CH2- contained in a methyl group is replaced by -NR 7-), oxy group (a group in which -CH2- in a methylene group is replaced with -O-), carbonyl group (a group in which -CH2- in a methylene group is replaced with -CO-), thio group (a group in which -CH2- in a methylene group is replaced with -S-), sulfonyl group (a group in which -CH2- in a methylene group is replaced with -SO2-), peptide group (a group in which -CH2-CH2- in an ethylene group is replaced with -CO-NR 7 -), alkoxy group (a group in which -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl group (a group in which -CH2-CH2- at any position in an alkyl group is replaced with -O-CO-), alkylcarbonyl group (a group in which -CH2- at any position in an alkyl group is replaced with -CO-), alkylcarbonyloxy group (a group in which -CH2-CH2- at any position in an alkyl group is replaced with -CO-O-), alkoxycarbonyloxy group (also alkyl group (a group in which two -CH2- at any position in the alkyl group are replaced with -O-CO-O-), alkoxyalkoxy group (a group in which two -CH2- at any position in the alkyl group are each replaced with -O-), alkylthio group (a group in which -CH2- at any position in the alkyl group is replaced with -S-), alkylsulfonyl group (a group in which -CH2- at any position in the alkyl group is replaced with -SO2-), alkylamino group (a group in which -CH2- at any position in the alkyl group is replaced with -NR 7 -), alkyl peptide group (wherein -CH2-CH2- at any position in the alkyl group is replaced by -CO-NR 7-replaced group), an alkanediyl-oxy group (a group in which any -CH2- in the alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -O-CO-), an alkanediyl-carbonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -CO-), an alkanediyl-carbonyl-oxy group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-O-), an alkanediyl-oxycarbonyl-oxy group (a group in which any -CH2-CH2-CH2- in the alkanediyl group is replaced by -O-CO-O-), an alkanediyl-thio group (a group in which any -CH2- in the alkanediyl group is replaced by -S-), an alkanediyl-sulfonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -SO2-), an alkanediyl-amino group (a group in which any -CH2- in the alkanediyl group is replaced by -NR 7 -replaced group), an alkanediyl-peptide group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-NR 7 -replaced group), a cycloalkoxy group, a cycloalkylalkoxy group, an aromatic hydrocarbon group-carbonyl-oxy group, an aromatic hydrocarbon group-carbonyl group, an aromatic hydrocarbon group-oxy group, a haloalkoxy group (a group in which any -CH2- in the haloalkyl group is replaced by -O-), a haloalkoxycarbonyl group (a group in which any -CH2-CH2- in the haloalkyl group is replaced by -O-CO-), a haloalkylcarbonyl group (a group in which any -CH2- in the haloalkyl group is replaced by -CO-), a haloalkylcarbonyl-oxy group (a group in which any -CH2-CH2- in the haloalkyl group is replaced by -CO-O-), a group formed by combining two or more of these groups, and the like. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylamino group include alkylamino groups having 1 to 17 carbon atoms, such as methylamino group, ethylamino group, dimethylamino group, propylamino group, butylamino group, pentylamino group, pentylamino group, hexylamino group and the like. The number of carbon atoms of the alkylamino group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkyl peptide group include alkyl peptide groups having 1 to 17 carbon atoms, such as methyl peptide group, ethyl peptide group, propyl peptide group and the like. The number of carbon atoms of the alkyl peptide group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the alkoxyalkoxy group include alkoxyalkoxy groups having 2 to 16 carbon atoms, such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxycarbonyloxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, undecylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 17 carbon atoms, such as methyleneoxy group, ethyleneoxy group, propanediyl-oxy group, butanediyl-oxy group, pentanediyl-oxy group and the like. The number of carbon atoms of the alkanediyl-oxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 17 carbon atoms, such as a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propanediyl-oxycarbonyl group, and a butanediyl-oxycarbonyl group. Examples of the alkanediyl-carbonyl group include alkanediyl-carbonyl groups having 2 to 18 carbon atoms, such as a methylene-carbonyl group, an ethylene-carbonyl group, a propanediyl-carbonyl group, a butanediyl-carbonyl group, and a pentanediyl-carbonyl group. Examples of the alkanediyl-carbonyl-oxy group include alkanediyl-carbonyl-oxy groups having 2 to 17 carbon atoms, such as a methylene-carbonyl-oxy group, an ethylene-carbonyl-oxy group, a propanediyl-carbonyl-oxy group, and a butanediyl-carbonyl-oxy group. Examples of the alkanediyl-oxycarbonyl-oxy group include alkoxycarbonyl-oxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyl-oxy group. The number of carbon atoms of the alkanediyl-oxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkanediyl-carbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkanediyl-carbonyl-oxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkanediyl-oxycarbonyl-oxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkanediyl-thio group include alkanediyl-thio groups having 1 to 17 carbon atoms, such as a methylene-thio group, an ethylene-thio group, and a propylene-thio group. The number of carbon atoms of the alkanediyl-thio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, a propylenesulfonyl group, etc. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and still more preferably 1 to 3. Examples of the alkanediylamino group include alkanediylamino groups having 1 to 17 carbon atoms, such as a methyleneamino group, an ethyleneamino group, a dimethyleneamino group, a propyleneamino group, a butyleneamino group, a pentyleneamino group, a hexyleneamino group, etc. The number of carbon atoms in the alkanediylamino group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and still more preferably 1 to 3. Examples of the alkanediyl peptide group include alkanediyl peptide groups having 1 to 17 carbon atoms, such as a methylene peptide group, an ethylene peptide group, a propylene peptide group, etc. The number of carbon atoms in the alkanediyl peptide group is preferably 1 to 11, more preferably 1 to 6, even more preferably 1 to 4, and still more preferably 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. Examples of aromatic hydrocarbon group-carbonyl groups include aromatic hydrocarbon group-carbonyl groups having 7 to 18 carbon atoms, such as a benzoyl group. Examples of aromatic hydrocarbon group-oxy groups include aromatic hydrocarbon group-oxy groups having 6 to 17 carbon atoms, such as a phenyloxy group. Examples of the haloalkoxy group, haloalkoxycarbonyl group, haloalkylcarbonyl group, and haloalkylcarbonyloxy group include a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxycarbonyl group having 2 to 11 carbon atoms, a haloalkylcarbonyl group having 2 to 12 carbon atoms, and a haloalkylcarbonyloxy group having 2 to 11 carbon atoms. For example, a group in which one or more hydrogen atoms of the groups exemplified above are replaced with a halogen atom can be mentioned.
[0011] In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2- include the groups represented below. The bonding site can be at any position. TIFF2025113198000010.tif54167R 1 Examples of the substituent that the hydrocarbon group may have include a halogen atom, a cyano group, a nitro group, etc. R 1 When -CH2- contained in R 7 is replaced with -O-, -S-, -CO-, -SO-, -NR 1 -, or -SO2-, substantially, R 1 can have substituents such as a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an alkoxyalkoxy group, a thiol group, an alkylthio group, an alkylsulfonyl group, an amino group, an alkylamino group, and an alkylpeptide group. Further, when R is a group in which an alicyclic hydrocarbon group or an aromatic hydrocarbon group is combined with a chain hydrocarbon group such as an alkyl group, the chain hydrocarbon group such as an alkyl group can be substantially a substituent of the alicyclic hydrocarbon group or the aromatic hydrocarbon group. The hydrocarbon group may have one substituent or a plurality of substituents. R 1is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group or the haloalkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) or a haloalkyl group having 1 to 4 carbon atoms, still more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a carboxy group or a fluoroalkyl group having 1 to 3 carbon atoms, even more preferably an iodine atom, a fluorine atom, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group or a perfluoroalkyl group having 1 to 3 carbon atoms, and even still more preferably an iodine atom, a fluorine atom, a hydroxy group, a methoxy group or a trifluoromethyl group. m1 is preferably 0, 2 or 4, more preferably 0 or 4, and still more preferably 0. R 1 The bonding position to the benzene ring of is SO3 - It may be any of the ortho, meta or para positions with respect to the bonding position of. X 1 is preferably *-CO-O- (* represents the bonding site to the benzene ring). X 1 The bonding position to the benzene ring of is SO3 - It may be any of the ortho, meta or para positions with respect to the bonding position of, but preferably bonds to the meta or para position.
[0012] L 1Examples of the aliphatic hydrocarbon group include linear or branched chain hydrocarbon groups such as alkanediyl groups, and monocyclic or polycyclic (including spiro rings, condensed rings, bridged rings, etc.) alicyclic hydrocarbon groups. A group formed by combining two or more of these groups (for example, a divalent hydrocarbon group formed from an alicyclic hydrocarbon group and a chain hydrocarbon group) may also be used. The number of carbon atoms in the aliphatic hydrocarbon group is preferably from 1 to 26, more preferably from 1 to 24, still more preferably from 1 to 20, even more preferably from 1 to 18. Examples of the alkanediyl group include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group. The terminal of the branched alkanediyl group may be an alkyl group such as a methyl group. The number of carbon atoms in the chain hydrocarbon group may be from 1 to 18, preferably from 1 to 12, more preferably from 1 to 10, still more preferably from 1 to 9, even more preferably from 1 to 8, still even more preferably from 1 to 6, and even more preferably from 1 to 4. Examples of the monocyclic or polycyclic divalent alicyclic hydrocarbon group include the following alicyclic hydrocarbon groups, etc. The bonding site can be at any position. TIFF2025113198000011.tif46168Specifically, it is a monocyclic divalent alicyclic hydrocarbon group which is a monocyclic cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclooctane-1,5-diyl group, etc. A polycyclic divalent alicyclic hydrocarbon group which is a polycyclic cycloalkanediyl group such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane-1,5-diyl group, an adamantane-2,6-diyl group, etc. and Examples include a spiro ring having a cycloalkyl group such as a spirocyclohexane-1,2'-cyclopentane group, a spiroadamantane-2,3'-cyclopentane group, etc., a norbornyl group or an adamantyl group and a cycloalkyl group bonded thereto by spiro. The number of carbon atoms of the alicyclic hydrocarbon group may be 3 to 18, preferably 3 to 16, more preferably 3 to 12.
[0013] Examples of the group formed by combining two or more kinds of groups include a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group. In the combination, two or more kinds of alicyclic hydrocarbon groups and chain hydrocarbon groups may be combined respectively. Also, any group may be bonded to X 1 . Examples of the group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group include, for example, -divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-, etc.
[0014] L 1 The -CH2- contained in the aliphatic hydrocarbon group of may be replaced by -O-, -S-, -SO2-, -SO-, -NR 7 - or -CO-. L 1 When the -CH2- contained in the aliphatic hydrocarbon group of is -O-, -S-, -SO2-, -SO-, -NR 7-or, when replaced by -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the aliphatic hydrocarbon group. When -CH2- contained in the aliphatic hydrocarbon group is replaced by -O-, -S-, -SO2-, -SO-, -NR 7 Examples of the group replaced by -or -CO- include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an amino group (a group in which -CH2- contained in a methyl group is replaced by -NR 7 -), an oxy group (a group in which -CH2- contained in a methylene group is replaced by -O-), a carbonyl group (a group in which -CH2- contained in a methylene group is replaced by -CO-), a thio group (a group in which -CH2- contained in a methylene group is replaced by -S-), a sulfonyl group (a group in which -CH2- contained in a methylene group is replaced by -SO2-), a peptide group (a group in which -CH2-CH2- contained in an ethylene group is replaced by -CO-NR 7 -), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), an alkylamino group (a group in which -CH2- at any position contained in an alkyl group is replaced by -NR 7 -), an alkyl peptide group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-NR 7-replaced group), alkoxycarbonyl group (a group in which any -CH2-CH2- in the alkyl group is replaced by -O-CO-), alkylcarbonyl group (a group in which any -CH2- in the alkyl group is replaced by -CO-), alkylcarbonyloxy group (a group in which any -CH2-CH2- in the alkyl group is replaced by -CO-O-), alkoxycarbonyloxy group (a group in which any -CH2-CH2-CH2- in the alkyl group is replaced by -O-CO-O-), alkoxyalkoxy group (a group in which two -CH2- at any position in the alkyl group are each replaced by -O-), alkanedioxy group (a group in which any -CH2- in the alkanedioxy group is replaced by -O-), alkanedioxycarbonyl group (a group in which any -CH2-CH2- in the alkanedioxy group is replaced by -O-CO-), alkanediylcarbonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -CO-), alkanediylcarbonyloxy group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-O-), alkanedioxycarbonyloxy group (a group in which any -CH2-CH2-CH2- in the alkanediyl group is replaced by -O-CO-O-), alkanediylsulfonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -SO2-), alkanediylthio group (a group in which any -CH2- in the alkanediyl group is replaced by -S-), alkanediylamino group (a group in which any -CH2- in the alkanediyl group is replaced by -NR 7 -replaced group), alkanediylpeptide group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-NR 7 -replaced group), cycloalkoxy group, cycloalkylalkoxy group, a group formed by combining two or more of these groups, etc.
[0015] Examples of the alkoxy group include alkoxy groups having 1 to 27 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group and the like. The number of carbon atoms of the alkoxy group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 27 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group and the like. The number of carbon atoms of the alkylthio group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylamino group include alkylamino groups having 1 to 27 carbon atoms, such as methylamino group, ethylamino group, dimethylamino group, propylamino group, butylamino group, pentylamino group, pentylamino group, hexylamino group and the like. The number of carbon atoms of the alkylamino group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylpeptide group include alkylpeptide groups having 1 to 27 carbon atoms, such as methylpeptide group, ethylpeptide group, propylpeptide group and the like. The number of carbon atoms of the alkylpeptide group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 27 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 28 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 27 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 26 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the alkoxyalkoxy group include alkoxyalkoxy groups having 2 to 26 carbon atoms, such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group and the like. The number of carbon atoms of the alkoxycarbonyl group may be 2 to 17, preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group may be 2 to 18, preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group may be 2 to 17, preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxycarbonyloxy group may be 2 to 16, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxyalkoxy group may be 2 to 16, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 27 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, undecylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 27 carbon atoms, such as methylene-oxy group, ethylene-oxy group, propanediyl-oxy group, butanediyl-oxy group, pentanediyl-oxy group and the like. The number of carbon atoms of the alkanediyl-oxy group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 27 carbon atoms, such as a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propanediyl-oxycarbonyl group, and a butanediyl-oxycarbonyl group. Examples of the alkanediyl-carbonyl group include alkanediyl-carbonyl groups having 2 to 28 carbon atoms, such as a methylene-carbonyl group, an ethylene-carbonyl group, a propanediyl-carbonyl group, a butanediyl-carbonyl group, and a pentanediyl-carbonyl group. Examples of the alkanediyl-carbonyl-oxy group include alkanediyl-carbonyl-oxy groups having 2 to 27 carbon atoms, such as a methylene-carbonyl-oxy group, an ethylene-carbonyl-oxy group, a propanediyl-carbonyl-oxy group, and a butanediyl-carbonyl-oxy group. Examples of the alkanediyl-oxycarbonyl-oxy group include alkoxycarbonyl-oxy groups having 2 to 26 carbon atoms, such as a butoxycarbonyl-oxy group. The number of carbon atoms in the alkanediyl-oxycarbonyl group may be 2 to 17, preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-carbonyl group may be 2 to 18, preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-carbonyl-oxy group may be 2 to 17, preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-oxycarbonyl-oxy group may be 2 to 16, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 27 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, and a propylenesulfonyl group. The number of carbon atoms in the alkanediylsulfonyl group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylthio group include alkanediylthio groups having 1 to 27 carbon atoms, such as a methylenethio group, an ethylenethio group, and a propylenethio group. The number of carbon atoms in the alkanediylthio group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylamino group include alkanediylamino groups having 1 to 27 carbon atoms, such as a methyleneamino group, an ethylenamino group, a dimethyleneamino group, a propylenamino group, a butylenamino group, a pentylenamino group, and a hexylenamino group. The number of carbon atoms in the alkanediylamino group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylpeptide group include alkanediylpeptide groups having 1 to 27 carbon atoms, such as a methylenepeptide group, an ethylenpeptide group, and a propylenpeptide group. The number of carbon atoms in the alkanediylpeptide group may be 1 to 17, preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 27 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 27 carbon atoms, such as a cyclohexylmethoxy group.
[0016] In addition, -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO-, -SO-, -NR 7Examples of the group replaced by - or -SO2- include the following groups. Among the groups represented below, groups in which -O- is replaced by -S- and -CO- is replaced by -SO2- respectively are also included. The bonding site can be at any position. TIFF2025113198000012.tif54167
[0017] L 1 Examples of the substituent that may be possessed include a halogen atom, a cyano group, a nitro group, etc. L 1 When L is a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group such as an alkyl group, the chain hydrocarbon group such as an alkyl group can be substantially a substituent of the alicyclic hydrocarbon group. Also, L 1 When -CH2- contained in the chain hydrocarbon group such as an alkyl group contained in L is replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO2-, L 1 can substantially have substituents such as a hydroxy group, a carboxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an alkoxyalkoxy group, a thiol group, an alkylthio group, an alkylsulfonyl group, an amino group, an alkylamino group, an alkylpeptide group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc. L 1 The aliphatic hydrocarbon group of L may have one substituent or a plurality of substituents. L 1 The substituent in L is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom, and still more preferably a methyl group or a fluorine atom.
[0018] L 1Examples include a single bond, a chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO2-), or a group formed by combining these. Preferably, it is a single bond, a chain hydrocarbon group having 1 to 10 carbon atoms (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or a group formed by combining these. More preferably, it is a single bond, a linear or branched alkanediyl group having 1 to 8 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 12 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or a group formed by combining these. Even more preferably, it is a single bond or a linear alkanediyl group having 1 to 6 carbon atoms. L 1 When L is a group formed by combining an alicyclic hydrocarbon group and an alkanediyl group, it is preferably a group represented by the formula (L1-A). TIFF2025113198000013.tif1377[In the formula (L1-A), L 11 represents a single bond or an alkanediyl group having 1 to 3 carbon atoms which may have a substituent, W 11 represents an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), X 11 represents ***-O-CO-, ***-CO-O-, ***-O-CO-O- or -O-, L 12represents an alkane diyl group having 1 to 3 carbon atoms which may have a single bond or a substituent, *, **, and *** each represent a bonding site, * represents the bonding site with X 1 **, represents the bonding site with the benzene ring, and *** represents the bonding site with W 11 .] L 11 and L 12 As the alkane diyl groups of, within the range allowed by the upper limit of the number of carbon atoms, groups similar to the alkane diyl groups exemplified by L 1 can be mentioned. W 11 As the alicyclic hydrocarbon group of, within the range allowed by the upper limit of the number of carbon atoms, the alicyclic hydrocarbon groups exemplified by L 1 can be mentioned. W 11 is preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms. L 11 and L 12 are each independently preferably a single bond or a methylene group. L 1 The bonding position of to the benzene ring may be any of the ortho, meta, or para positions with respect to the bonding position of the carbon atom to which R 5 is bonded, but it is preferably bonded to the ortho or para position.
[0019] R 3 and R 4 Examples of the halogen atoms of include fluorine atom, chlorine atom, bromine atom, iodine atom, and the like. R 3 and R 4The C1-C12 haloalkyl group represents an alkyl group having 1 to 12 carbon atoms and a halogen atom, and examples thereof include a C1-C12 fluoroalkyl group, a C1-C12 chloroalkyl group, a C1-C12 bromoalkyl group, and a C1-C12 iodoalkyl group. Examples of the haloalkyl group include a C1-C12 perfluoroalkyl group (such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc.), a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a difluoromethyl group, etc. The number of carbon atoms of the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. R 3 and R 4 Examples of the C1-C18 hydrocarbon group of R and R include chain hydrocarbon groups such as alkyl groups and alkanediyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. The alkyl group is a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The alkanediyl group is a linear or branched alkanediyl group, and examples of the linear alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group, and Examples of the branched alkanediyl group include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. The terminal of the branched alkanediyl group may be an alkyl group such as a methyl group. The number of carbon atoms in the chain hydrocarbon group may be 1 to 16, preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples include the groups represented below. The bonding site can be at any position. TIFF2025113198000014.tif46168Specifically, examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group. Examples of the polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, a spirocyclohexane-1,2'-cyclopentane group, and a spiroadamantane-2,3'-cyclopentane group, and polycyclic cycloalkyl groups such as a spiro ring having a cycloalkyl group spiro-bonded to each of a norbornyl group or an adamantyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and still more preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and a binaphthyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.
[0020] Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group - alkane diyl group - *, alkyl group - aromatic hydrocarbon group - *, alkyl group - aromatic hydrocarbon group - alkane diyl group - *, where -CH2- contained in the alkane diyl group and the alkyl group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO2-.), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group - alkane diyl group - *, alkyl group - alicyclic hydrocarbon group - *, alkyl group - alicyclic hydrocarbon group - alkane diyl group - *, where -CH2- contained in the alicyclic hydrocarbon group, the alkane diyl group and the alkyl group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO2-.), a group formed by combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *, where -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO2-.). * represents a bonding site. Examples of the aromatic hydrocarbon group - alkane diyl group - * include aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group - aromatic hydrocarbon group - * include tolyl group, xylyl group, cumenyl group, etc. Examples of the alicyclic hydrocarbon group - alkane diyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl group, etc. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include phenylcyclohexyl group, etc. Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group-* include a cyclohexylphenyl group and the like. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined with each other. Further, any of these groups may be bonded to the benzene ring.
[0021] R 3 and R 4 When -CH2- contained in the haloalkyl group or hydrocarbon group represented by is replaced by -O-, -CO-, -S-, -SO-, -NR 7 -, or -SO2-, the number of carbon atoms before replacement is defined as the total number of carbon atoms of the haloalkyl group or the hydrocarbon group. Further, the number may be one or two or more. Examples of the group in which -CH2- contained in the haloalkyl group and hydrocarbon group is replaced by -O-, -S-, -SO2-, -SO-, -NR 7 -, or -CO- include a hydroxy group (a group in which -CH2- contained in the methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in the ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in the methyl group is replaced by -S-), an amino group (a group in which -CH2- contained in the methyl group is replaced by -NR 7 -), an oxy group (a group in which -CH2- contained in the methylene group is replaced by -O-), a carbonyl group (a group in which -CH2- contained in the methylene group is replaced by -CO-), a thio group (a group in which -CH2- contained in the methylene group is replaced by -S-), a sulfonyl group (a group in which -CH2- contained in the methylene group is replaced by -SO2-), a peptide group (a group in which -CH2-CH2- contained in the ethylene group is replaced by -CO-NR 7-replaced group), alkoxy group (a group in which any -CH2- in the alkyl group is replaced by -O-), alkoxycarbonyl group (a group in which any -CH2-CH2- in the alkyl group is replaced by -O-CO-), alkylcarbonyl group (a group in which any -CH2- in the alkyl group is replaced by -CO-), alkylcarbonyloxy group (a group in which any -CH2-CH2- in the alkyl group is replaced by -CO-O-), alkoxycarbonyloxy group (a group in which any -CH2-CH2-CH2- in the alkyl group is replaced by -O-CO-O-), alkoxyalkoxy group (a group in which two -CH2- at any position in the alkyl group are replaced by -O-), alkylthio group (a group in which any -CH2- in the alkyl group is replaced by -S-), alkylsulfonyl group (a group in which any -CH2- in the alkyl group is replaced by -SO2-), alkylamino group (a group in which any -CH2- in the alkyl group is replaced by -NR 7 -replaced group), alkylpeptide group (a group in which any -CH2-CH2- in the alkyl group is replaced by -CO-NR 7-replaced group), an alkanediyl-oxy group (a group in which any -CH2- in the alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -O-CO-), an alkanediyl-carbonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -CO-), an alkanediyl-carbonyl-oxy group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-O-), an alkanediyl-oxycarbonyl-oxy group (a group in which any -CH2-CH2-CH2- in the alkanediyl group is replaced by -O-CO-O-), an alkanediyl-thio group (a group in which any -CH2- in the alkanediyl group is replaced by -S-), an alkanediyl-sulfonyl group (a group in which any -CH2- in the alkanediyl group is replaced by -SO2-), an alkanediyl-amino group (a group in which any -CH2- in the alkanediyl group is replaced by -NR 7 -replaced group), an alkanediyl-peptide group (a group in which any -CH2-CH2- in the alkanediyl group is replaced by -CO-NR 7 -replaced group), a cycloalkoxy group, a cycloalkyl-alkoxy group, an aromatic-hydrocarbon group-carbonyl-oxy group, an aromatic-hydrocarbon group-carbonyl group, an aromatic-hydrocarbon group-oxy group, a haloalkoxy group (a group in which any -CH2- in the haloalkyl group is replaced by -O-), a haloalkoxycarbonyl group (a group in which any -CH2-CH2- in the haloalkyl group is replaced by -O-CO-), a haloalkyl-carbonyl group (a group in which any -CH2- in the haloalkyl group is replaced by -CO-), a haloalkyl-carbonyl-oxy group (a group in which any -CH2-CH2- in the haloalkyl group is replaced by -CO-O-), a group formed by combining two or more of these groups, and the like. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylamino group include alkylamino groups having 1 to 17 carbon atoms, such as methylamino group, ethylamino group, dimethylamino group, propylamino group, butylamino group, pentylamino group, pentylamino group, hexylamino group and the like. The number of carbon atoms of the alkylamino group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylpeptide group include alkylpeptide groups having 1 to 17 carbon atoms, such as methylpeptide group, ethylpeptide group, propylpeptide group and the like. The number of carbon atoms of the alkylpeptide group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as butoxycarbonyloxy group and the like. Examples of the alkoxyalkoxy group include alkoxyalkoxy groups having 2 to 16 carbon atoms, such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxycarbonyloxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, undecylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 17 carbon atoms, such as methylene-oxy group, ethylene-oxy group, propanediyl-oxy group, butanediyl-oxy group, pentanediyl-oxy group and the like. The number of carbon atoms of the alkanediyl-oxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 17 carbon atoms, such as a methylene-oxycarbonyl group, an ethylene-oxycarbonyl group, a propanediyl-oxycarbonyl group, and a butanediyl-oxycarbonyl group. Examples of the alkanediyl-carbonyl group include alkanediyl-carbonyl groups having 2 to 18 carbon atoms, such as a methylene-carbonyl group, an ethylene-carbonyl group, a propanediyl-carbonyl group, a butanediyl-carbonyl group, and a pentanediyl-carbonyl group. Examples of the alkanediyl-carbonyl-oxy group include alkanediyl-carbonyl-oxy groups having 2 to 17 carbon atoms, such as a methylene-carbonyl-oxy group, an ethylene-carbonyl-oxy group, a propanediyl-carbonyl-oxy group, and a butanediyl-carbonyl-oxy group. Examples of the alkanediyl-oxycarbonyl-oxy group include alkoxycarbonyl-oxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyl-oxy group. The number of carbon atoms in the alkanediyl-oxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-carbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-carbonyl-oxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkanediyl-oxycarbonyl-oxy group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkanediyl-thio group include alkanediyl-thio groups having 1 to 17 carbon atoms, such as a methylene-thio group, an ethylene-thio group, and a propylene-thio group. The number of carbon atoms in the alkanediyl-thio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, and a propylenesulfonyl group. The number of carbon atoms of the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylamino group include alkanediylamino groups having 1 to 17 carbon atoms, such as a methyleneamino group, an ethyleneamino group, a dimethyleneamino group, a propyleneamino group, a butyleneamino group, a pentyleneamino group, and a hexyleneamino group. The number of carbon atoms of the alkanediylamino group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylpeptide group include alkanediylpeptide groups having 1 to 17 carbon atoms, such as a methylenepeptide group, an ethylenepeptide group, and a propylenepeptide group. The number of carbon atoms of the alkanediylpeptide group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of the aromatic hydrocarbon group-carbonyloxy group include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. Examples of the aromatic hydrocarbon group-carbonyl group include aromatic hydrocarbon group-carbonyl groups having 7 to 18 carbon atoms, such as a benzoyl group. Examples of the aromatic hydrocarbon group-oxy group include aromatic hydrocarbon group-oxy groups having 6 to 17 carbon atoms, such as a phenyloxy group. Examples of the haloalkoxy group, haloalkoxycarbonyl group, haloalkylcarbonyl group, and haloalkylcarbonyloxy group include a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxycarbonyl group having 2 to 11 carbon atoms, a haloalkylcarbonyl group having 2 to 12 carbon atoms, and a haloalkylcarbonyloxy group having 2 to 11 carbon atoms. For example, groups in which one or more hydrogen atoms of the groups exemplified above are replaced with a halogen atom can be mentioned.
[0022] In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -SO2-, -SO-, -NR 7 -, or -CO- include the groups represented below. Among the groups represented below, groups in which -O- is replaced with -S- and -CO- is replaced with -SO2- are also included. The bonding site can be at any position. TIFF2025113198000015.tif54167 Examples of the group in which -CH2- contained in a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group is replaced with -O-, -CO-, -S-, -SO-, -SO2- or -NR 7 - include the following groups. -O- or -CO- in the groups represented below may be replaced with -S-, -SO-, -SO2- or -NR 7 - respectively. The bonding site can be at any position. TIFF2025113198000016.tif38164
[0023] R 3 and R 4 Examples of the substituent that the hydrocarbon group of may have include a halogen atom, a cyano group, a nitro group, etc. R 3 and R 4 By replacing -CH2- contained in with -O-, -S-, -CO-, -SO-, -NR 7 -, or -SO2-, substantially, R 3 and R 4can have substituents such as a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an alkoxyalkoxy group, a thiol group, an alkylthio group, an alkylsulfonyl group, an amino group, an alkylamino group, an alkylpeptide group, etc. Also, R 3 and R 4 When they are a group combining an alicyclic hydrocarbon group or an aromatic hydrocarbon group with a chain hydrocarbon group such as an alkyl group, the chain hydrocarbon group such as an alkyl group can be substantially a substituent of the alicyclic hydrocarbon group or the aromatic hydrocarbon group. Examples of the halogen atom include the same groups as those described above. The hydrocarbon group may have one substituent or a plurality of substituents. R 3 and R 4 are preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group or the haloalkyl group may be replaced by -O- or -CO-), more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) or a haloalkyl group having 1 to 4 carbon atoms, still more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a carboxy group or a fluoroalkyl group having 1 to 3 carbon atoms, even more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, a carboxy group or a perfluoroalkyl group having 1 to 3 carbon atoms, and even still more preferably an iodine atom, a fluorine atom, a hydroxy group, a methoxy group or a trifluoromethyl group. m3 is any integer from 1 to 4, preferably any integer from 1 to 3, and more preferably 1 or 2. When m3 is an integer of 1 or more, at least one of R 3 is preferably an alkoxy group having 1 to 3 carbon atoms or an iodine atom. m4 is an integer of any one of 0 to 4, preferably an integer of any one of 0 to 3, more preferably an integer of any one of 0 to 2, and still more preferably 1 or 2. When m4 is an integer of 1 or more, R 4 at least one of them is preferably an alkoxy group having 1 to 3 carbon atoms or an iodine atom. R 3 and R 4 The bonding positions to the benzene ring of each may be independently any of the ortho, meta, or para positions with respect to the bonding position of the carbon atom to which R 5 is bonded, but at least one is preferably bonded to the meta position. R 3 and R 4 When at least one of them is an iodine atom, the bonding position of the iodine atom to the benzene ring may be any of the ortho, meta, or para positions with respect to the bonding position of the carbon atom to which R 5 is bonded, but at least one is preferably bonded to the meta position.
[0024] R 5 Examples of the halogen atom of R 1 include the same halogen atoms as the substituents that L R 5 The alkyl group having 1 to 6 carbon atoms in R 5 is a linear or branched alkyl group, and examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and hexyl group. The alkyl group of R R 5is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
[0025] Examples of the anion (I) include the following anions. TIFF2025113198000017.tif79164
[0026] TIFF2025113198000018.tif190162
[0027] 〔Cation (I)〕 ZI + Examples of the organic cation of [ZI] include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, cations represented by any of formulas (b2-1) to (b2-5) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) are included. TIFF2025113198000019.tif82159[In formulas (b2-1) to (b2-5), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Rb4 and R b5 may combine with each other to form a ring together with the sulfur atom to which they are attached, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of any one of 0 to 5. When m2 is 2 or more, the plurality of R b7 may be the same or different, and when n2 is 2 or more, the plurality of R b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may combine with each other to form a ring together with the sulfur atom to which they are attached, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 may combine with each other to form a ring including -CH-CO- to which they are attached, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13~R b18 and R b21 ~R b26 ~R each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b13 R and b14 R and b21 R and b22 R and R may be bonded to each other to form a ring containing a sulfur atom together with the benzene ring to which they are bonded, and -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b27 ~R b29 ~R each independently represents a hydrogen atom or a group containing an acid-labile group. L b31 and L b41 ~L b43 ~L each independently represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of any one of 0 to 5. q2 and r2 each independently represent an integer of any one of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, a plurality of R b13 are the same or different, when p2 is 2 or more, a plurality of R b14 are the same or different, when q2 is 2 or more, a plurality of R b15 are the same or different, when r2 is 2 or more, a plurality of R b16 are the same or different, when s2 is 2 or more, a plurality of R b17 are the same or different, when t2 is 2 or more, a plurality of R b18 are the same or different. u3 represents an integer of any one of 1 to 3, and satisfies 1 ≦ u3 + q23 ≦ 5. u4 and u5 each independently represent an integer of any one of 0 to 3, and satisfy 0 ≦ u4 + o21 ≦ 5 and 0 ≦ u5 + p22 ≦ 5. o21, p22, q23, r24, t25, and s26 each independently represent an integer of any one of 0 to 4. When u3, u4, and u5 are each 2 or more, the groups within the plurality of parentheses are each the same or different. When o21, p22, q23, r24, t25, and s26 are each 2 or more, the plurality of Rs b21 ~R b26 are each the same or different.] When u2 is 0, any one of o2, p2, q2, and r2 is 1 or more, and at least one of R b13 ~R b16 is preferably a halogen atom. When u2 is 1, any one of o2, p2, s2, t2, q2, and r2 is 1 or more, and at least one of R b13 ~R b18 is preferably a halogen atom. Furthermore, when u2 is 0, r2 is preferably 1 or more, and more preferably 1. Also, when u2 is 0 and r2 is 1 or more, R b16 is preferably a halogen atom.
[0028] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, the chain hydrocarbon group of R b9 ~R b12 is preferably 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. TIFF2025113198000020.tif11157 In particular, R b9 ~R b12The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
[0029] Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornil group, an isobornyl group, and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
[0030] The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4.
[0031] Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group, and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include a p-cyclohexylphenyl group and a p-adamantylphenyl group. When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferable. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.
[0032] Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group.
[0033] R b4 and R b5 The ring formed by R and R being bonded to each other together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings, and examples thereof are shown below. * represents a bonding site. TIFF2025113198000021.tif24142
[0034] R b9 and R b10The ring formed by combining them may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. For example, thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. may be mentioned. R b11 and R b12 The ring formed by combining them may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring, etc. may be mentioned. R b27 ~R b29 Examples of the group containing an acid-labile group of ~R c30 include -R c30 or -L c10 -CO-O-R c30 wherein the group represented by (L c10 represents an alkanediyl group having 1 to 6 carbon atoms, and R c30 represents an acid-labile group.). etc. may be mentioned. R b27 ~R b29 Examples of the acid-labile group of ~R include the group represented by formula (1) or formula (2) exemplified in this specification.
[0035] Among cations (b2-1) to (b2-5), preferably, cation (b2-1), cation (b2-4) or cation (b2-5). Examples of cation (b2-1) include the following cations. TIFF2025113198000022.tif158165 Examples of cation (b2-2) include the following cations. TIFF2025113198000023.tif18150 Examples of cation (b2-3) include the following cations. TIFF2025113198000024.tif26140 Examples of cation (b2-4) include the following cations. For the cation (b2-5), the following cations can be mentioned. TIFF2025113198000026.tif115158
[0036] Specific examples of the salt (I) include salts formed by arbitrarily combining the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the following table. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation, and "~" indicates that each of the salt (I) and the anion (I) corresponds. For example, the salt (I-1) is a salt composed of the anion represented by the formula (Ia-1) and the cation represented by the formula (b2-c-1), the salt (I-2) is a salt composed of the anion represented by the formula (Ia-2) and the cation represented by the formula (b2-c-1), and the salt (I-11) is a salt composed of the anion represented by the formula (Ia-1) and the cation represented by the formula (b2-c-10). TIFF2025113198000027.tif3294
Table 1
[0037] Among them, as the salt (I), it is preferable that the salt is a combination of an anion represented by any of the formulas (Ia-1) to (Ia-20) and a cation represented by any of the formulas (b2-c-1), (b2-c-10), (b2-c-13), (b2-c-14), (b2-c-18) to (b2-c-20), (b2-c-27), (b2-c-30), (b2-c-31), (b2-c-47), (b2-c-48), (b2-c-50) to (b2-c-68).
[0038] <Method for producing the salt (I)> In the salt (I), X 1The salt where *-O-CO- (the salt represented by formula (I1-1) or formula (I2-1)) can be produced, for example, by reacting a compound represented by formula (I1-b1) or a compound represented by formula (I2-b1) with carbonyldiimidazole in a solvent and then further reacting with a salt represented by formula (I1-a). TIFF2025113198000030.tif71156(wherein all the symbols have the same meanings as described above.) Examples of the solvent in this reaction include chloroform, acetonitrile, etc. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours. Examples of the salt represented by formula (I1-a) include salts represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods.
[0039] Examples of the salt represented by formula (I1-a) include salts represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods. TIFF2025113198000031.tif167155Examples of the compound represented by formula (I1-b1) include compounds represented by the following formula, etc., which can be easily obtained from the market. TIFF2025113198000032.tif2422Examples of the compound represented by formula (I2-b1) include compounds represented by the following formula, etc., which can be easily obtained from the market. TIFF2025113198000033.tif1725In salt (I), X 1 The salt where *-CO-O- (the salt represented by formula (I1-2) or formula (I2-2)) can be produced, for example, by reacting a salt represented by formula (I2-a) with carbonyldiimidazole in a solvent and then further reacting with a compound represented by formula (I2-b1) or a compound represented by formula (I2-b2). TIFF2025113198000034.tif58153(wherein all the symbols have the same meanings as described above.) Examples of the solvent in this reaction include chloroform and acetonitrile etc. The reaction temperature is generally 5°C to 80°C, and the reaction time is generally 0.5 hour to 24 hours. Examples of the salt represented by formula (I2-a) include salts represented by the following formula, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF2025113198000035.tif160163
[0040] Examples of the compound represented by formula (I1-b2) include compounds represented by the following formula, which can be easily obtained from the market. TIFF2025113198000036.tif2257 Examples of the compound represented by formula (I2-b2) include compounds represented by the following formula, which can be easily obtained from the market. TIFF2025113198000037.tif1721
[0041] In salt (I), X 1 The salt in which X is *-O-CO-O- (the salt represented by formula (I1-3) or formula (I2-3)) can be produced, for example, by reacting a compound represented by formula (I2-b1) or a compound represented by formula (I2-b2) with carbonyldiimidazole in a solvent and then further reacting with the salt represented by formula (I1-a). TIFF2025113198000038.tif62162 (In the formula, all symbols have the same meanings as described above.) Examples of the solvent in this reaction include chloroform and acetonitrile etc. The reaction temperature is generally 5°C to 80°C, and the reaction time is generally 0.5 hour to 24 hours.
[0042] In salt (I), X 1The salt having -O- (the salt represented by the formula (I1-4) or the formula (I2-4)) can be produced, for example, by reacting a compound represented by the formula (I2-b1) or a compound represented by the formula (I2-b2) with the salt represented by the formula (I1-a) in a solvent in the presence of a base. TIFF2025113198000039.tif62140(In the formula, all the symbols have the same meanings as described above respectively.) Examples of the base in this reaction include potassium hydroxide. Examples of the solvent in this reaction include chloroform and acetonitrile. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours.
[0043] [Structural unit derived from the salt represented by the formula (I)] The structural units derived from the salt represented by the formula (I1) and the salt represented by the formula (I2) of the present invention are the structural unit represented by the following formula (IP1) (hereinafter sometimes referred to as "structural unit (IP1)") and the structural unit represented by the formula (IP2) (hereinafter sometimes referred to as "structural unit (IP2)"). The structural unit (IP1) and the structural unit (IP2) together may be referred to as the structural unit (IP). TIFF2025113198000040.tif50158[In the formula (IP1) and the formula (IP2), all the symbols have the same meanings as described above respectively.] The structural unit (IP) shows a state in which the double bond of CH2=C-R contained in the salt (I) is cleaved. 5 Such a structural unit (IP) functions as an acid generator as well as the salt (I), and also functions as a structural unit constituting a compound or a resin.
[0044] [Resin containing the structural unit (IP) derived from the salt (I)] The resin of the present invention is a resin containing the structural unit (IP) (hereinafter sometimes referred to as "resin (Ap)"). The resin (Ap) may be a homopolymer containing one type of structural unit (IP), or a copolymer containing two or more types of structural units (IP). In addition, the resin (Ap) may contain structural units other than the structural unit (IP). Examples of the structural units other than the structural unit (IP) include a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)") and structural units other than the structural unit (a1), as described later. Examples of the structural units other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), and other structural units known in the art. Here, the "acid-labile group" means a group having a leaving group, and when contacted with an acid, the leaving group is eliminated, and the constituent unit is converted into a constituent unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). The content of the structural unit (IP) is 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 0.8 mol% or more, and still more preferably 1 mol% or more, based on all the structural units of the resin (Ap). Also, it is 100 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably 10 mol% or less. Specifically, it is 0.1 to 100 mol%, preferably 0.5 to 50 mol%, more preferably 0.8 to 30 mol%, and still more preferably 1 to 10 mol%.
[0045] In particular, when the resin (Ap) is used in a resist composition, as described later, in addition to the structural unit (IP), it may further contain the structural unit (a1). In addition, when the resin (Ap) is used in a resist composition, as described later, regardless of whether it contains the structural unit (a1) or not, it may be used in combination with a resin containing the structural unit (a1) (hereinafter sometimes referred to as "resin (A)") and / or a resin other than the resin (A). Hereinafter, the resin (Ap) and / or the resin (A) may sometimes be referred to as "resin (A) etc.". The resin (Ap) and the resin (A) preferably further contain structural units other than the structural unit (a1), respectively.
[0046] 〈Structural unit (a1)〉 The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid-labile group contained in the resin (A) or the like is preferably a group represented by the formula (1) (hereinafter also referred to as group (1)) and / or a group represented by the formula (2) (hereinafter also referred to as group (2)). TIFF2025113198000041.tif2298[In the formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding site.] TIFF2025113198000042.tif2278[In the formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-, and the hydrocarbon group and the heterocyclic group may have a halogen atom. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bonding site.]
[0047] R a1 、R a2 and Ra3 Examples of the alkyl group in [description] include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. R a1 、R a2 and R a3 Examples of the alkenyl group in [description] include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group. R a1 、R a2 and R a3 The alicyclic hydrocarbon group in [description], [description], and [description] may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding site), etc. The number of carbon atoms of the alicyclic hydrocarbon group in [description], [description], and [description] is preferably 3 to 16. a1 、R a2 and R a3 Examples of the aromatic hydrocarbon group in [description], [description], and [description] include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. TIFF2025113198000043.tif10159R a1 、R a2 and R a3 Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), an aralkyl group such as benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as phenylcyclohexyl group, and the like. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, examples of -C(R a1 )(R a2 )(R a3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding site with -O-. TIFF2025113198000044.tif30138
[0048] R a1’ 、R a2’ and R a3’ Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and the group formed by combining these are the same as the groups exemplified for R a1 、R a2 and R a3 . R a2’ and R a3’ When they are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’)-X-R a3’ Examples thereof include the following groups. * represents a bonding site. TIFF2025113198000045.tif19124R a1’ and R a2’ At least one of them is preferably a hydrogen atom. na’ is preferably 0. R a1 R a2 R a3 R a1 R a2’ and R a3’ The halogen atom that may be possessed by R, R, R, R, R, R, and R includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
[0049] Examples of the group (1) include the following groups. In formula (1), R, R, and R are alkyl groups, ma = 0, and na = 1. Preferred examples of such a group include a tert-butoxycarbonyl group. a1 R a2 and R a3 In formula (1), R, R, and R are alkyl groups, ma = 0, and na = 1. Preferred examples of such a group include a tert-butoxycarbonyl group. In formula (1), R and R together with the carbon atom to which they are attached form an adamantyl group, R is an alkyl group, ma = 0, and na = 1. a1 R a2 In formula (1), R and R together with the carbon atom to which they are attached form an adamantyl group, R is an alkyl group, ma = 0, and na = 1. a3 In formula (1), R and R are each independently an alkyl group, R is an adamantyl group, ma = 0, and na = 1. In formula (1), R and R are each independently an alkyl group, R is an adamantyl group, ma = 0, and na = 1. a1 and R a2 In formula (1), R and R are each independently an alkyl group, R is an adamantyl group, ma = 0, and na = 1. a3 Specific examples of the group (1) include the following groups. * represents a bonding site. Specific examples of the group (1) include the following groups. * represents a bonding site. TIFF2025113198000046.tif151166
[0050] Specific examples of the group (2) include the following groups. * represents a bonding site. TIFF2025113198000047.tif56153
[0051] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group. Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferable. If a resin (A) or the like having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.
[0052] Examples of the structural unit derived from the (meth)acrylic monomer having the group (1) include a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as the structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2), more preferably at least one or two structural units selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF2025113198000048.tif46153[In the formula (a1-0), the formula (a1-1), and the formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. R a01 、R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 、R a03 and R a04Each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. R a6 and R a7 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. m1’ represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.
[0053] R a01 、R a4 、R a5 Examples of the halogen atom in R, R, and R include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R a01 、R a4 、R a5 Examples of the alkyl group that may have a halogen atom in R, R, and R include a chloromethyl group, a bromomethyl group, an iodomethyl group, a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group. R a01 、Ra4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 R a03 R a04 R a6 and R a7 Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and combinations thereof in R a1 R a2 and R a3 are the same as those exemplified for the groups in R R a02 R a03 and R a04 The alkyl group in R R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group. R a6 and R a7 The alkyl group in R R a02 R a03 R a04 R a6 and R a7 The number of carbon atoms of the alicyclic hydrocarbon group of R R a02 R a03 R a04 Ra6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group of and R is preferably 6 to 12, more preferably 6 to 10. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and alicyclic hydrocarbon group combined is 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and aromatic hydrocarbon group combined is 18 or less. R a02 and R a03 and R are preferably an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a halogen atom, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group which may have a halogen atom. R a04 R is preferably an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or an alicyclic hydrocarbon group having 5 to 12 carbon atoms which may have a halogen atom, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group which may have a halogen atom. R a6 and R a7 and R are preferably an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkenyl group having 2 to 6 carbon atoms which may have a halogen atom or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a halogen atom, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group which may have a halogen atom, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group which may have a halogen atom. m1' is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.
[0054] Examples of the structural unit (a1-0) include a structural unit represented by any of Formula (a1-0-1) to Formula (a1-0-24) and an R in the structural unit (a1-0). a01 Examples of the structural unit include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group (alkyl group having a halogen atom), or another alkyl group, and a structural unit represented by any of Formula (a1-0-1) to Formula (a1-0-10), Formula (a1-0-13), Formula (a1-0-14), Formula (a1-0-19) to Formula (a1-0-24) is preferable. TIFF2025113198000049.tif120160
[0055] Examples of the structural unit (a1-1) include a structural unit derived from the monomers described in JP-A-2010-204646. Among them, a structural unit represented by any of Formula (a1-1-1) to Formula (a1-1-7) and an R in the structural unit (a1-1). a4 Examples of the structural unit include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and a structural unit represented by any of Formula (a1-1-1) to Formula (a1-1-4) is more preferable. TIFF2025113198000050.tif33170
[0056] Examples of the structural unit (a1-2) include a structural unit represented by any of Formula (a1-2-1) to Formula (a1-2-20) and an R in the structural unit (a1-2). a5 Examples of the structural unit include a structural unit in which the methyl group corresponding to R is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and a structural unit represented by any of Formula (a1-2-2), Formula (a1-2-5), Formula (a1-2-6), and Formula (a1-2-10) to Formula (a1-2-20) is preferable. TIFF2025113198000051.tif91163
[0057] When resin (A), etc. contains structural unit (a1-0) and / or structural unit (a1-1) and / or structural unit (a1-2), the total content thereof is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, even more preferably 30 mol% or more, still even more preferably 40 mol% or more, and even more preferably 50 mol% or more, based on all the structural units of resin (A), etc. Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, it is 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, and even more preferably 30 to 70 mol%. When resin (A), etc. contains structural unit (a1-0), the content thereof is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, even more preferably 25 mol% or more, still even more preferably 30 mol% or more, and even more preferably 35 mol% or more, based on all the structural units of resin (A), etc. Also, it is 80 mol% or less, preferably 75 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, and even more preferably 60 mol% or less. Specifically, it is 5 to 80 mol%, preferably 5 to 75 mol%, and more preferably 10 to 70 mol%. When resin (A) etc. contain structural unit (a1-1) and / or structural unit (a1-2), their total content rate is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, even more preferably 30 mol% or more, still even more preferably 40 mol% or more, and even more preferably 50 mol% or more with respect to all the structural units of resin (A) etc. Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, even more preferably 75 mol% or less, still even more preferably 70 mol% or less, and even more preferably 65 mol% or less. Specifically, 10 to 90 mol% is mentioned, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, even more preferably 20 to 75 mol%, still even more preferably 20 to 70 mol%, more preferably 20 to 60 mol%, and even more preferably 20 to 55 mol%.
[0058] Examples of the structural unit having group (2) in structural unit (a1) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025113198000052.tif31118[In formula (a1-4), R a1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a17 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a11represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -CO- or -NR a18 -. R a18 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a1 represents a single bond or a carbonyl group. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C-O- to which they are bonded, and -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. na1 represents any integer from 1 to 5. When na1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. na11 represents any integer from 0 to 4. When na11 is 2 or more, the plurality of R a17 may be the same as or different from each other. mc represents any integer from 0 to 2.]
[0059] R a1 and R a17 Examples of the halogen atom and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R a01 are the same as those exemplified by R of formula (a1-0) and the like. R a1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a17Examples of the alkoxy group in [compound name] include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, still more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. R a17 Examples of the alkoxyalkyl group in [compound name] include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably an alkoxyalkyl group having 2 to 4 carbon atoms, still more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a17 Examples of the alkoxyalkoxy group in [compound name] include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy groups. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably an alkoxyalkoxy group having 2 to 4 carbon atoms, and still more preferably a methoxyethoxy or ethoxyethoxy group. R a17 Examples of the alkylcarbonyl group in [compound name] include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 4 carbon atoms, more preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and still more preferably an acetyl group. R a17 Examples of the alkylcarbonyloxy group in [compound name] include acetyloxy, propionyloxy, and butyryloxy groups. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms, more preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and still more preferably an acetyloxy group. Ra17 is preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy methoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group.
[0060] A a11 Examples of the alkanediyl group of A include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, and branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, heptane-1,6-diyl group, octane-1,7-diyl group, nonane-1,8-diyl group, decane-1,9-diyl group, undecane-1,10-diyl group. The number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, still more preferably 1 to 4, even still more preferably 1 to 3, and even more preferably 1 or 2. R a18 Examples of the alkyl group of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and tert-butyl group. A a11 When -CH2- contained in the alkanediyl group of A is replaced by -O-, -CO- or -NR a18 -, the number of carbon atoms before replacement is defined as the number of carbon atoms of the alkanediyl group. A a11The -CH2- contained in the alkanediyl group of a18 Examples of the group replaced by -O-, -CO- or -NR For example, A a11 The -CH2- contained in the alkanediyl group of a18 Examples of the group replaced by -O-, -CO- or -NR a12 -CO-O-, *-O-CO-, *-CO-O-A a12 -CO-O-, *-O-A a12 -CO-O-, *-CO-O-A a12 -O-CO-, *-O-CO-A a12 -O-CO-, *-CO-NR a18 - are included. Among them, *-CO-O-, *-CO-O-A a12 -CO-O-, *-O-A a12 -CO-O-, *-CO-NR a18 - are preferred. Here, A a12 represents an alkanediyl group having 1 to 8 carbon atoms, and * represents the bonding site with the carbon atom to which R a1 is bonded. The alkanediyl group of A a12 includes alkanediyl groups similar to A a11 within the range allowed by the upper limit of the number of carbon atoms. A a11 is preferably a single bond, *-CO-O- or *-CO-O-A a12 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-. na1 is preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, and even more preferably 1 or 2. na11 is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and even more preferably 0 or 1. mc is preferably 0 or 1.
[0061] R a34 , R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these groups are combined. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, and norbornyl groups, as well as the following groups (* indicates a bonding site): TIFF2025113198000053.tif10151 Examples of aromatic hydrocarbon groups include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, etc. In particular, R a36 Examples of R include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups. R a35 and R a36 Examples of the divalent hydrocarbon group having 2 to 20 carbon atoms formed by R and R bonding to each other together with the -C-O- to which they are bonded include the following groups. * represents the bonding site, and one is the bonding site with R a34 and the other is the bonding site with R. TIFF2025113198000054.tif15105
[0062] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R a36The alkyl group and alicyclic hydrocarbon group in are preferably unsubstituted. R a36 The aromatic hydrocarbon group in preferably has an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.
[0063] -O-C(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) is eliminated by contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group or a carboxy group. -X a1 -O-C(R a34 )(R a35 )-O-R a36 in the case of a benzene ring may be bonded to any of the o-position, m-position, or p-position with respect to the bonding position of A a11 . Among them, it is preferable that at least one is bonded to the o-position or p-position, and more preferably bonded to the p-position. In the case of a naphthalene ring, when the bonding position of A a11 is the 1-position, it may be bonded to any of the 2nd to 8th positions, and when the bonding position of A a11 is the 2nd position, it may be bonded to any of the 1st and 3rd to 8th positions. Among them, when the bonding position of A a11 is the 1st position, it is preferable that at least one is bonded to the 3rd to 6th positions, and more preferably bonded to the 3rd or 4th position. When the bonding position of A a11 is the 2nd position, it is preferable that it is bonded to the 4th to 7th positions, and more preferably bonded to the 5th or 6th position.
[0064] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by the formulas (a1-4-1) to (a1-4-42) and R in the structural unit (a1-4) a1Examples of the structural unit in which the hydrogen atom corresponding to the formula is replaced with a halogen atom, a haloalkyl group, or an alkyl group include, more preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), formula (a1-4-14), formula (a1-4-19), and formula (a1-4-20). TIFF2025113198000055.tif228165
[0065] When the resin (A) or the like contains the structural unit (a1-4), the content thereof is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, further preferably 25 mol% or more, even more preferably 30 mol% or more, still even more preferably 40 mol% or more, and still further preferably 50 mol% or more with respect to the total of all the structural units of the resin (A) or the like. Also, it is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, further preferably 80 mol% or less, even more preferably 75 mol% or less, still even more preferably 70 mol% or less, and still further preferably 65 mol% or less. Specifically, it is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and still even more preferably 20 to 60 mol%.
[0066] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF2025113198000056.tif4558[In formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54represents -, h3 represents any integer from 1 to 4, and * represents the bonding site with L 51 represents the bonding site with L L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents any integer from 1 to 3. s1’ represents any integer from 0 to 3.]
[0067] R a8 Examples of the halogen atom and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include those exemplified by R of formula (a1-0), formula (a1-1) and formula (a1-2). a01 R a4 and R a5 include the same ones as those exemplified by R In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably any integer from 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.
[0068] Examples of the structural unit (a1-5) include, for example, the structural unit derived from the monomer described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. TIFF2025113198000057.tif31130
[0069] When the resin (A) etc. contains the structural unit (a1-5), the content thereof is 1 mol% or more, preferably 2 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, even more preferably 10 mol% or more, still even more preferably 20 mol% or more, and even more preferably 25 mol% or more, based on all the structural units of the resin (A) etc. Also, it is 80 mol% or less, preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 45 mol% or less, still even more preferably 40 mol% or less, and even more preferably 30 mol% or less. Specifically, 1 to 50 mol% is preferable, 3 to 45 mol% is more preferable, 5 to 40 mol% is still more preferable, and 5 to 30 mol% is even more preferable.
[0070] Examples of the structural unit having the group (1) in the structural unit (a1) include a structural unit represented by the formula (a1-6) (hereinafter sometimes referred to as "structural unit (a1-6)"). TIFF2025113198000058.tif3581[In the formula (a1-6), R a61 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a62 、R a63 and R a64 each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, or R a62 and R a63 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. X a61 represents a single bond, -CO-O-*, or -CO-NR a65 -*, where * represents the bonding site to Ar, and R a65 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a62 represents a single bond, *-O-L a61 - or *-CO-O-L a62- represents, * represents the bonding site with Ar, and L a61 and L a62 each independently represents an alkanediyl group having 1 to 4 carbon atoms. Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
[0071] R a61 As the halogen atom and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R a01 , R a4 and R a5 the same ones as exemplified by are mentioned. R a61 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. R a62 , R a63 , R a64 and R a65 As the alkyl group in, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like are mentioned. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group. R a62 , R a63 and R a64 As the cyclic hydrocarbon group in, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are mentioned. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 16, more preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenylene group, a naphthylene group and the like. Examples of the substituent that the cyclic hydrocarbon group may have include a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. R a62 and R a63 Examples of the ring formed by R a62 and R a63 bonding to each other include an adamantane ring, a cyclopentane ring, or a cyclohexane ring. Specifically, when R a62 (R a63 (R a64 ) represents -C(R a62 (R a63 (R a64 ) bonded to each other to form a ring, the following groups can be mentioned. * represents the bonding site to the oxygen atom. The number of carbon atoms in the ring is preferably 3 to 16, more preferably 3 to 12. TIFF2025113198000059.tif33109
[0072] L a61 and L a62 Examples of the alkanediyl group having 1 to 4 carbon atoms in L L a61 and L a62 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, etc. L a61 and L a62 are each independently preferably a methylene group or an ethylene group. X a61 is preferably a single bond or -CO-O-*, more preferably a single bond. X a62 is preferably a single bond or *-O-L a61 -, more preferably a single bond.
[0073] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms for Ar include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group. Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group.
[0074] Examples of the halogen atom include a fluorine atom, an iodine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group preferably has 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group preferably has 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. Preferred substituents include a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms. More preferred are a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group. Even more preferred are a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. Ar is preferably a phenylene group which may have a substituent, more preferably a phenylene group which may have a hydroxy group.
[0075] Examples of the structural unit (a1-6) include structural units represented by Formula (a1-6-1) to Formula (a1-6-44). Structural units represented by Formula (a1-6-1) to Formula (a1-6-9) are preferred, structural units represented by Formula (a1-6-1), Formula (a1-6-2), Formula (a1-6-4), Formula (a1-6-5), Formula (a1-6-7), or Formula (a1-6-8) are more preferred, and structural units represented by Formula (a1-6-1) or Formula (a1-6-2) are even more preferred. In the following structural units, R a61A structural unit in which a hydrogen atom corresponding to is replaced with a methyl group or the like, and in the following structural units, R a61 A structural unit in which a methyl group corresponding to a61 is replaced with a hydrogen atom is also included as the structural unit (a1-6). TIFF2025113198000060.tif226161
[0076] When the resin (A) or the like contains the structural unit (a1-6), the content thereof is 3 mol% or more, preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 10 mol% or more, even more preferably 20 mol% or more, still even more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on all the structural units of the resin (A) or the like. Also, 80 mol% or less, preferably 75 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less. Specifically, it is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, still more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 65 mol%.
[0077] Also, as the structural unit (a1), the following structural units are also included. TIFF2025113198000061.tif33167
[0078] When the resin (A) etc. contain structural units represented by the formulas (a1-7-1) to (a1-7-7), the content thereof is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, even more preferably 30 mol% or more, still even more preferably 40 mol% or more, and even more preferably 50 mol% or more, based on all the structural units of the resin (A) etc. Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, even more preferably 75 mol% or less, still even more preferably 70 mol% or less, and even more preferably 60 mol% or less. Specifically, 10 to 95 mol% is preferable, 15 to 90 mol% is more preferable, 20 to 85 mol% is still more preferable, 20 to 70 mol% is even more preferable, and 20 to 60 mol% is particularly preferable.
[0079] Moreover, examples of the structural unit (a1) also include the following structural units. TIFF2025113198000062.tif51121 When the resin (A) etc. contain structural units represented by the formulas (a1-8-1) to (a1-8-3), the content thereof is 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, even more preferably 30 mol% or more, still even more preferably 40 mol% or more, and even more preferably 50 mol% or more, based on all the structural units of the resin (A) etc. Also, it is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, even more preferably 75 mol% or less, still even more preferably 70 mol% or less, and even more preferably 60 mol% or less. Specifically, 10 to 60 mol% is preferable, 15 to 55 mol% is more preferable, 20 to 50 mol% is still more preferable, 20 to 45 mol% is even more preferable, and 20 to 40 mol% is particularly preferable.
[0080] 〈Structural unit (s)〉 The structural unit(s) is / are derived from monomers having no acid-labile group (hereinafter sometimes referred to as "monomer(s)"). As the monomer(s) from which the structural unit(s) is / are derived, monomers having no acid-labile group known in the resist field can be used. The structural unit(s) preferably has a hydroxy group, a carboxy group or a lactone ring. By using a resin containing a structural unit having a hydroxy group or a carboxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved. In addition to the above-described structural units, the structural unit(s) includes a structural unit having a halogen atom (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)"), a structural unit having a sultone structure (hereinafter sometimes referred to as "structural unit (a6)"), or a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as "structural unit (a7)"), and the like.
[0081] 〈Structural unit (a2)〉 The structural unit (a2) is a structural unit represented by formula (a2) and has an alcoholic hydroxy group, a phenolic hydroxy group or a carboxy group. TIFF2025113198000063.tif4093[In formula (a2), R a2 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -CO- or -NR a28 -. R a28 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L a21represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms, and the hydrocarbon group may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO2-. L a22 represents a single bond or a chain hydrocarbon group having 1 to 12 carbon atoms which may have a fluorine atom, and -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-. na2 represents any integer from 1 to 5. When na2 is 2 or more, a plurality of Ls a22 may be the same as or different from each other. R a2 Examples of the halogen atom in R include a fluorine atom, an iodine atom, a chlorine atom, a bromine atom and the like. R a2 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, a perfluorohexyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. R a2 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 still more preferably a hydrogen atom or a methyl group.
[0082] A a21Examples of the alkanediyl group include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, etc., and branched alkanediyl groups such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, heptane-1,6-diyl, octane-1,7-diyl, nonane-1,8-diyl, decane-1,9-diyl, undecane-1,10-diyl, etc. The number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, even more preferably 1 to 4, still even more preferably 1 to 3, and even more preferably 1 or 2. R a28 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. A a21 When -CH2- contained in the alkanediyl group of A is replaced by -O-, -CO- or -NR a28 -, the number of carbon atoms before replacement is defined as the number of carbon atoms of the alkanediyl group. A a21 Examples of the group in which -CH2- contained in the alkanediyl group of A is replaced by -O-, -CO- or -NR a28 - include hydroxy, carboxy, carbonyl, oxy, amino, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylamino, peptide, alkanediyl-oxy, alkanediyl-oxycarbonyl, alkanediyl-carbonyl, alkanediyl-carbonyl-oxy, alkanediyl-sulfonyl, alkanediyl-thio, alkanediyl-amino, etc. These replaced groups include those similar to those exemplified in this specification as long as the upper limit of the number of carbon atoms permits. A a21 The -CH2- contained in the alkanediyl group of is replaced by -O-, -CO-, or -NR a28 - include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a22 -CO-O-, *-O-CO-A a22 -O-, *-O-A a22 -CO-O-, *-CO-O-A a22 -O-CO-, *-O-CO-A a22 -O-CO-, *-CO-NR a28 - are mentioned. Among them, *-CO-O-, *-CO-O-A a22 -CO-O-, *-O-A a22 -CO-O-, *-CO-NR a28 - are preferred. Here, A a22 represents an alkanediyl group having 1 to 8 carbon atoms, and * represents the bonding site with the carbon atom to which R a2 is bonded. The alkanediyl group of A a22 includes alkanediyl groups similar to A a21 within the range allowed by the upper limit of the number of carbon atoms. A a21 is preferably a single bond, *-CO-O- or *-CO-O-A a22 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-. L a21 The hydrocarbon group in is a (na2 + 1)-valent hydrocarbon group, and examples include linear or branched chain hydrocarbon groups, monocyclic or polycyclic (including spiro rings, condensed rings, bridged rings, etc.) alicyclic hydrocarbon groups, and cyclic hydrocarbon groups such as aromatic hydrocarbon groups. A group formed by combining two or more of these groups (for example, a hydrocarbon group formed from an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group) may also be used. L a21 Examples of the chain hydrocarbon group of include divalent to hexavalent chain hydrocarbon groups such as alkanediyl groups, alkanetriyl groups, alkanetetrayl groups, alkanepentayl groups, and alkanexayl groups. Examples of the alkandiyl group include, for example, A a21 The same alkandiyl groups as those described above can be mentioned. Examples of the alkanetriyl group include a methanetriyl group, an ethanetriyl group, a propanetriyl group, a butanetriyl group, a pentanetriyl group, a hexanetriyl group, a heptanetriyl group, an octanetriyl group, a nonanetriyl group, a decanetriyl group, an undecanetriyl group, a dodecanetriyl group, a tridecanetriyl group, a tetradecanetriyl group, a pentadecanetriyl group, a hexadecanetriyl group, a heptadecanetriyl group, and the like. Examples of the alkanetetrayl group include a methanetetrayl group, an ethanetetrayl group, a propanetetrayl group, a butanetetrayl group, a pentanetetrayl group, a hexanetetrayl group, a heptanetetrayl group, an octanetetrayl group, a nonanetetrayl group, a decanetetrayl group, an undecanetetrayl group, a dodecanetetrayl group, a tridecanetetrayl group, a tetradecanetetrayl group, a pentadecanetetrayl group, a hexadecanetetrayl group, a heptadecanetetrayl group, and the like. Examples of the alkanepentayl group include a methanepentayl group, an ethanepentayl group, a propanepentayl group, a butanepentayl group, a pentanepentayl group, a hexanepentayl group, and the like. Examples also include a group in which one or more hydrogen atoms of the above-described groups are replaced by a bonding site. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 10, even more preferably 1 to 9, still even more preferably 1 to 8, still more preferably 1 to 6, still even more preferably 1 to 5, and particularly preferably 1 to 4. L a21 Examples of the monocyclic and polycyclic alicyclic hydrocarbon groups in L include the following alicyclic hydrocarbon groups and the like. The bonding site can be at any position. TIFF2025113198000064.tif46168For example, divalent to hexavalent alicyclic hydrocarbon groups such as cycloalkanediyl groups, cycloalkanetriyl groups, cycloalkanetetrayl groups, cycloalkanepentayl groups, cycloalkanhexayl groups, etc. can be mentioned. Specifically, monocyclic alicyclic hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclodecanetriyl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclodecanetetrayl group, etc. and polycyclic alicyclic hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, decahydronaphthalenediyl group, bicyclo[3.3.0]octanediy group, norbornanetriyl group, adamantanetriyl group, decahydronaphthalenetriyl group, bicyclo[3.3.0]octanetriyl group, norbornanetetrayl group, adamantanetetrayl group, decahydronaphthalenetetrayl group, bicyclo[3.3.0]octanetetrayl group, etc. can be mentioned. In addition, groups in which one or more hydrogen atoms of the above-mentioned groups are replaced with bonding sites, etc. can also be mentioned. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 18, still more preferably 3 to 16, even more preferably 3 to 12, still even more preferably 6 to 12, and particularly preferably 6 to 10. L a21 As the aromatic hydrocarbon group in L, divalent to hexavalent aromatic hydrocarbon groups such as arylene groups, arenetriyl groups, arenetetrayl groups, arenepentayl groups, arenhexayl groups, etc. can be mentioned. Specifically, aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, a phenanthrylene group, a benzenetriyl group, a naphthalenetriyl group, an anthracenetriyl group, a biphenylenetriyl group, a phenanthrenetriyl group, a benzenetetrayl group, a naphthalenetetrayl group, an anthracenetetrayl group, a biphenylenetetrayl group, a phenanthrenetetrayl group, etc. can be mentioned. In addition, groups in which one or more hydrogen atoms of the above-mentioned groups are replaced with a bonding site, etc. can also be mentioned. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 12, and even more preferably 6 to 10. Examples of the group combined with two or more types include a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group, a group combining an aromatic hydrocarbon group and a chain hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group, a chain hydrocarbon group, and an aromatic hydrocarbon group, etc. In the combination, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the chain hydrocarbon group may each be combined with two or more types. Also, any group may be bonded to A a21 and L a22 and may be bonded. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO- include a hydroxy group, a carboxy group, a thiol group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an oxy group, a carbonyl group, a thio group, a sulfonyl group, an alkanedioxy group, an alkanedioxycarbonyl group, an alkanediylcarbonyl group, an alkanediylcarbonyloxy group, an alkanediylsulfonyl group, an alkanediylthio group, a cycloalkoxy group, a cycloalkylalkoxy group, an aromatic hydrocarbon group-carbonyl-oxy group, an aromatic hydrocarbon group-carbonyl group, an aromatic hydrocarbon group-oxy group, a group formed by combining two or more of these groups, and the like. Further, examples also include a group in which one or more hydrogen atoms of these groups are replaced by a bonding site. These replaced groups include those similar to the groups exemplified in this specification within the range allowed by the upper limit of the number of carbon atoms.
[0083] Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group and the group formed by combining the alicyclic hydrocarbon group and the aromatic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include those similar to the groups exemplified in this specification within the range allowed by the upper limit of the number of carbon atoms. L a21 The hydrocarbon group in L may have one or more substituents. Examples of the substituent include a halogen atom, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 16 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), an acryloyloxy group, a methacryloyloxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. L a21The hydrocarbon group in [substance] can have a substituent such as a haloalkyl group by having a halogen atom as a substituent. Examples of the haloalkyl group include an alkyl fluoride group, an alkyl chloride group, an alkyl bromide group, an alkyl iodide group, etc. For example, a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, etc. may be mentioned. The number of carbon atoms in the haloalkyl group is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 1 to 4, and even more preferably from 1 to 3. L a21 The hydrocarbon group of [substance] can have a substituent such as an alkyl group by including a branched structure. a21 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. The number of carbon atoms in the alkyl group is preferably from 1 to 12, more preferably from 1 to 10, still more preferably from 1 to 8, even more preferably from 1 to 6, still even more preferably from 1 to 4, and even more preferably from 1 to 3. L a21 L is [substance] due to a group in which -CH2- contained in the hydrocarbon group of [substance] is replaced by -O- or -CO-. a21can substantially have substituents such as a hydroxy group, a carboxy group, an alkoxy group, a thiol group, a sulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an acryloyloxy group, a methacryloyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. The number of carbon atoms of the alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 to 3. The number of carbon atoms of the alkoxyalkyl group and the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 8, still more preferably 2 to 6, and even more preferably 2 to 4. Examples of the above groups include the same ones as those exemplified in this specification. L a21 The substituents that the hydrocarbon group in L may have include a halogen atom, a haloalkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 12 carbon atoms (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-). A halogen atom, a haloalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 10 carbon atoms (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-) is more preferable. A halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms is still more preferable. A fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a hydroxy group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group is even more preferable. A fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a hydroxy group, a methoxy group, or an ethoxyethoxy group is still even more preferable. Also, when the alkanediyl group of L is replaced by -O-, -CO-, etc., for example, *-L a21 -X a23 -(L a21 -(La23 represents an alkanediyl group having 1 to 8 carbon atoms, and X a21 represents -O-, -O-CO-, -CO-O- or -O-CO-O-, and * represents the bonding site with A a21 It is also preferable that it is). L a21 is a single bond, an optionally substituted chain hydrocarbon group having 1 to 12 carbon atoms (however, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an optionally substituted cyclic hydrocarbon group having 3 to 20 carbon atoms (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or a group formed by combining an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and an optionally substituted cyclic hydrocarbon group having 3 to 20 carbon atoms (however, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-). It is preferably a single bond, an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (however, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or a group formed by combining an optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms and an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-). It is more preferably).
[0084] L a22Examples of the chain hydrocarbon group having 1 to 12 carbon atoms include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, etc., and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-dimethylpropane-1,3-diyl group, pentane-2,4-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. The number of carbon atoms of the chain hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and even more preferably 1 to 4. L a22 The fluorine atom(s) that L has may be one or two or more. L a22 The -CH2- contained in the chain hydrocarbon group of L may be replaced by -O- or -CO-, and these replaced groups are the same as those exemplified for L within the range where the upper limit of the number of carbon atoms permits. a21 The same ones as those exemplified for L can be mentioned. na2 is preferably any integer from 1 to 4, and more preferably any integer from 1 to 3. L a21 Examples of the structural unit (a2) when L is a single bond or a chain hydrocarbon group include, for example, the following structural units. Among the following structural units, the structural units in which the methyl group corresponding to R is replaced by a hydrogen atom or the like are also suitable structural units of the structural unit (a2) in the same manner as the following structural units. a2 The structural units in which the methyl group corresponding to R is replaced by a hydrogen atom or the like are also suitable structural units of the structural unit (a2) in the same manner as the following structural units. TIFF2025113198000065.tif69168
[0085] When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as an exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-C) described later. The structural unit (a2) may contain one kind alone or two or more kinds.
[0086] In the structural unit (a2), L a21 When it is a cyclic hydrocarbon group, examples of the structural unit having a phenolic hydroxy group or a carboxy group include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF2025113198000066.tif31128[In the formula (a2-A), R a2 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a27 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O-, -CO-, or -NR a28 -. R a28 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a2 represents a single bond or a carbonyl group. nA2 represents any integer from 1 to 5. When nA2 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. na21 represents any integer from 0 to 4. When na21 is 2 or more, the plurality of Rs a27 may be the same as or different from each other. mc represents any integer from 0 to 2.
[0087] R a2 and A a21 are each exemplified by the same groups as those exemplified in formula (a2). R a27 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, and the like. R a27 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, a perfluorohexyl group, a chloromethyl group, a bromomethyl group, and an iodomethyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a27 Examples of the alkoxy group of R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, still more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a27Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably an alkoxyalkyl group having 2 to 4 carbon atoms, still more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a27 Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably an alkoxyalkoxy group having 2 to 4 carbon atoms, and still more preferably a methoxyethoxy group or an ethoxyethoxy group. R a27 Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 4 carbon atoms, more preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and still more preferably an acetyl group. R a27 Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms, more preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and still more preferably an acetyloxy group. R a27 is preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and still more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. nA2 is preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, and even more preferably 1 or 2. na21 is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and even more preferably 0 or 1. mc is preferably 0 or 1. -X a2 -OH, in the case of a benzene ring, may be bonded to any of the o-position, m-position or p-position with respect to the bonding position of A a21 and, among these, at least one is preferably bonded to the m-position or p-position, and more preferably bonded to the m-position. In the case of a naphthalene ring, when the bonding position of A a21 is at the 1-position, it may be bonded to any of the 2nd to 8th positions, and when the bonding position of A a21 is at the 2nd position, it may be bonded to any of the 1st and 3rd to 8th positions. Among these, when the bonding position of A a21 is at the 1-position, at least one is preferably bonded to the 3rd to 6th positions, and more preferably bonded to the 3rd or 4th position. When the bonding position of A a21 is at the 2nd position, it is preferably bonded to the 4th to 7th positions, and more preferably bonded to the 5th or 6th position.
[0088] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include structural units represented by formula (a2-2-1) to formula (a2-2-32), formula (a2-3-1) to formula (a2-3-24), and structural units in which the methyl group corresponding to R a2 in the structural unit (a2-A) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group. TIFF2025113198000067.tif107169
[0089] When the structural unit (a2-A) is included in the resin (A) etc., the content of the structural unit (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and even more preferably 20 mol% or more with respect to all the structural units. Also, it is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, even more preferably 60 mol% or less, still even more preferably 50 mol% or less, still more preferably 45 mol% or less, and even more preferably 40 mol% or less. Specifically, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%. The structural unit (a2-A) can be included in the resin (A) etc. by polymerizing a compound that induces the structural unit (a2-A) (for example, a compound (a2-A’) etc. in which the -CH2-C(-R a2 )- of the structural unit (a2-A) is in the state of CH2=C(-R a2 ) of the double bond before cleavage). Also, for example, after polymerization using the structural unit (a1-4), it can be included in the resin (A) etc. by treatment with an acid such as p-toluenesulfonic acid. Also, after polymerization using acetoxystyrene etc., the structural unit (a2-A) can be included in the resin (A) etc. by treatment with an alkali such as tetramethylammonium hydroxide.
[0090] In the structural unit (a2), when L a21 is a cyclic hydrocarbon group, examples of the structural unit having an alcoholic hydroxy group or a carboxy group include the structural unit represented by the formula (a2-B) (hereinafter sometimes referred to as "structural unit (a2-B)"), the structural unit represented by the formula (a2-C) (hereinafter sometimes referred to as "structural unit (a2-C)"), and the structural unit represented by the formula (a2-D) (hereinafter sometimes referred to as "structural unit (a2-D)"). In formulas (a2-B) and (a2-C), R a2 represents the same meaning as in formula (a2). R a27 represents the same meaning as in formula (a2-A). L a25 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents an integer from 1 to 7. * represents the bonding site with -CO-. X a2 represents a single bond or -CO-. R a25 and R a26 each independently represent a hydrogen atom, a methyl group, or a hydroxy group. nB2 represents an integer from 1 to 5. When nB2 is 2 or more, the plurality of X a2 may be the same as or different from each other. nB22 represents an integer from 0 to 8. When nB22 is 2 or more, the plurality of R a27 may be the same as or different from each other. nC22 represents an integer from 0 to 10. When nC22 is 2 or more, the plurality of R a27 may be the same as or different from each other.] L a25 is preferably -O-, -O-(CH2) f1 -CO-O- (where f1 represents an integer from 1 to 4), and more preferably -O-. R a2 is preferably a methyl group. X a2 is preferably a single bond. R a25 is preferably a hydrogen atom. R a26 is preferably a hydrogen atom or a hydroxy group. R a27is preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy methoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group. nB2 is preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, and even more preferably 1 or 2. nB22 is preferably any integer from 0 to 3, more preferably 0, 1 or 2, and even more preferably 0 or 1. nC22 is preferably any integer from 0 to 6, more preferably any integer from 0 to 3, and even more preferably 0 or 1.
[0091] Examples of the structural unit (a2-B) and the structural unit (a2-C) include structural units derived from the monomers described in JP-A-2010-204646, the following structural units, and methyl groups or hydrogen atoms corresponding to R in the following structural units, which are replaced by hydrogen atoms, halogen atoms, haloalkyl groups or other alkyl groups. Among them, the structural units represented by any of formula (a2-B-1) to formula (a2-B-5) and formula (a2-C-1) to formula (a2-C-9) are preferred. a2 When the resin (A) etc. contains the structural unit (a2-B) or the structural unit (a2-C), the content thereof is 1 mol% or more, preferably 2 mol% or more, based on all the structural units of the resin (A) etc. Further, it is 45 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 20 mol% or less, and still more preferably 10 mol% or less. Specifically, it is 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and still more preferably 1 to 10 mol%. TIFF2025113198000070.tif80164 When the resin (A) etc. contains the structural unit (a2-B) or the structural unit (a2-C), the content thereof is 1 mol% or more, preferably 2 mol% or more, based on all the structural units of the resin (A) etc. Further, it is 45 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 20 mol% or less, and still more preferably 10 mol% or less. Specifically, it is 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and still more preferably 1 to 10 mol%.
[0092] TIFF2025113198000071.tif51106[In formula (a2-D), R a2 and A a21 each represent the same meaning as in formula (a2). R a27 represents the same meaning as in formula (a2-A). R a21 and R a22 each independently represent an alkyl fluoride group having 1 to 4 carbon atoms. L a24 represents a single bond or an alkanediyl group having 1 to 3 carbon atoms, and the alkanediyl group may be substituted with a fluorine atom. nD2 represents any integer from 1 to 5. When nD2 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. nD22 represents any integer from 0 to 4. When nD22 is 2 or more, the plurality of R a27 may be the same as or different from each other. However, 1 ≦ nD2 + nD22 ≦ 5.] R a21 and R a22 Examples of the alkyl fluoride group of and include, independently of each other, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, and the like. R a21 and R a22 is preferably a trifluoromethyl group. L a24 Examples of the alkanediyl group of include a methylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, and the like. L a24 is preferably a single bond or a methylene group. R a27is preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy methoxy group, and still more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group. nD2 is preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, still more preferably 1 or 2, and even more preferably 1. Further, preferably, nD2 is 1 and the group in parentheses is bonded to the para position. nD22 is preferably any integer from 0 to 3, more preferably any integer from 0 to 2, still more preferably 0 or 1, and even more preferably 0.
[0093] As the structural unit (a2-D), a structural unit represented by the following formula (a2-D1) (hereinafter sometimes referred to as "structural unit (a2-D1)") is more preferable. TIFF2025113198000072.tif51107[In formula (a2-D1), R a2 、A a21 、R a27 、nD2 and nD22 represent the same meanings as in formula (a2-D).] In formula (a2-D1), R a2 is preferably a hydrogen atom or a methyl group. A a21 is preferably a single bond.
[0094] Examples of the structural unit (a2-D) include the structural units described below. TIFF2025113198000073.tif62167
[0095] In the structural units represented by formulas (a2-D-1) to (a2-D-8), R a2A structural unit in which a hydrogen atom corresponding to is replaced with a methyl group or the like, and in the structural units represented by Formula (a2-D-9) to Formula (a2-D-16), R a2 Structural units in which the methyl group corresponding to is replaced with a hydrogen atom or the like can also be cited as specific examples of the structural unit (a2-D). Among them, the structural units represented by Formula (a2-D-1) to Formula (a2-D-8) are preferable, the structural units represented by Formula (a2-D-1) to Formula (a2-D-4) are more preferable, and the structural unit represented by Formula (a2-D-1) is even more preferable.
[0096] When the resin (A) or the like contains the structural unit (a2-D), the content is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more with respect to all the structural units of the resin (A) or the like. Also, it is preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, and still more preferably 65 mol% or less. Specifically, it is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, even more preferably 10 to 70 mol%, and still more preferably 10 to 65 mol%.
[0097] 〈Structural unit (a3)〉 The lactone ring contained in the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, the structural unit represented by the following Formula (a3-2)) can be cited.
[0098] The structural unit (a3) is preferably a structural unit represented by Formula (a3-1), Formula (a3-2), Formula (a3-3), or Formula (a3-4). These may be contained alone or in combination of two or more. TIFF2025113198000074.tif50162[In Formula (a3-1), Formula (a3-2), Formula (a3-3), and Formula (a3-4), L a4 、La5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -CO-O- (where k3 represents an integer from 1 to 7). L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding site with the carbonyl group. R a18 R a19 R a20 and R a24 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 R a23 and R a25 each independently represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents an integer from 0 to 5. q1 represents an integer from 0 to 3. r1 represents an integer from 0 to 3. w1 represents an integer from 0 to 8. When p1, q1, r1, and / or w1 is 2 or more, the plurality of R a21 R a22 R a23 and / or R a25 may be the same as or different from each other.]
[0099] R a21, R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in R, R, and R include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, and tert-butyl group. R a18 , R a19 , R a20 and R a24 Examples of the halogen atom and the alkyl group which may have a halogen atom in R, R, R, and R include those exemplified by R, R, and R of formula (a1-0), formula (a1-1), and formula (a1-2). a01 , R a4 and R a5 include the same ones as those exemplified by R, R, and R. L a8 and L a9 Examples of the alkanediyl group in L and L include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.
[0100] L a4 , L a5 and L a6 are each independently preferably -O- or, in *-O-(CH2) k3 -CO-O-, a group in which k3 is any integer from 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, still more preferably an oxygen atom.
[0101] L a7 is preferably -O- or *-O-L a8 -CO-O-, and more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. R a18 , R a19 , R a20 and R a24is 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 still more preferably a hydrogen atom or a methyl group. R a21 is preferably a methyl group. R a22 , R a23 and R a25 are each independently preferably a carboxy group, a cyano group or a methyl group. p1, q1 and r1 are each independently preferably any integer from 0 to 2, more preferably 0 or 1. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF2025113198000075.tif4051 (wherein R a24 , L a7 represents the same meaning as above.)
[0102] Examples of the structural unit (a3) include structural units derived from the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include structural units represented by any of the formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and, in the above structural units, structural units in which the methyl groups corresponding to R a18 , R a19 , R a20 and R a24 are replaced by hydrogen atoms are preferred. TIFF2025113198000076.tif107164
[0103] When the resin (A) etc. contains the structural unit (a3), the total content rate is 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, with respect to all the structural units of the resin (A) etc. Also, 70 mol% or less is mentioned, preferably 65 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 40 mol% or less, still even more preferably 30 mol% or less, still more preferably 25 mol% or less, and still even more preferably 20 mol% or less. Specifically, 1 to 70 mol% is mentioned, preferably 3 to 70 mol%, more preferably 3 to 65 mol%, still more preferably 5 to 65 mol%, even more preferably 5 to 60 mol%, and still even more preferably 10 to 60 mol%. Also, the content rate of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and still more preferably 10 mol% or more, with respect to all the structural units of the resin (A) etc. Also, it is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, even more preferably 40 mol% or less, still even more preferably 30 mol% or less, still more preferably 25 mol% or less, and still even more preferably 20 mol% or less. Specifically, 1 to 60 mol% is preferable, 3 to 60 mol% is more preferable, 3 to 55 mol% is still more preferable, 5 to 55 mol% is still more preferably, 5 to 50 mol% is even more preferable, and 10 to 50 mol% is still even more preferable.
[0104] 〈Structural unit (a4)〉 The structural unit represented by the formula (a4) is shown below. TIFF2025113198000077.tif2870 [In the formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42represents an aliphatic hydrocarbon group having a halogen atom with 1 to 48 carbon atoms, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-.
[0105] R 42 The aliphatic hydrocarbon group represented by includes a linear or branched chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these, etc. Examples of the chain hydrocarbon group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; and branched alkyl groups such as isopropyl group and isobutyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include monocyclic alicyclic hydrocarbon groups which are monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups which are polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding site). Examples of the group formed by the combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc. Examples of the alkanediyl group include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group. The terminal of the branched alkanediyl group may be a methyl group. R 42Examples of the halogen atom included in the aliphatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R 42 Examples of the group in which -CH2- of the aliphatic hydrocarbon group included in is replaced by -O- or -CO- include a hydroxy group, a carboxy group, a carbonyl group, an oxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkanedioxy group, an alkanedioxycarbonyl group, an alkanediylcarbonyl group, an alkanediylcarbonyloxy group, a cycloalkoxy group, a cycloalkylalkoxy group, a group formed by combining two or more of these groups, and the like. These replaced groups include the same groups as those exemplified in the present specification within the range where the upper limit of the number of carbon atoms allows.
[0106] As the structural unit (a4), R 42 is preferably an aliphatic hydrocarbon group having a fluorine atom, and an example of the structural unit (a4) in which R 42 is an aliphatic hydrocarbon group having a fluorine atom includes a structural unit represented by the formula (a4-1) (hereinafter, may be referred to as "structural unit (a4-1)"), a structural unit represented by the formula (a4-2) (hereinafter, may be referred to as "structural unit (a4-2)"), a structural unit represented by the formula (a4-3) (hereinafter, may be referred to as "structural unit (a4-3)"), and a structural unit represented by the formula (a4-A) (hereinafter, may be referred to as "structural unit (a4-A)"). The structural unit represented by the formula (a4-1) is the structural unit shown below. TIFF2025113198000079.tif3092[In the formula (a4-1), R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 42f represents an alkanediyl group having 1 to 8 carbon atoms and having a fluorine atom or a cycloalkanediyl group having 3 to 12 carbon atoms and having a fluorine atom. R 42frepresents a hydrogen atom or a fluorine atom.
[0107] L 41 Examples of the alkanediyl group in L include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group; and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. The terminal of the branched alkanediyl group may be a methyl group. L 42f Examples of the alkanediyl group having a fluorine atom in L include linear alkanediyl groups having a fluorine atom such as a methylene group having a fluorine atom, an ethylene group having a fluorine atom, a propane-1,3-diyl group having a fluorine atom, a butane-1,4-diyl group having a fluorine atom, a pentane-1,5-diyl group having a fluorine atom, a hexane-1,6-diyl group having a fluorine atom, a heptane-1,7-diyl group having a fluorine atom, and an octane-1,8-diyl group having a fluorine atom; branched alkanediyl groups having a fluorine atom such as an ethane-1,1-diyl group having a fluorine atom, a propane-1,1-diyl group having a fluorine atom, a propane-1,2-diyl group having a fluorine atom, a propane-2,2-diyl group having a fluorine atom, a pentane-2,4-diyl group having a fluorine atom, a 2-methylpropane-1,3-diyl group having a fluorine atom, a 2-methylpropane-1,2-diyl group having a fluorine atom, a pentane-1,4-diyl group having a fluorine atom, and a 2-methylbutane-1,4-diyl group having a fluorine atom. The terminal of the branched alkanediyl group may be a methyl group which may have a fluorine atom. L 42fExamples of the cycloalkanediyl group having a fluorine atom in L include monocyclic cycloalkanediyl groups having a fluorine atom such as a cyclobutane-1,3-diyl group having a fluorine atom, a cyclopentane-1,3-diyl group having a fluorine atom, a cyclohexane-1,4-diyl group having a fluorine atom, a cyclohexene-3,6-diyl group having a fluorine atom, a cycloheptane-1,4-diyl group having a fluorine atom, and a cyclooctane-1,5-diyl group having a fluorine atom. Examples of the polycyclic cycloalkanediyl group having a fluorine atom include a norbornane-1,4-diyl group having a fluorine atom, a norbornane-2,5-diyl group having a fluorine atom, a 5-norbornene-2,3-diyl group having a fluorine atom, an adamantane-1,5-diyl group having a fluorine atom, and an adamantane-2,6-diyl group having a fluorine atom. L 42f The number of fluorine atoms in the alkanediyl group having a fluorine atom and the cycloalkanediyl group in L may be 1 or more, and is preferably 2 or more. L 42f The alkanediyl group having a fluorine atom and the cycloalkanediyl group in L are preferably a perfluoroalkanediyl group and a perfluorocycloalkanediyl group, respectively.
[0108] L 42fExamples of the perfluoroalkanediyl group in [description] include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane-2,2-diyl group, a perfluorooctane-3,3-diyl group, a perfluorooctane-4,4-diyl group, and the like. L 42f Examples of the perfluorocycloalkanediyl group in [description] include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.
[0109] L 41 is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms, more preferably a single bond, a methylene group, or an ethylene group, and still more preferably a single bond or a methylene group. L 42f is preferably a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and still more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.
[0110] Examples of the structural unit (a4-1) include the structural units shown below and R in the structural unit (a4-1) in the following structural units 41Examples thereof include structural units in which the methyl group corresponding thereto is replaced with a hydrogen atom. TIFF2025113198000080.tif55167 The structural unit represented by formula (a4-2) is the structural unit shown below. TIFF2025113198000081.tif33102 [In formula (a4-2), R 41 represents a hydrogen atom or a methyl group. L 43f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-. R 43f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-. However, at least one of 43f L 43f and 43f R 43f has a fluorine atom, and the upper limit of the total number of carbon atoms of
[0111] L 43f and 43f R 43f and 43f is 21.] 43f Examples of the aliphatic hydrocarbon group in 43f L 42 and
[0112] R 43f include linear or branched chain hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these. Examples of the aliphatic hydrocarbon group in TIFF2025113198000082.tif13119 [In formula (L43f-1), s represents 0 or 1. L 45f and L 46f each independently represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a fluorine atom. L 47f represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a fluorine atom. X 46f and X 47f each independently represents -O-, -CO-, -CO-O- or -O-CO-. However, the total number of carbon atoms of L 45f , L 46f , L 47f , X 46f and X 47f is 7 or less. * and ** are bonding sites, and ** is the bonding site with -O-CO-R 43f .
[0113] In the group represented by formula (L43f-1), L 45f , L 46f and L 47f Examples of the divalent aliphatic hydrocarbon group represented by include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, etc. can be mentioned. s is preferably 0.
[0114] Examples of the group represented by formula (L43f-1) include the following groups. In the following examples, * and ** each represent a bonding site, and ** is the bonding site with -O-CO-R 43f . TIFF2025113198000083.tif47140
[0115] R43f The aliphatic hydrocarbon group having a fluorine atom is preferred. The structural unit represented by the formula (a4-2) in this case includes, for example, the structural unit represented by the formula (a4-2A) or (formula a4-2B). TIFF2025113198000084.tif41157 [In the formula (a4-2A) and the formula (a4-2B), R 41 and L 43f represent the same as those in the formula (a4-2). R 43fA represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. A 43f represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-. X 43 represents **-O-CO- or **-CO-O-, and ** represents the bonding site with A 43f and represents the bonding site with A. R 43fB represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, in the formula (a4-2A), the total number of carbon atoms of L 43f and R 43fA is 21 or less, and in the formula (a4-2B), the total number of carbon atoms of L 43f , A 43f , X 43 and R 43fB is 21 or less, and among A 43f and R 43fB at least one has at least one fluorine atom. R 43fA The aliphatic hydrocarbon group of R, as long as the upper limit of the number of carbon atoms permits, includes the same aliphatic hydrocarbon groups as those exemplified by R 42 . R 43fA is preferably an alkyl group having 1 to 13 carbon atoms and having a fluorine atom, a cycloalkyl group having 3 to 12 carbon atoms and having a fluorine atom, or a group combining them, *-(CF2) n43f -R 42’(* represents the bonding site with the carbonyl group. n43f represents an integer from 1 to 6. R 42’ represents a hydrogen atom or a fluorine atom.) or a perfluorocycloalkyl group having 3 to 12 carbon atoms is more preferable. A 43f and R 43fB 's aliphatic hydrocarbon group, as long as the upper limit of the number of carbon atoms permits, is an aliphatic hydrocarbon group similar to the aliphatic hydrocarbon group exemplified by R 42 in formula (a4). A 43f is preferably a divalent chain hydrocarbon group which may have a fluorine atom, a divalent alicyclic hydrocarbon group or a group combining them, more preferably a divalent chain hydrocarbon group having a fluorine atom, and even more preferably a fluoroalkanediyl group having 1 to 6 carbon atoms. R 43fB 's aliphatic hydrocarbon group which may have a fluorine atom is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group or a group combining them which may have a fluorine atom, more preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a group combining them which may have a fluorine atom, and even more preferably a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, a perfluorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group, a perfluorooctyl group and other fluoroalkyl groups, a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.
[0116] In formula (a4-2B), *-A 43f -X 43 -R 43fB An example of the structure that the group represented by can take is the following structure (* is the bonding site with the carbonyl group). TIFF2025113198000085.tif15170
[0117] Examples of the structural unit represented by formula (a4-2A) include the following structural units and the structural units represented by formula (a4-2A) in the following structural units where the methyl group corresponding to R 41 is replaced by a hydrogen atom. TIFF2025113198000086.tif99167
[0118] Examples of the structural unit represented by formula (a4-2B) include the following structural units and the structural units represented by formula (a4-2B) in the following structural units where the methyl group corresponding to R 41 is replaced by a hydrogen atom. TIFF2025113198000087.tif111163
[0119] Examples of the structural unit (a4) also include the structural unit represented by formula (a4-3). TIFF2025113198000088.tif3689[In formula (a4-3), R 41 represents a hydrogen atom or a methyl group. L 44f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-. R 44f represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-. However, at least one of L 44f and R 44f has a fluorine atom, and L 44f and R44f The upper limit of the total carbon number is 21.
[0120] L 44f and R 44f Examples of the aliphatic hydrocarbon group in L 44f and R 44f include linear or branched chain aliphatic hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and groups formed by combining these, etc. 44f and R 44f As long as the upper limit of the total carbon number of L 42 and R allows, examples of the aliphatic hydrocarbon group of R in formula (a4) include the same groups as the aliphatic hydrocarbon groups exemplified above. L 44f is preferably an alkanediyl group having 1 to 14 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), and -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 - (where j1 to j5 each independently represent an integer of 1 to 6). More preferably, it is an alkanediyl group having 1 to 4 carbon atoms (wherein one -CH2- contained in the alkanediyl group may be replaced by -O-, and one -CH2-CH2- contained in the alkanediyl group may be replaced by -CO-O- or -O-CO-). R 44f is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, an alicyclic hydrocarbon group having 3 to 10 carbon atoms having a fluorine atom, or a group combining them, still more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.
[0121] Examples of the structural unit represented by formula (a4-3) include the following structural units and structural units represented by the following formulas, where the methyl group corresponding to R in structural unit (a4-3) is replaced by a hydrogen atom. 41 Examples thereof include a structural unit in which the methyl group corresponding to R in 41 is replaced by a hydrogen atom. TIFF2025113198000089.tif86170
[0122] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-A). TIFF2025113198000090.tif3674[In formula (a4-A), R 44 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. X 44 represents a single bond or *-CO-O-. * represents the bonding site with the carbon atom to which R 44 is bonded. L 44 represents an aliphatic hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -SO2-, -SO- or -CO-. R 45 represents a fluorinated alkyl group having 1 to 8 carbon atoms. R 46 represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms, and the fluorinated alkyl group may be bonded to L 44 to form an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-. mi represents an integer of any one of 1 to 4. When mi is 2 or more, the groups in a plurality of parentheses may be the same as or different from each other.]
[0123] R 44 Examples of the halogen atom and the alkyl group which may have a halogen atom in R are the same as those exemplified by R in formulas (a1-0) to (a1-2). a01 R a4 R a5 Examples thereof include the same ones as those exemplified by R in formulas (a1-0) to (a1-2). R 44 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
[0124] L 44 Examples of the aliphatic hydrocarbon group in L include a chain hydrocarbon group, and an alicyclic hydrocarbon group which is monocyclic or polycyclic (including a spiro ring, a condensed ring, a bridged ring, etc.), and a group formed by combining two or more of these groups (for example, a hydrocarbon group formed from an alicyclic hydrocarbon group and a chain hydrocarbon group) may also be used. Examples of the chain hydrocarbon group include divalent to pentavalent chain hydrocarbon groups such as an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, and an alkanepentayl group. Examples of the alkanediyl group include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. Examples also include a group in which one or more hydrogen atoms of the above-described groups are replaced with a bonding site. The number of carbon atoms in the chain hydrocarbon group is preferably from 1 to 18, more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 9, yet even more preferably from 1 to 8, still even more preferably from 1 to 6, yet still even more preferably from 1 to 5, and particularly preferably from 1 to 4.
[0125] Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include the following alicyclic hydrocarbon groups and the like. The bonding site can be at any position. TIFF2025113198000091.tif45164For example, divalent to pentavalent alicyclic hydrocarbon groups such as cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, cycloalkanepentayl group and the like can be mentioned. Specifically, monocyclic alicyclic hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group and polycyclic alicyclic hydrocarbon groups such as spiro rings having a cycloalkanediyl group, norbornanediyl group or adamantanediyl group each having a cycloalkanediyl group, norbornanediyl group or adamantanediyl group spiro-bonded thereto, such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, decahydronaphthalenediyl group, bicyclo[3.3.0]octanediyl group, spirocyclohexane-1,2'-cyclopentane-diyl group, spiroadamantane-2,3'-cyclopentane-diyl group and the like can be mentioned. In addition, groups in which one or more hydrogen atoms of the above-described groups are replaced by a bonding site and the like can also be mentioned. The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 20, more preferably from 3 to 18, still more preferably from 3 to 16, and even more preferably from 3 to 12.
[0126] Examples of a group formed by combining two or more groups include a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group. In the combination, two or more alicyclic hydrocarbon groups and two or more chain hydrocarbon groups may be combined respectively. Also, any group may be bonded to X 11 . Examples of a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group include a group in which an alicyclic hydrocarbon group is bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-), a group in which a chain hydrocarbon group is bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-), a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-), a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-), a group in which an alicyclic hydrocarbon group, a chain hydrocarbon group, and an alicyclic hydrocarbon group are bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-), a group in which a chain hydrocarbon group, an alicyclic hydrocarbon group, and a chain hydrocarbon group are bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-), etc. * represents the bonding site with X 11 . Examples also include a group in which one or more hydrogen atoms of the above-described group are replaced with a bonding site, etc.
[0127] L 1 The -CH2- contained in the aliphatic hydrocarbon group having 1 to 28 carbon atoms of may be replaced with -O-, -S-, -SO-, -SO2- or -CO-. L 1 When the -CH2- contained in the aliphatic hydrocarbon group having 1 to 28 carbon atoms of is replaced with -O-, -S-, -SO-, -SO2- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the aliphatic hydrocarbon group. Examples of the group in which -CH2- contained in the aliphatic hydrocarbon group is replaced by -O-, -S-, -SO2-, -SO- or -CO- include a hydroxy group, a carboxy group, a thiol group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an oxy group, a carbonyl group, a thio group, a sulfonyl group, an alkanedioxy group, an alkanedioxycarbonyl group, an alkanediylcarbonyl group, an alkanediylcarbonyloxy group, an alkanediylsulfonyl group, an alkanediylthio group, a cycloalkoxy group, a cycloalkylalkoxy group, a group formed by combining two or more of these groups, and the like. These replaced groups include those similar to the groups exemplified in this specification within the range allowed by the upper limit of the number of carbon atoms. Examples also include a group in which one or more hydrogen atoms of the above-described group are replaced by a bonding site. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include those similar to the groups exemplified in this specification within the range allowed by the upper limit of the number of carbon atoms.
[0128] L 44 The aliphatic hydrocarbon group in L may have one or more substituents. Examples of the substituent include a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the -CH2- contained in the alkyl group or the alicyclic hydrocarbon group may be replaced by -O- or -CO-). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The haloalkyl groups having 1 to 4 carbon atoms include fluoroalkyl groups having 1 to 4 carbon atoms, chloroalkyl groups having 1 to 4 carbon atoms, bromoalkyl groups having 1 to 4 carbon atoms, iodoalkyl groups having 1 to 4 carbon atoms, and the like. Examples of the haloalkyl group include perfluoroalkyl groups having 1 to 4 carbon atoms (such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, iodomethyl group, and the like. The number of carbon atoms of the haloalkyl group is preferably 1 to 3, more preferably 1 or 2. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and the like. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 16, more preferably 3 to 12, and still more preferably 3 to 10. Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group, and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 12, and still more preferably 6 to 10. When -CH2- contained in an alkyl group is replaced by -O- or -CO-, the total number of carbon atoms of the alkyl group is the number of carbon atoms before replacement. Examples of the replaced group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, and the like. These replaced groups include those similar to the groups exemplified in this specification within the range where the upper limit of the number of carbon atoms is allowed. The number of carbon atoms of the alkoxy group is preferably from 1 to 9, more preferably from 1 to 6, still more preferably from 1 to 4, and even more preferably from 1 to 3. The number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 9, more preferably from 2 to 6, still more preferably from 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably from 2 to 10, more preferably from 2 to 6, still more preferably from 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably from 2 to 9, more preferably from 2 to 6, still more preferably from 2 to 4, and even more preferably 2 or 3. In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O- or -CO- include those similar to the groups exemplified in this specification within the range where the upper limit of the number of carbon atoms is allowed. L 44 Examples of the substituent that the aliphatic hydrocarbon group in L may have include a halogen atom, a haloalkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms (wherein -CH2- contained in the alkyl group or the alicyclic hydrocarbon group may be replaced by -O- or -CO-). A fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-) is more preferred, and a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, a hydroxy group, or a methoxy group is even more preferred. L 44 is R 46When it does not form an alkyl fluoride group and an alicyclic hydrocarbon group, it may have a substituent and has 1 to 12 carbon atoms. A chain hydrocarbon group (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group formed by combining a chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-). Preferably, it is a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a substituent, or a group formed by combining a chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-). More preferably, it is a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 5 to 12 carbon atoms which may have a substituent, a group formed by combining a chain hydrocarbon group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 5 to 12 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), or a group formed by combining an alicyclic hydrocarbon group having 5 to 12 carbon atoms, a chain hydrocarbon group having 1 to 6 carbon atoms, and an alicyclic hydrocarbon group having 5 to 12 carbon atoms which may have a substituent (the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-). Even more preferably, it is such a group.
[0129] R 45Examples of the C1-C8 fluoroalkyl group include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl group, 2-(perfluoropropyl)ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2-(perfluorobutyl)ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group. The carbon number of the fluoroalkyl group is preferably 1-6, more preferably 1-5, still more preferably 1-4, and even more preferably 1-3. R 46 The C1-C6 fluoroalkyl group in is, as long as the upper limit of the carbon number permits, the same as the C1-C6 fluoroalkyl groups exemplified in the examples of the fluoroalkyl group of R 45 R 45 is preferably a C1-C6 fluoroalkyl group when R 46 is a C1-C6 fluoroalkyl group, more preferably a C1-C3 fluoroalkyl group, still more preferably a trifluoromethyl group, a perfluoroethyl group or a perfluoropropyl group, and even more preferably a trifluoromethyl group. R45 is, when R 46 is a hydrogen atom, preferably an alkyl fluoride group having 1 to 6 carbon atoms, more preferably an alkyl fluoride group having 1 to 5 carbon atoms, and still more preferably an alkyl fluoride group having 3 to 5 carbon atoms. R 46 is L 44 and combines to form an alicyclic hydrocarbon group having 3 to 12 carbon atoms, R 46 is L 44 Examples of the group formed by combining with L 45 include, for example, groups represented by the following formulas. In the following formulas, * and ** represent bonding sites, and the two ** represent, one represents the bonding site with a hydroxy group, and the other represents the bonding site with R 44A is, L 44 is a part of the hydrocarbon group of L 46 is L 44 and represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. The number of carbon atoms of the alicyclic hydrocarbon group formed by combining R TIFF2025113198000092.tif22138R 46 is preferably a hydrogen atom or an alkyl fluoride group having 1 to 3 carbon atoms. mi is preferably any integer from 1 to 3, more preferably 1 or 2, and still more preferably 1.
[0130] Examples of the structural unit (a4-A) include the following structural units and the like. In the following structural units, structural units in which the methyl group corresponding to R 44 is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or an alkyl group other than a methyl group, and structural units in which the hydrogen atom corresponding to R 44 is replaced with a halogen atom, a haloalkyl group or an alkyl group can also be cited as specific examples of the structural unit (a4-A). TIFF2025113198000093.tif192167
[0131] When the resin (A) etc. contains the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A) etc.
[0132] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group that the structural unit (a5) has include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1). TIFF2025113198000094.tif3971[In the formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.]
[0133] R 52 The alicyclic hydrocarbon group in R may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group etc. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group etc. R 52is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group. L 55 Examples of the divalent saturated hydrocarbon group in include divalent chain saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include alkane diyl groups such as methylene group, ethylene group, propane diyl group, butane diyl group and pentane diyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkane diyl groups such as cyclopentane diyl group and cyclohexane diyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantane diyl group and norbornane diyl group.
[0134] L 55 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include the groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF2025113198000095.tif18165[In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents the bonding site with L x1 .). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, x1 and x2 the total number of carbon atoms of is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, the total number of carbon atoms in L x3 and L x4 is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the total number of carbon atoms in L x5 , L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, the total number of carbon atoms in L x8 , L x9 and W x1 is 15 or less.
[0135] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.
[0136] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF2025113198000096.tif36148 Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF2025113198000097.tif23130 Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF2025113198000098.tif16147 Examples of the group represented by the formula (L1-4) include the following divalent groups. TIFF2025113198000099.tif13168L 55 is preferably a single bond or a group represented by the formula (L1-1).
[0137] Examples of the structural unit (a5-1) include the following structural units and the structural units in which the methyl group corresponding to R in the following structural units in the structural unit (a5-1) is replaced by a hydrogen atom. 51 are mentioned. When resin (A) etc. contains structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, still more preferably 3 to 15 mol% with respect to all the structural units of resin (A) etc.
[0138] 〈Structural unit (a6)〉 Structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.
[0139] Examples of the sultone ring include the rings represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and examples include the rings represented by formula (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a heteroatom in addition to -SO2-O- as an atomic group constituting the ring, like the ring represented by formula (T 1 -2). Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, and preferably an oxygen atom. TIFF2025113198000101.tif3484
[0140] The sultone ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms, etc.
[0141] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group, preferably a trifluoromethyl group. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a hydroxyalkyl group such as a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. From the viewpoint of easy production of the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferred.
[0142] As the sultone ring, a ring represented by the following formula (T1') is preferred. TIFF2025113198000102.tif2864[In the formula (T1'), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R 41 includes the same groups as the substituents of the above-described sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferred. ma is preferably 0 or 1, and more preferably 0.
[0143] Examples of the ring represented by formula (T1’) include the following rings. The bonding site can be at any position. Among them, the bonding site is preferably at the 1-position or 3-position. TIFF2025113198000103.tif46148
[0144] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.
[0145] The structural unit (a6) is preferably a structural unit represented by formula (a6-0). TIFF2025113198000104.tif4964[In formula (a6-0), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. A xx represents an oxygen atom, -N(R c )-, or a sulfur atom. A x represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -N(R d )-. X 11 , R 41 and ma have the same meanings as described above. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]
[0146] Examples of the halogen atom of R x include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R x Examples of the alkyl group of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, etc., preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom of R include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. R x R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.
[0147] A x Examples of the divalent saturated hydrocarbon group of A include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination of two or more of these groups may also be used. Specifically, linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, a heptadecane-1,17-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-2,2-diyl group; Branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like can be mentioned. A x The bonding position to the sultone ring of A can be any position, but the one at the 1-position is preferred.
[0148] Examples of the structural unit (a6-0) include the following structural units. TIFF2025113198000105.tif84143
[0149] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferred, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferred. When resin (A) etc. contain the structural unit (a6), the content rate is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, still more preferably 3 to 30 mol% with respect to all the structural units of resin (A) etc.
[0150] <Structural unit (a7)> Resin (A), etc. may further contain a structural unit that decomposes upon exposure other than the structural unit (IP) to generate an acid (hereinafter sometimes referred to as "structural unit (a7)"). However, the structural unit (IP) is excluded. Specific examples of the structural unit (a7) include the structural units described in JP-A-2016-79235, and it is preferably a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain. The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by the formula (a7-A). TIFF2025113198000106.tif26124[In the formula (a7-A), R a7 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. X a71 represents a single bond, *-O-*, *-CO-O-*, *-O-CO-O-*, *-CO-NR a71 -*, *-NR a71 -CO-O-*, *-O-CO-NR a71 -* or *-Ax-Ph-Ay-*. R a71 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ph represents a phenylene group which may have a substituent. Ax and Ay each independently represent one or more bond types selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amide bond, and a carbonate ester bond. * and ** represent bonding sites, and * represents the bonding site with the carbon atom to which R a7 is bonded. L a71 and L a72 each independently represent a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO-, or -SO2-. X a72represents ***-CO-O-, ***-O-CO-, ***-O-CO-O-, ***-O-, where *** is L a71 represents the binding site with L. na7 represents any integer from 0 to 2. When na7 is 2, the groups in multiple parentheses may be the same or different from each other. RA - represents a sulfonate anion or a carboxylate anion. ZA + represents an organic cation.
[0151] R a7 As the halogen atom and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R, R in formula (a1-0), formula (a1-1) and formula (a1-2) a01 R a4 and R a5 are the same as those exemplified by. R a7 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, further preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a71 The alkyl group having 1 to 6 carbon atoms in R includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. X a71 When X is a group represented by *-Ax-Ph-Ay-**, it is preferably a linking group represented by the following formula (X10). TIFF2025113198000107.tif3351 [In formula (X10), Ax represents the bonding species that binds to the carbon atom to which R a7 is bonded, and represents one or more bonding species selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, a carbonate ester bond, and an amide bond. Ay is L a71Represents a bonding type that binds to, and represents one or more bonding types selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, a carbonate bond, and an amide bond. Rx represents a halogen atom, a hydroxy group, a C1-C6 fluoroalkyl group, a C1-C18 alkyl group, or a C1-C6 alkoxy group. mx represents any integer from 0 to 4. When mx is an integer of 2 or more, a plurality of Rx's may be the same or different from each other. When either Ax or Ay is a single bond, it is preferable that the other is one or more selected from the group consisting of an ether bond, a thioether bond, an ester bond, a carbonate bond, and an amide bond. When either Ax or Ay is an amide bond, it is preferably a bond represented by -CO-NR a71 - The bonding position of Ay in the phenylene group is preferably the m-position or the p-position with respect to the bonding position of Ax, and more preferably the p-position. Among them, Rx is preferably a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, or an ethyl group. mx is preferably 0, 1, or 2. X a71 Examples of X 10 -1) to the group represented by formula (X 10 -10). * represents the bonding site with the carbon atom to which -R a7 is bonded. ** represents the bonding site with L a71 . X 20 represents -O- or -NR a71 -. TIFF2025113198000108.tif44162 Formula (X 10 -1) to the group represented by formula (X 10 -10) include the following groups as specific examples. TIFF2025113198000109.tif79162 Among them, X a71 is a single bond or the formula (X 10 -1’) and the formula (X 10 -3’) to the formula (X10 It is preferably a group represented by any one of -(X-1’), -(X-4’), -(X-5’), -(X-6’) and -(X-9’), and is a single bond or a group represented by the formula (X 10 -1’), the formula (X 10 -4’), the formula (X 10 -5’), the formula (X 10 -6’) and the formula (X 10 -9’), more preferably a single bond, a group represented by the formula (X 10 -1’), a group represented by the formula (X 10 -5’), a group represented by the formula (X 10 -6’) or a group represented by the formula (X 10 -9’).
[0152] L a71 Examples of the hydrocarbon group of include a group obtained by removing one hydrogen atom from a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group combining two or more of these groups, and bonding to X a71 and X a72 . Also, examples of the hydrocarbon group of L a72 include a group obtained by removing one hydrogen atom from a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group combining two or more of these groups, and bonding to X a72 and RA - . L a71 and L a72 Examples of the chain hydrocarbon group of include a group obtained by removing one hydrogen atom from an alkyl group or an alkenyl group. The alkyl group may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, etc. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group, etc. The number of carbon atoms in the chain hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 18, and even more preferably from 1 to 10. L a71 and L a72 Examples of the alicyclic hydrocarbon group of L and L include a group obtained by removing one hydrogen atom from a monocyclic or polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group, and the like. L a71 and L a72 Examples of the polycyclic cycloalkyl group of L and L include a cycloalkyl group having a cross-linked structure, a cycloalkyl group in which two or more rings are condensed, or a cycloalkyl group in which two rings are spiro-bonded. Examples of the cycloalkyl group having a cross-linked structure include a norbornyl group, an adamantyl group, and the like. Examples of the cycloalkyl group in which two or more rings are condensed include a bicyclo[4,4,0]decane group, a steroid group (steroid skeleton), and the like. Examples of the cycloalkyl group in which two rings are spiro-bonded include a spirocyclic cycloalkyl group in which one cycloalkyl group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group and a cycloalkyl group having 5 to 8 carbon atoms are spiro-bonded. Further, a double bond may be formed between two carbon atoms contained in the alicyclic hydrocarbon group. More specifically, the alicyclic hydrocarbon group represented by the following formula can be mentioned. TIFF2025113198000110.tif28158 When the alicyclic hydrocarbon group is a monocyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 18, more preferably from 3 to 12, and even more preferably from 3 to 8. When the alicyclic hydrocarbon group is a polycyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably from 6 to 18, more preferably from 7 to 12. L a71 and L a72Examples of the aromatic hydrocarbon group include a group obtained by removing one hydrogen atom from an aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a fluorenyl group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 5 to 14, more preferably 6 to 14, and even more preferably 6 to 10. L a71 and L a72 When -CH2- contained in the hydrocarbon group of and L is replaced by -O-, -CO-, -S- or -SO2-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the hydrocarbon group. L a71 and L a72 Among the hydrocarbon groups of and L, examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2- include a hydroxy group, a carboxy group, a carbonyl group, an oxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkanedioxy group, an alkanedioxycarbonyl group, an alkanediylcarbonyl group, and an alkanediylcarbonyloxy group. These replaced groups include those similar to those exemplified in this specification as long as the upper limit of the number of carbon atoms permits. L a71 and L a72 Among the hydrocarbon groups of and L, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2- include a group containing a cyclic ether, a cyclic ketone, a cyclic ester (lactone), a cyclic thioether, a cyclic acetal, or a cyclic sulfonic acid ester ( sultone) structure. Specifically, alicyclic hydrocarbon groups represented by the following formulas can be mentioned. The bonding position of the alicyclic hydrocarbon groups listed in the following formulas can be any position. TIFF2025113198000111.tif46146L a71 and L a72 Among the hydrocarbon groups of and L, -CH2- contained in the aromatic hydrocarbon group may be replaced by -O- or -S-. Examples of the group in which -CH2- is replaced by -O- or -S- include groups derived from a furan ring or a thiophene ring, respectively. L a71 and L a72 Examples of the group formed by combining two or more of the chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group of L and L include the group formed by combining the above chain hydrocarbon group and the above alicyclic hydrocarbon group, the group formed by combining the above chain hydrocarbon group and the above aromatic hydrocarbon group, the group formed by combining the above alicyclic hydrocarbon group and the above aromatic hydrocarbon group, and the group formed by combining the above chain hydrocarbon group, the above alicyclic hydrocarbon group, and the above aromatic hydrocarbon group. The group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group may be a condensed ring. L a71 and L a72 Examples of the substituent that the hydrocarbon group of L and L may have include a halogen atom, a cyano group, and a nitro group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. L a71 and L a72 When L and L are a group formed by combining an alicyclic hydrocarbon group or an aromatic hydrocarbon group with a chain hydrocarbon group, substantially, the chain hydrocarbon group may be regarded as a substituent that the alicyclic hydrocarbon group or the aromatic hydrocarbon group has. Also, a71 and L a72 When -CH2- of the chain hydrocarbon group contained in the hydrocarbon group of L and L is replaced by -O-, -CO-, -S-, or -SO2-, a71 and L a72 the hydrocarbon group of L and L can substantially have substituents such as a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, a thiol group, an alkylthio group, and an alkylsulfonyl group. na7 is preferably 0 or 1. ZA in formula (a7-A) + is the same as the cation in the salt represented by formula (B1) and the like.
[0153] In formula (a7-A), when the hydrocarbon groups of L a71 and L a72 are saturated hydrocarbon groups, in formula (a7-B) described later, A b7It may contain a group similar to the group exemplified as the divalent linking group. Examples of the structural unit represented by the formula (a7-A) include the structural unit represented by the formula (a7-A1) and the like. TIFF2025113198000112.tif30138[In the formula (a7-A1), R a7 、X a71 、L a71 、X a72 、na7、RA - and ZA + represent the same meaning as described above. z7 represents any integer from 0 to 6. Q a7 、Q b7 、R z71 and R z72 each 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. When z7 is 2 or more, a plurality of R z71 and R z72 may be the same as or different from each other.] Q a7 、Q b7 、R z71 and R z72 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms or the alkyl group having 1 to 6 carbon atoms in include groups similar to the groups exemplified by R a7 .
[0154] Examples of the structural unit represented by the formula (a7-A) include, for example, the following structural units, a group corresponding to the methyl group of R a7 replaced by a hydrogen atom, a halogen atom (for example, a fluorine atom), or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom (for example, a trifluoromethyl group, etc.), and the structural units described in WO 2012 / 050015. ZA + represents an organic cation. TIFF2025113198000113.tif131158
[0155] TIFF2025113198000114.tif244163
[0156] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by formula (a7-B). TIFF2025113198000115.tif28104[In formula (a7-B), R a7 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A b7 represents a single bond or a divalent linking group. R b71 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. R b72 and R b73 each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and R b72 and R b73 may combine with each other to form a ring together with the sulfur atom to which they are attached. A - represents an organic anion.] R a7 Examples of the halogen atom and the alkyl group which may have a halogen atom of R include the same halogen atoms and alkyl groups which may have a halogen atom as those in formula (a7-A). R b71 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by include a phenylene group and a naphthylene group. R b72 and R b73 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the group formed by combining these are the same as those described above. A b7 Examples of the divalent linking group represented by include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S-, or -CO-. Examples of the divalent saturated hydrocarbon group include a divalent chain saturated hydrocarbon group such as a linear or branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof may also be used. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; divalent monocyclic alicyclic saturated hydrocarbon groups which are monocyclic cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; divalent polycyclic alicyclic saturated hydrocarbon groups which are polycyclic cycloalkanediyl groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. may be mentioned. Examples of the group in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by the following. However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following formula, * and ** represent bonding sites, and * represents the bonding site with R b71 and represents the bonding site with. TIFF2025113198000116.tif123161[wherein X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
[0157] As the structural unit containing the cation in formula (a7-B), there are structural units represented by the following and groups corresponding to the methyl group of R a7 in which the hydrogen atom, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group, etc.) are replaced, and the like. JPEG2025113198000117.jpg72163
[0158] A - Examples of the organic anion represented by include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, and the like. A - The organic anion represented by is preferably a sulfonate anion, and as the sulfonate anion, it is more preferably the same as the anion exemplified by the acid generator (B). Examples of the sulfonylimide anion, sulfonylmethide anion, and carboxylic acid anion include the same anions as those exemplified by the acid generator (B).
[0159] Examples of the structural unit represented by formula (a7-B) include structural units represented by the following. JPEG2025113198000118.jpg96157
[0160] When the resin (A) etc. contain the structural unit (a7), the structural unit (a7) may be contained alone or may contain two or more kinds. The total content rate of the structural unit (a7) is preferably 1 to 30 mol%, more preferably 1 to 25 mol%, still more preferably 2 to 20 mol%, even more preferably 3 to 15 mol%, and even more preferably 3 to 10 mol% with respect to all the structural units of the resin (A) etc.
[0161] The resin (A) etc. are preferably resins containing the structural unit (a1). In particular, the resin (Ap) is more preferably a resin composed of the structural unit (IP), the structural unit (a1), and the structural unit (s), that is, a copolymer of the salt (I), the monomer (a1), and the monomer (s). The resin (A) that does not contain the structural unit (IP) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), the structural unit represented by the formula (a1-4), the structural unit represented by the formula (a1-5), and the structural unit represented by the formula (a1-6), more preferably at least two kinds, and still more preferably at least two kinds selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-C) or the structural unit (a2-A). The structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4).
[0162] Each structural unit constituting the resin (A) etc. may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomer leading to these structural units. The content ratio of each structural unit possessed by the resin (A) etc. can be adjusted by the amount of monomer used in the polymerization. The resin (A) and the resin (Ap) preferably have a weight average molecular weight of, for example, 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less), but may contain an oligomer having a weight average molecular weight of less than 2,000. In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the examples. Note that the structural unit (IP) may constitute a dimer, a trimer, a compound or an oligomer having a weight average molecular weight of less than 2,000.
[0163] <Acid generator> The acid generator of the present invention is an acid generator containing the salt (I) of the present invention and / or the structural unit (IP). The structural unit (IP) can be contained as a polymerized compound or resin. In the acid generator, one kind of the salt (I) may be contained, or two or more kinds of the salt (I) may be contained. Also, one kind of the compound or resin containing the structural unit (IP) may be used alone, or two or more kinds may be used in combination. Further, the acid generator of the present invention may contain both the salt (I) and the structural unit (IP). In addition to the salt (I) and / or the structural unit (IP), the acid generator of the present invention may contain a known compound (hereinafter sometimes referred to as "compound (B)" or "acid generator (B)") that acts as an acid generator in the resist field. The compound (B) may be used alone or in combination of two or more. When the acid generator contains salt (I) and compound (B), the content ratio (mass ratio, salt (I): compound (B)) of salt (I) and compound (B) is, for example, 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, still more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 40:60 to 60:40. When the acid generator contains structural unit (IP) and compound (B), the content ratio (mass ratio, structural unit (IP): compound (B)) of structural unit (IP) and compound (B) is, for example, 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, still more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 40:60 to 60:40.
[0164] [Resist composition] The resist composition of the present invention contains the acid generator of the present invention. The acid generator here may be salt (I) or may be resin (Ap) containing structural unit (IP). The resist composition of the present invention may contain a resin in addition to the acid generator of the present invention. The resin may be a resin containing structural unit (a1) having an acid-labile group or may be a resin not containing structural unit (a1). However, the resist composition of the present invention contains at least one of salt (I) and structural unit (IP) and may contain both. That is, the resist composition of the present invention only needs to contain an acid generator containing structural unit (IP) of the present invention or salt (I) of the present invention. 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 resin (Ap) and salt (I) as an acid generator. The resist composition of the present invention preferably contains a resin containing structural unit (a1) having an acid-labile group. That is, at least, (a) contains salt (I) and resin (A) containing structural unit (a1) having an acid-labile group, or (b) contains resin (Ap) containing structural unit (IP) and structural unit (a1) having an acid-labile group, Preferably, it contains a resin (Ap) containing a structural unit (IP) and a resin (A) containing a structural unit (a1) having an acid-labile group. Among them, the resist composition of (b) above is preferable. The resist composition of the present invention may contain two or more kinds of resins (A) and / or resins (Ap). Further, (b) and (c) above may further contain a salt (I). The resist composition of the present invention preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). Further, the resist composition of the present invention may further contain a resin other than the resin (A) and the like described above.
[0165] <Resin other than resin (A) etc.> The resist composition of the present invention may contain a resin other than the resin (Ap) and the resin (A). Examples of the resin other than the resin (Ap) and the resin (A) include a resin containing the same structural unit as the resin (A) other than the resin (A) not containing the structural unit (a1) in the above-described resin (A) (hereinafter sometimes referred to as "resin (AX)"), a resin containing the structural unit (a4) and / or the structural unit (a5) (however, not containing the structural unit (IP) and the structural unit (a1); hereinafter sometimes referred to as "resin (X)") and the like.
[0166] Examples of the resin (AX) include a resin containing the structural unit (a2), and a resin containing the structural unit (a2-A) is preferable. In the resin (AX), the content of the structural unit (a2-A) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more with respect to the total of all the structural units of the resin (AX). Further, it is preferably 80 mol% or less, and more preferably 70 mol% or less. Examples of the structural units that resin (X) may further have include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. Among them, resin (X) is preferably a resin composed only of structural unit (a4) and / or structural unit (a5), and more preferably a resin composed only of structural unit (a4). When resin (X) contains structural unit (a4), in resin (X), the content of structural unit (a4) is 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 45 mol% or more, based on the total of all the structural units of resin (X). Also, it is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, it is 20 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. When resin (X) contains structural unit (a5), the content of structural unit (a5) is 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 45 mol% or more, based on the total of all the structural units of resin (X). Also, it is 100 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, and even more preferably 55 mol% or less. Specifically, it is 20 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. When resin (X) contains structural unit (a4) and structural unit (a5), the total content of structural unit (a4) and structural unit (a5) is 40 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more, based on the total of all the structural units of resin (X). Further, it is 100 mol% or less. Specifically, it is 40 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5). In this case, the ratio of the structural unit (a4) to the structural unit (a5) is 0:100 to 100:0, preferably 10:90 to 90:10, more preferably 30:70 to 70:30 or 40:60 to 60:40. Each structural unit constituting the resin (AX) and the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units. The content of each structural unit of the resin (AX) and the resin (X) can be adjusted by the amount of the monomers used in the polymerization. The resin (AX) and the resin (X) preferably have a weight average molecular weight of 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less), but may contain oligomers having a weight average molecular weight of less than 6,000. The measuring means for the weight average molecular weight of the resin (AX) and the resin (X) is the same as that of the resin (A) and the like.
[0167] When the resist composition of the present invention contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass, based on 100 parts by mass in total of the resin (A) and the like.
[0168] The total content of resin (A) etc. in the resist composition is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 99% by mass or less, still more preferably 80% by mass or more and 99% by mass or less, and even more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. The content of resin (Ap) is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 99% by mass or less, still more preferably 80% by mass or more and 99% by mass or less, and even more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When a resin other than resin (A) etc. is included, the total content of resin (A) etc. and the resin other than resin (A) etc. is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 99% by mass or less, still more preferably 80% by mass or more and 99% by mass or less, and even more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.
[0169] <Acid generator> As described above, the acid generator of the present invention may be any of an acid generator containing only salt (I) and / or structural unit (IP), and an acid generator containing salt (I) and / or structural unit (IP) and a known compound (B) that acts as an acid generator in the resist field.
[0170] <Compound (B)> Either non-ionic compounds or ionic compounds may be used as compound (B). Examples of non-ionic compounds include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic compounds include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, benzenesulfonyl anions, sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions, etc. Also, compound (B) may be a structural unit having an acid-generating function, and for example, it may be a part of a resin containing the above-mentioned structural unit (a7) etc.
[0171] As compound (B), compounds that generate an acid upon irradiation as described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Also, compounds produced by known methods may be used. Also, compound (B) may be an acid generator having an acid-labile group. For example, the compound or resin serving as the acid generator may contain a partial structure that becomes an acid-labile group, and the acid-labile group preferably contains the above-mentioned group (1) or group (2). When the resist composition of the present invention contains a compound having an acid-labile group, a resin containing a structural unit having an acid-labile group may not be included.
[0172] Compound (B) is preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "salt (B1)" or "compound (B1)", provided that salt (I) is excluded) or a salt represented by formula (B2) (hereinafter sometimes referred to as "salt (B2)" or "compound (B2)"). TIFF2025113198000119.tif1391[In formula (B1), L b1 represents a single bond or an (nb1 + 1)-valent hydrocarbon group which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. L b2 represents a single bond or a divalent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. Y b1 represents a methyl group which may have a substituent or a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. nb1 represents any integer from 1 to 6. When nb1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. Z1 + represents an organic cation.]
[0173] In formula (B1), as the (nb1 + 1)-valent hydrocarbon group of L b1 there may be mentioned a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a monovalent group formed by combining two or more of these groups, from which nb1 hydrogen atoms are removed and which is bonded to one or more L b2 groups. The number of carbon atoms of the hydrocarbon group is preferably from 1 to 48, more preferably from 1 to 42, still more preferably from 1 to 36, even more preferably from 1 to 30, and even more preferably from 1 to 24. Examples of the chain hydrocarbon group include a group in which nb1 hydrogen atoms are removed from an alkyl group or an alkenyl group. The alkyl group may be linear or branched, and specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group, and the like. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, isooctenyl group, nonenyl group. The number of carbon atoms of the chain hydrocarbon group is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 20, even more preferably 1 to 18, even further preferably 1 to 12, and even further preferably 1 to 10. Examples of the alicyclic hydrocarbon group include a group in which nb1 hydrogen atoms are removed from a monocyclic or polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and the like. Examples of the polycyclic cycloalkyl group include a cycloalkyl group having a crosslinked structure, a cycloalkyl group in which two or more rings are condensed, or a cycloalkyl group in which two rings are spiro-bonded. Examples of the cycloalkyl group having a crosslinked structure include norbornyl group, adamantyl group, and the like. Examples of the cycloalkyl group in which two or more rings are condensed include bicyclo[4,4,0]decane group, steroid group (steroid skeleton), and the like. Examples of the cycloalkyl group in which two rings are spiro-bonded include a spirocyclic cycloalkyl group in which one cycloalkyl group selected from the group consisting of cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group and a cycloalkyl group having 5 to 8 carbon atoms are spiro-bonded. Further, a double bond may be formed between two carbon atoms contained in the alicyclic hydrocarbon group. More specifically, examples of the alicyclic hydrocarbon group include those represented by the following formula. TIFF2025113198000120.tif26168 When the alicyclic hydrocarbon group is a monocyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 24, more preferably 3 to 20, still more preferably 3 to 18, even more preferably 3 to 12, still even more preferably 3 to 10, and still more preferably 3 to 8. When the alicyclic hydrocarbon group is a polycyclic cycloalkyl group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 6 to 24, more preferably 6 to 20, still more preferably 6 to 18, even more preferably 6 to 12, and still even more preferably 7 to 12. Examples of the aromatic hydrocarbon group include a group obtained by removing nb1 hydrogen atoms from an aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a fluorenyl group, and the like. More specifically, examples of the aromatic hydrocarbon group include those represented by the following formula. TIFF2025113198000121.tif1185 The number of carbon atoms in the aromatic hydrocarbon group is preferably 4 to 24, more preferably 4 to 20, still more preferably 4 to 18, even more preferably 5 to 14, still even more preferably 5 to 10, and still more preferably 6 to 10. L b1 When -CH2- contained in the hydrocarbon group of L is replaced by -O-, -CO-, -S- or -SO2-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the hydrocarbon group. L b1Among the hydrocarbon groups, examples of the group in which -CH2- contained in the chain hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2- include a hydroxy group, a carboxy group, a carbonyl group, an oxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkanedioxy group, an alkanedioxycarbonyl group, an alkanediylcarbonyl group, an alkanediylcarbonyloxy group, etc. These replaced groups include, within the range where the upper limit of the number of carbon atoms allows, the same groups as those exemplified in this specification. L b1 Among the hydrocarbon groups, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -CO-, -S- or -SO2- include groups containing structures such as cyclic ethers, cyclic ketones, cyclic esters (lactones), cyclic thioethers, cyclic acetals, cyclic sulfonic acid esters (sultones), etc. Specifically, within the range where the upper limit of the number of carbon atoms allows, the same groups as those exemplified in this specification are included. Also included are alicyclic hydrocarbon groups represented by the following formulas. The bonding positions of the alicyclic hydrocarbon groups listed in the following formulas can be at any position. TIFF2025113198000122.tif48165L b1 Among the hydrocarbon groups, -CH2- contained in the aromatic hydrocarbon group may be replaced by -O- or -S-. Examples of the group in which -CH2- is replaced by -O- or -S- include groups derived from a furan ring or a thiophene ring, respectively. Specifically, aromatic hydrocarbon groups represented by the following formulas are included. TIFF2025113198000123.tif1326Examples of the group in which -CH2- contained in a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include, within the range where the upper limit of the number of carbon atoms allows, the same groups as those exemplified in this specification. Examples of a group formed by combining two or more of an alicyclic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group include a group formed by combining the above alicyclic hydrocarbon group and the above alicyclic hydrocarbon group, a group formed by combining the above alicyclic hydrocarbon group and the above aromatic hydrocarbon group, a group formed by combining the above alicyclic hydrocarbon group and the above aromatic hydrocarbon group, and a group formed by combining the above alicyclic hydrocarbon group, the above alicyclic hydrocarbon group, and the above aromatic hydrocarbon group. The group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group may be a condensed ring. L b2 Examples of the divalent hydrocarbon group of include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by combining two or more of these groups, and removing one hydrogen atom from a monovalent hydrocarbon group to form a group that binds to Y b1 and. L b2 Examples of the divalent chain hydrocarbon group, divalent alicyclic hydrocarbon group, divalent aromatic hydrocarbon group, and divalent group formed by combining two or more of these groups of are, respectively, within the range allowed by the upper limit of the number of carbon atoms, the monovalent chain hydrocarbon group, monovalent alicyclic hydrocarbon group, monovalent aromatic hydrocarbon group, and monovalent group formed by combining two or more of these exemplified by L b1 and a group obtained by removing one hydrogen atom from the monovalent group formed by combining two or more of these. L b1 and L b2 Examples of the substituent that the hydrocarbon group of and L may have include a halogen atom, a cyano group, a nitro group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. L b1 and L b2 When and are a group formed by combining an alicyclic hydrocarbon group or an aromatic hydrocarbon group and a chain hydrocarbon group, the chain hydrocarbon group may be substantially regarded as a substituent that the alicyclic hydrocarbon group or aromatic hydrocarbon group has. Further, when -CH2- of the chain hydrocarbon group contained in the hydrocarbon group of and is replaced by -O-, -CO-, -S-, or -SO2-, and b1 and L b2 and b1 and L b2The hydrocarbon group can substantially have substituents such as a hydroxy group, a carboxy group, a carbonyl group, an oxycarbonyl group, a carbonyloxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a thiol group, an alkylthio group, an alkylsulfonyl group, etc. L b1 and L b2 The number of substituents that may be possessed is not particularly limited, and a plurality of substituents may be possessed. Y b1 Examples of the cyclic hydrocarbon group of Y include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Y b1 The alicyclic hydrocarbon group and the aromatic hydrocarbon group of Y are respectively the same as the alicyclic hydrocarbon group and the aromatic hydrocarbon group exemplified by L b1 and when they have no substituents, they may be monovalent alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Y b1 Examples of the substituents that the methyl group of Y may have include a halogen atom, a cyano group, a hydroxy group, a nitro group, etc. Y b1 Examples of the substituents that the cyclic hydrocarbon group of Y may have include a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 18 carbon atoms that may have a halogen atom, a cyano group or a nitro group (the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). Y b1 The number of carbon atoms of the hydrocarbon group that the cyclic hydrocarbon group of Y may have is not included in the number of carbon atoms of the cyclic hydrocarbon group of Y b1 Examples of the halogen atom include the same halogen atoms as the halogen atoms exemplified as the substituents of L b1 and L b2 Y b1 The hydrocarbon group having 1 to 18 carbon atoms which may have a cyclic hydrocarbon group as a substituent includes a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these groups. Examples of the chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group combining two or more of these groups include, within the range allowed by the upper limit of the number of carbon atoms, L b1 The same groups as the chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group combining two or more of these groups exemplified by b1 can be mentioned. Also, Y b1 Examples of the group in which -CH2- contained in the hydrocarbon group having 1 to 18 carbon atoms which may have a cyclic hydrocarbon group of Y as a substituent is replaced by -O-, -S-, -CO- or -SO2- include, within the range allowed by the upper limit of the number of carbon atoms, L b1 The same groups as the groups exemplified by the group in which -CH2- contained in the hydrocarbon group of b1 is replaced by -O-, -S-, -CO- or -SO2- can be mentioned. Also, Y b1 The hydrocarbon group having 1 to 18 carbon atoms which may have a cyclic hydrocarbon group of Y as a substituent may constitute a protecting group or a leaving group (acid-labile group or base-labile group) generally used in the art.
[0174] Examples of the anion of the salt represented by formula (B1) include, for example, the anion represented by the following formula (B1-A1) (hereinafter sometimes referred to as "anion (B1-A1)") or the anion represented by formula (B1-A2) (hereinafter sometimes referred to as "anion (B1-A2)"). TIFF2025113198000124.tif31117[In formula (B1-A1), L b2 and Y b1 represent the same meaning as in formula (B1). Q b1 Q b2 Q b3 and Q b4 each 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. z1 represents any integer from 0 to 6. When z1 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other. X 1 represents -O-CO-, -CO-O-, -O-CO-O- or -O-. L b3 represents a single bond or an (nb2 + 1)-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. nb2 represents any integer from 1 to 3. When nb2 is 2 or more, the groups in the plurality of parentheses may be the same as or different from each other.]
[0175] Q b1 Q b2 Q b3 and Q b4 Examples of the perfluoroalkyl group of Q Q b1 Q b2 Q b3 and Q b4 Examples of the alkyl group of Q Q b1 and Q b2 are preferably included in at least one of Q b1 and Q b2 a fluorine atom or a perfluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, even more preferably a fluorine atom or a trifluoromethyl group, and even more preferably both are fluorine atoms. Q b3 and Q b4 are each independently preferably a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, and Q b3 is preferably a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, and Qb4 is preferably a hydrogen atom or a fluorine atom. z1 is preferably any integer from 0 to 3, more preferably 0, 1 or 2. X 1 is preferably -O-CO- or -CO-O-.
[0176] L b3 As the hydrocarbon group in, within the range allowed by the upper limit of the number of carbon atoms, the L exemplified in the formula (B1) b1 has the same hydrocarbon groups as the examples. L b3 is a single bond, an optionally substituted chain hydrocarbon group having 1 to 12 carbon atoms (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-), an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms (wherein -CH2- contained in the aromatic hydrocarbon group may be replaced by -O- or -S-), or a group formed by combining two or more of these groups, preferably a single bond, a chain hydrocarbon group having 1 to 6 carbon atoms or a group represented by the following formula (Lb3-1). When -CH2- contained in the chain hydrocarbon group is replaced by -O- or -CO-, the number thereof is preferably 1 to 4, and preferably one -CH2-CH2- contained in the chain hydrocarbon group is replaced by -O-CO- or -CO-O-, or one -CH2-CH2-CH2- contained in the chain hydrocarbon group is replaced by -O-CO-O-. TIFF2025113198000125.tif1682 [In the formula (Lb3-1), nb2 has the same meaning as in the formula (B1-A1). L b31 represents a single bond or a chain hydrocarbon group having 1 to 12 carbon atoms, wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the chain hydrocarbon group may have a substituent. W b3represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the aromatic hydrocarbon group may be replaced by -O- or -S-, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have substituents. * and ** represent bonding sites, and * represents X 1 and represents the bonding site with.] In formula (Lb3-1), L b31 The chain hydrocarbon group of may be the same group as the chain hydrocarbon group exemplified by L b1 within the limit allowed by the upper limit of the number of carbon atoms. In formula (Lb3-1), W b3 The alicyclic hydrocarbon group and the aromatic hydrocarbon group of may be the same groups as the alicyclic hydrocarbon group and the aromatic hydrocarbon group exemplified by L b1 within the limit allowed by the upper limit of the number of carbon atoms. In formula (Lb3-1), L b31 The substituents that the chain hydrocarbon group of may have and W b3 The substituents that the alicyclic hydrocarbon group and the aromatic hydrocarbon group of may have are the same groups as the substituents exemplified as the substituents that the hydrocarbon group of L b1 may have. L b31 is preferably a single bond or an alkanediyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). Among them, as the alicyclic hydrocarbon group and the aromatic hydrocarbon group of W b3 the alicyclic hydrocarbon group and the aromatic hydrocarbon group represented below are preferable. In the alicyclic hydrocarbon group and the aromatic hydrocarbon group represented below, * and ** represent bonding sites, and * represents X 1 or L b31 and represents the bonding site with, and ** represents a hydrogen atom, a substituent or L b2 and represents the bonding site with, and at least one ** is L b2represents a binding site thereto. Further, in the alicyclic hydrocarbon group represented below, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. When -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- o...
Claims
1. An acid generator containing a salt represented by formula (I1) or formula (I2) or a structural unit represented by formula (IP1) or formula (IP2). [In formula (I1), formula (I2), formula (IP1) and formula (IP2), R 1 represents a halogen atom, a cyano group, a nitro group, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group may have a substituent, and the -CH contained in the haloalkyl group and the hydrocarbon group 2 - is -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 - may be replaced by. R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m1 represents any integer from 0 to 4. When m1 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * represents the bonding site with the benzene ring). L 1 represents an aliphatic hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or substituents, and -CH 2 - in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 - and may be replaced. R 3 and R 4 each independently represents 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 a substituent, and -CH 2 - in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO 2 - may be replaced. m3 represents any integer from 1 to 4, and when m3 is 2 or more, the plurality of Rs 3 may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs 4 may be the same as or different from each other. R 5 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZI + represents an organic cation.
2. R 3 and R 4 The acid generator according to claim 1, wherein R and R are each a fluorine atom, an iodine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a perfluoroalkyl group having 1 to 3 carbon atoms.
3. X 1 The acid generator according to claim 1, wherein X is *-CO-O- or *-O-CO-.
4. L 1 The acid generator according to claim 1, wherein L is a single bond or a linear alkanediyl group having 1 to 6 carbon atoms.
5. The acid generator according to claim 1, wherein m3 and m4 are each independently 1 or 2.
6. A resist composition containing the acid generator according to any one of claims 1 to 5.
7. The acid generator is a salt represented by formula (I1) or formula (I2), The resist composition according to claim 6, further containing a resin containing a structural unit (a1) having an acid-labile group.
8. The acid generator is a resin containing a structural unit represented by formula (IP1) or formula (IP2), The resist composition according to claim 6, wherein the resin further contains a structural unit (a1) having an acid-labile group.
9. The resist composition according to claim 8, further containing a salt represented by formula (I1) or formula (I2).
10. The resist composition according to claim 7, wherein the structural unit (a1) having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a1-4), a structural unit represented by formula (a1-5) and a structural unit represented by formula (a1-6). [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 、 L a1 and L a2 each independently represents -O- or *-O-(CH 2 ), k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents the bonding site with -CO-. R a01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. m1' represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3. ] [In formula (a1-4), R a1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a17 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a11 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and -CH 2 - in the alkanediyl group may be replaced by -O-, -CO- or -NR a18 -. R a18 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a1 represents a single bond or a carbonyl group. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH 2 - contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. na1 represents any integer from 1 to 5. When na1 is 2 or more, the groups within multiple parentheses may be the same as or different from each other. na11 represents any integer from 0 to 4, and when na11 is 2 or more, a plurality of Rs a17 may be the same as or different from each other. mc represents any integer from 0 to 2. ] [In formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. Z a1 represents a single bond or *-(CH 2 ) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding site with L 51 . L 51 、 L 52 、 L 53 and L 54 each independently represents -O- or -S-. s1 represents any integer from 1 to 3. s1' represents any integer from 0 to 3. ] [In formula (a1-6), R a61 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a62 , R a63 and R a64 each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, or R a62 and R a63 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. X a61 represents a single bond, -CO-O-*, or -CO-NR a65 -*, where * represents the bonding site with Ar, and R a65 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a62 represents a single bond, *-O-L a61 - or *-CO-O-L a62 -, where * represents the bonding site with Ar, and L a61 and L a62 each independently represents an alkanediyl group having 1 to 4 carbon atoms. Ar represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. ]
11. The resist composition according to claim 7, wherein the resin containing a structural unit (a1) having an acid-labile group further contains a structural unit represented by formula (a2-A). [In formula (a2-A), R a2 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a27 represents a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a21 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the -CH 2 - in the alkanediyl group may be replaced by -O-, -CO- or -NR a28 -. R a28 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a2 represents a single bond or a carbonyl group. nA2 represents any integer from 1 to 5, and when nA2 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. na21 represents any integer from 0 to 4, and when na21 is 2 or more, a plurality of Rs a27 may be the same as or different from each other. mc represents any integer from 0 to 2. ]
12. The resist composition according to claim 6, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator.
13. (1) A step of applying the resist composition according to claim 6 onto a substrate, (2) A step of drying the applied resist composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including these steps.
14. A salt represented by formula (I1) or formula (I2). [In formula (I1) and formula (I2), R 1 represents a halogen atom, a cyano group, a nitro group, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group may have a substituent, and the -CH 2 - is optionally replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 - may be replaced by. R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m1 represents any integer from 0 to 4, and when m1 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * represents the bonding site with the benzene ring). L 1 represents an aliphatic hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and the -CH 2 - in it may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 -. R 3 and R 4 each independently represents 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 a substituent, and -CH 2 - in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO 2 - may be replaced. m3 represents any integer from 1 to 4, and when m3 is 2 or more, the plurality of Rs 3 may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs 4 may be the same as or different from each other. R 5 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZI + represents an organic cation.
15. R 3 and R 4 The salt according to claim 14, wherein R and R are each a fluorine atom, an iodine atom, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a perfluoroalkyl group having 1 to 3 carbon atoms.
16. X 1 The salt according to claim 14 or 15, wherein X is *-CO-O- or *-O-CO-.
17. L 1 The salt according to claim 14 or 15, wherein L is a single bond or a linear alkanediyl group having 1 to 6 carbon atoms.
18. The salt according to claim 14 or 15, wherein m3 and m4 are each independently 1 or 2.
19. A resin containing a structural unit represented by formula (IP1) or formula (IP2). [In formula (IP1) and formula (IP2), R 1 represents a halogen atom, a cyano group, a nitro group, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group may have a substituent, and -CH contained in the haloalkyl group and the hydrocarbon group 2 - is -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 - may be replaced with. R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m1 represents any integer from 0 to 4, and when m1 is 2 or more, the groups within the plurality of parentheses may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * represents the bonding site with the benzene ring). L 1 represents an aliphatic hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and the -CH 2 - in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO-, -SO-, -NR 7 - or -SO 2 -. R 3 and R 4 each independently represents 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 a substituent, and -CH 2 - in the haloalkyl group and the hydrocarbon group may be replaced by -O-, -CO-, -S-, -SO-, -NR 7 - or -SO 2 - may be replaced. m3 represents any integer from 1 to 4, and when m3 is 2 or more, the plurality of Rs 3 may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs 4 may be the same as or different from each other. R 5 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZI + represents an organic cation.
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Actinic-ray- or radiation-sensitive resin composition and method of forming pattern using the same
JP2011175253A