Resist composition and method for producing resist pattern

Abstract

To provide a resist composition having good CD uniformity (CDU).SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin having an acid-labile group. The resin having an acid-labile group contains a structural unit represented by formula (a2-A).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition and a method for manufacturing a resist pattern.

Background Art

[0002] Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025102839000001.tif2864 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025102839000002.tif2866 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025102839000003.tif2881

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a salt capable of manufacturing a resist pattern with better CD uniformity (CDU) than a resist pattern formed from a resist composition containing the above salt. This is the problem.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025102839000004.tif20110 [In formula (I), Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents. R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents. z represents any integer from 0 to 6, and when z is 2 or more, a plurality of R 1 and R 2 may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O- or *-O-CO-O-, * represents the bonding site with C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ). L 1 represents a single bond or * -L 4 -O- (wherein L 4 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -S O2- or -CO-. * represents the bonding site with X 1 ). R 3 and R 4 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. . Ar represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. Z + represents an organic cation. ] [2] R 4 ​The salt described in [1], wherein the salt is a hydrogen atom. [3] Ar is a phenyl group which may have a substituent, the salt described in [1] or [2] . [4] X 1 is *-CO-O- or *-O-CO-O- (wherein * represents a bonding site with C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ), and represents the salt described in any one of [1] to [3].) [5] An acid generator containing the salt described in any one of [1] to [4]. [6] A resist composition containing the acid generator described in [5] and a resin having an acid-labile group. [7] The resist composition described in [6], wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1- 2). TIFF2025102839000005.tif4292 [In the formula (a1-1) and the formula (a1-2), 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 a bond with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkene nyl 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 combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1’ represents an integer of any one of 0 to 3. [8] The resin having an acid-labile group contains a structural unit represented by the formula (a2-A) [6] or is the resist composition described in [7]. TIFF2025102839000006.tif4450 [In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb - represents, and * represents the bonding site with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of any one of 0 to 4. When mb is an integer of 2 or more, a plurality of R may be the same as or different from each other. a51 [9] Further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator. The resist composition according to any one of [6] to [8].

[10] (1) Apply the resist composition according to any one of [6] to [9] onto a substrate. Step, (2) A step of drying the applied composition to form a composition layer. (3) A step of exposing the composition layer. (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, a method for manufacturing a resist pattern including these steps.

Effect of the Invention

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

Mode for Carrying Out the Invention

[0007] In this specification, the “(meth)acrylic monomer” means at least one selected from the group consisting of monomers having the structure of “CH2=CH-CO-” and monomers having the structure of “CH2=C(CH3)-CO-”. Similarly, “(meth)acrylate” and “(meth)acrylic acid” mean at least one selected from the group consisting of “acrylate and methacrylate” and at least one selected from the group consisting of “acrylic acid and methacrylic acid”, respectively. When a structural unit having “CH2=C(CH3)-CO-” or “CH2=CH-C O-” is exemplified, structural units having both groups are similarly exemplified. Also, for the groups described in this specification that can take both a linear structure and a branched structure, either one is acceptable. “Derived from” or “induced from” means that the polymerizable C=C bond contained in its molecule becomes a -C-C- group by polymerization. Both the linear structure and the branched structure are possible for the groups described in this specification. “Derived from” or “induced from” means that the polymerizable C=C bond contained in its molecule becomes a -C-C- group by polymerization. ​refers to. When stereoisomers exist, all stereoisomers are included. Also, "combined groups" means groups formed by combining two or more of the exemplified groups with their valences appropriately changed and bonded together . In this specification, "the solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later .

[0008] <Salt represented by formula (I)> The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). Among salts (I), the side having a negative charge is sometimes referred to as "anion (I)", and the side having a positive charge is sometimes referred to as "cation (I)". TIFF2025102839000007.tif22115[In the formula, all symbols have the same meanings as described above respectively.]

[0009] In formula (I), Q 1 , Q 2 , R 1 and R 2 Examples of the perfluoroalkyl group of include tri fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro isopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro t ert-butyl group, perfluoropentyl group, perfluorohexyl group, etc. . Q 1 and Q 2 are each independently preferably a trifluoromethyl group or a fluorine atom , more preferably a fluorine atom. R 1 and R 2 are each independently preferably a hydrogen atom or a fluorine atom, more preferably a hydrogen atom. z is preferably 0 or 1. X1 is preferably *-CO-O-, *-O-CO-O- or *-O-CO- , more preferably *-CO-O- or *-O-CO-O- (* represents C(R 1 )) (R 2 ) or C(Q 1 )(Q 2 ) and represents the bonding position with.).

[0010] L 4 The divalent hydrocarbon group in is a divalent chain hydrocarbon group such as an alkanediyl group , a monocyclic or polycyclic (including spiro ring) divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by combining two or more of these groups (for example, an alicyclic hydrocarbon group and a divalent hydrocarbon group formed from an alkanediyl group) may also be used. Examples of the 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-1,1 2-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 other linear alkanediyl groups; and 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, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups. The number of carbon atoms in the chain hydrocarbon group is preferably from 1 to 18, more preferably from 1 to 12, even more preferably from 1 to 9, still more preferably from 1 to 6, and yet more preferably from 1 to 4. Examples of the monocyclic or polycyclic divalent alicyclic hydrocarbon group include the following groups. The bonding hand can be at any position. TIFF2025102839000008.tif41165 The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 18, more preferably from 3 to 16, even more preferably from 3 to 12. Specifically, monocyclic divalent 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 other cycloalkanediyl groups; and polycyclic divalent 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 and the like are included. Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups such as arylene groups such as phenylene group, naphthylene group, anthrylene group, biphenylene group, phenanthrylene group and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 18, more preferably from 6 to 14, even more preferably from 6 to 10. Examples of the group formed by combining two or more types include a group formed by combining an alicyclic hydrocarbon group and an alkanediyl group, a group formed by combining an aromatic hydrocarbon group and an alkanediyl group, and a group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In the combination, the alicyclic carbon The hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may each be combined in two or more kinds. Also, any of these groups may be bonded to X. 1 Examples of the group formed by combining an alicyclic hydrocarbon group and an alkanediyl group include, for example, a divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-, etc. . Examples of the group formed by combining an aromatic hydrocarbon group and an alkanediyl group include, for example, a divalent aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . Examples of the group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-alicyclic hydrocarbon group-, etc. L 4 The -CH2- contained in the divalent hydrocarbon group having 1 to 28 carbon atoms of L may be replaced by -O-, -S-, -SO2- or -CO-. L 4 When the -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms of L is replaced by -O-, -S-, -SO2 - or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the hydrocarbon group. Examples of the group in which the -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO- include a hydroxy group (a group in which the -CH2- contained in the methyl group is replaced by -O-), a carboxy group (a group in which the -CH2-CH2- contained in the ethyl group is replaced by -O-CO- (a group in which -CH2- at any position in the alkyl group is replaced with), an alkoxy group (a group in which -CH2- at any position in the alkyl group is replaced with -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position in the alkyl group is replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -CO-O-), an alkanediyl-oxy group (a group in which -CH2- at any position in the alkanediyl group is replaced with -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -O-CO-), an alkanediyl-carbonyl group (a group in which -CH2- at any position in the alkanediyl group is replaced with -CO-), an alkanediyl-carbonyloxy group (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -CO-O-), an alkylthio group (a group in which -CH2- at any position in the alkyl group is replaced with -S-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, etc. can be mentioned. (a group in which -CH2- at any position in the alkyl group is replaced with -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -O-CO-), (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -O-CO-), an alkylcarbonyl group ( (a group in which -CH2- at any position in the alkyl group is replaced with -CO-), an al kylcarbonyloxy group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with - CO-O-), an alkanediyl-oxy group (a group in which -CH2- at any position in the alkanediyl group is included and is replaced with -O-), an alkanediyl-oxycarbonyl group ( (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -O-CO- ), an alkanediyl-carbonyl group (a group in which -CH2- at any position in the alkanediyl group is included and is replaced with -CO-), an alkanediyl-carbonyloxy group ( (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -CO-O- ), an alkylthio group (a group in which -CH2- at any position in the alkyl group is replaced with, -S-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, etc. can be mentioned. (a group in which -CH2- at any position in the alkyl group is replaced with -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position in the alkyl group is replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position in the alkyl group is replaced with -CO-O-), an alkanediyl-oxy group (a group in which -CH2- at any position in the alkanediyl group is included and is replaced with -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -O-CO-), an alkanediyl-carbonyl group (a group in which -CH2- at any position in the alkanediyl group is included and is replaced with -CO-), an alkanediyl-carbonyloxy group (a group in which -CH2-CH2- at any position in the alkanediyl group is replaced with -CO-O-), an alkylthio group (a group in which -CH2- at any position in the alkyl group is replaced with -S-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, etc. can be mentioned. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an o ctyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an und An alkoxycarbonyl group, an alkylcarbonyl group, and an alkylcarbonyloxy group are groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. They represent groups. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as an acetyloxy group, a propionyloxy group, and a butyryloxy group. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 17 carbon atoms, such as a methyleneoxy group, an ethyleneoxy group, a propanediyl-oxy group, a butanediyl-oxy group, and a pentanediyl-oxy group. They are mentioned. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 17 carbon atoms, such as a methyleneoxycarbonyl group, an ethyleneoxycarbonyl 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 methylenecarbonyl group, an ethylenecarbonyl 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 methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanediyl-oxycarbonyl group, a butanediyl-oxycarbonyl group, etc. They are mentioned. Examples of the alkanediyl-carbonyl group include alkanediyl-carbonyl groups having 2 to 18 carbon atoms, such as a methylenecarbonyl group, an ethylenecarbonyl group, a propanediyl-carbonyl group, a butanediyl-carbonyl group, and a pentanediyl-carbonyl group. They are mentioned. Examples of the alkanediyl-carbonyl-oxy group include alkanediyl-carbonyl-oxy groups having 2 to 17 carbon atoms, Examples of the carbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, a butanediylcarbonyloxy group, and the like. Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, such as a methylthio group, an ethylthio group, and a propylthio group. Examples of the cycloalkoxy group include a cycloalkoxy group having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include a cycloalkylalkoxy group having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include an aromatic hydrocarbon group-carbonyl-oxy group having 7 to 17 carbon atoms, such as a benzoyloxy group. In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include the following groups. The bond can be at any position. TIFF2025102839000009.tif46155

[0011] L 4 Examples of the substituent that may be included include a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group formed by combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc. and the like. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and the like. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a but oxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexy loxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group and the like. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, a butoxycarbonyl group, and the like. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group, and the like. Examples of the alkylcarbonyloxy group having 2 to 1 3 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like. The substituent 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. 4 L is an alkanediyl group having 1 to 6 carbon atoms (however, -CH2- may be replaced by -O- or -CO-.), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -S O2- or -CO-).), an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, an alkane diyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms combined (however, -CH2- contained in the alkane diyl group may be replaced by - O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by - O-, -S-, -SO2- or -CO-).) or a group formed by combining an alkane diyl group having 1 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (however, -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), and it is preferably such a group, an alkane diyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, a group formed by combining an alkane diyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group formed by combining an alkane diyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent (however, -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), and it is more preferably such a group.

[0012] L 1 is a single bond, *-an alkanediyl group having 1 to 6 carbon atoms -O- (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). *, an alicyclic hydrocarbon group having 3 to 18 carbon atoms -O- (provided that -CH 2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-). *, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms -O-, *-an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms combined -O- (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO- and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-). Or *-an alkanediyl group having 1 to 6 carbon atoms and an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms combined -O-( provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). Preferably, it is a single bond, *-an alkanediyl group having 1 to 4 carbon atoms -O-, *-an alicyclic hydrocarbon group having 3 to 18 carbon atoms -O- (provided that -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), *-an optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms -O-, *-an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms combined -O- (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO- and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO- as well). ​​​Good. ) Or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 1 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-).) is more preferred. Here, examples of the group formed by combining the alkanediyl group with the alicyclic hydrocarbon group or the aromatic hydrocarbon group include *-alkanediyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic hydrocarbon group or aromatic hydrocarbon group-alkanediyl group-, *-a lkane diyl group - alicyclic hydrocarbon group or aromatic hydrocarbon group - alkanediyl group - and the like. * represents a bond to X and. For the saturated hydrocarbon group having 1 to 6 carbon atoms of R and R , examples include chain saturated hydrocarbon groups such as alkyl groups, alicyclic saturated hydrocarbon groups, and groups formed by combining these. 1

[0013] R 3 and R 4 Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isobutyl group, s ec-butyl group, tert-butyl group, pentyl group, hexyl group and the like. The number of carbon atoms of the chain saturated hydrocarbon group is preferably 1 to 4, more preferably 1 to 3. Examples of the alicyclic saturated hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. The number of carbon atoms of the alicyclic saturated hydrocarbon group is preferably 3 to 5, more preferably 3 or 4. R and R are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and one is a hydrogen atom and the other is a hydrogen atom R 3 and R 4 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and one is a hydrogen atom and the other is a hydrogen atom atom, and the other is a methyl group is even more preferred. It is more preferably a hydrogen atom or a methyl group.

[0014] Examples of the aromatic hydrocarbon group of Ar include aryl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a bi phenyl group, an anthryl group, a phenanthryl group, and a binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 24, more preferably 6 to 1 8, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the substituent of the aromatic hydrocarbon group include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms , an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group , and a dodecyl group. Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetra fluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, and a perfluorohexyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexy loxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group, etc. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. etc.

[0015] Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** is a bond to the aromatic hydrocarbon group. TIFF2025102839000010.tif15155 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a cyclohexylphenyl group, etc. Examples of the combined group in the substituent of the aromatic hydrocarbon group include a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, etc. Examples of the group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxy alkyl groups having 1 to 12 carbon atoms such as a methyl group and a hydroxyethyl group, etc. and the like. Examples of the group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms include alkoxyalkoxy groups having 2 to 24 carbon atoms such as an ethoxyethoxy group, etc. and the like. and the like. Examples of the group formed by combining an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms include alkoxyalkyl groups having 2 to 24 carbon atoms such as an ethoxyethyl group, etc. and the like. Examples of the group formed by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as a benzyl group, etc. and the like. The substituent is preferably a hydroxy group, a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a group formed by combining these, more preferably a hydroxy group, a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a group formed by combining these, even more preferably a hydroxy group, a trifluoromethyl group, a fluorine atom or an iodine atom. and the like.

[0016] Ar is preferably a phenyl group which may have a substituent, more preferably a phenyl group which may have a hydroxy group, a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a group formed by combining these, even more preferably a phenyl group which may have a hydroxy group, a trifluoromethyl group, a fluorine atom or an iodine atom. and the like. It is more preferable that it is a phenyl group which may have an iodine atom. For example, when Ar is a phenyl group having a substituent, in the benzene ring of the substituent the bonding position may be any of the ortho-position, meta-position, and para-position with respect to the bonding position of the carbonyl group. Among them, it is preferably bonded to at least the ortho-position or para-position with respect to the bonding position of the carbonyl group and more preferably bonded to at least the para-position.

[0017] Examples of the anion (I) include anions represented by the following formulas (Ia-1) to (Ia-34). TIFF2025102839000011.tif164168

[0018] TIFF2025102839000012.tif181167

[0019] Z + Examples of the organic cation of include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations and the like. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, cations represented by any of the formulas (b2-1) to (b2-4) (hereinafter may be referred to as "cation (b2-1)" etc. according to the formula number.) are included.

[0020] TIFF2025102839000013.tif49168In the formulas (b2-1) to (b2-4), R b4 ~R b6 are each independently a chain hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 36 carbon atoms, represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atoms 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, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms , an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 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- as well. R b7 and R b8 each independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 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 may be the same or different. b8 R b9 and R b10 each independently represent 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- as well.​ 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 with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl oxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. R b13 to R b18 each independently represents a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 s may be the same or different, and when p2 is 2 or more, the plurality of R b14 s may be the same or different, and when q2 is 2 or more, the plurality of R b15 s may be the same or different, and when r2 is 2 or more, the plurality of R b16 s may be the same or different, and when s2 is 2 or more, the plurality of R b17 s When t2 is 2 or more, whether the same or different, a plurality of Rs b18 are the same or different.

[0021] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and an alkyl group such as a 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups. TIFF2025102839000014.tif11158 In particular, the alicyclic hydrocarbon group of R b9 ~R b12 is preferably 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

[0022] 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-ethyl adamantan-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 ​ Or it is 20 or less.

[0023] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group having a chain hydrocarbon group (such as tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and the aromatic hydrocarbon group having an alicyclic hydrocarbon group (such as p-cyclohexylphenyl group, p-adamantyl phenyl group, etc.) and the like can be mentioned. In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferable. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group and the like. 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, phen ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc.

[0024] Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pent yloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group and the like. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group and the like. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom and the like. ​ Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

[0025] R b4 and R b5 may combine with each other to form, together with the sulfur atom to which they are attached, a ring that may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of such rings include those having 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Examples of rings containing a sulfur atom include those having 3 to 12 members, preferably 3 to 7 members, and examples thereof include the following rings. * represents a bond. TIFF2025102839000015.tif23142

[0026] R b9 and R b10 may combine to form a ring that may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of such rings include those having 3 to 12 members, preferably 3 to 7 members. Examples thereof include a thiolan-1-ium ring (tetrahydrothiopyrylium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. R b11 and R b12 may combine to form a ring that may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of such rings include those having 3 to 12 members,​​ , preferably a 3-membered ring to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring and the like can be mentioned.

[0027] Among cations (b2-1) to (b2-4), preferably, cation (b2 -1). Examples of cation (b2-1) include the following cations. TIFF2025102839000016.tif81158

[0028] TIFF2025102839000017.tif74165

[0029] Examples of cation (b2-2) include the following cations. TIFF2025102839000018.tif18150

[0030] Examples of cation (b2-3) include the following cations. TIFF2025102839000019.tif26140

[0031] Examples of cation (b2-4) include the following cations. TIFF2025102839000020.tif81163

[0032] Salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. Examples of salt (I) preferably include an anion represented by any of formula (Ia-3), formula (Ia-4 ), formula (Ia-6) to formula (Ia-8), formula (Ia-17) to formula (Ia-22), formula (Ia -29) to formula (Ia-34), and a combination with cation (b2-1), cation (b2-2) or cation (b2-3).

[0033] Examples of the salt (I) include the salts described in Table 1. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned anion and cation. For example, the salt (I-1) refers to a salt composed of the anion represented by the formula (I a-1) and the cation represented by the formula (b2-c-1), and represents the salts shown below. a-1) and the cation represented by the formula (b2-c-1), and represents the salts shown below. taste, and represents the salts shown below. TIFF2025102839000021.tif31104 [Table 1] TIFF2025102839000023.tif223154 TIFF2025102839000024.tif223154 TIFF2025102839000025.tif223154 TIFF2025102839000026.tif223154 TIFF2025102839000027.tif223154 TIFF2025102839000028.tif104154 Among them, the salt (I) is the salt (I-3), salt (I-4), salt (I-6) to salt (I-8), salt (I-17) to salt (I-22), salt (I-31), salt (I-32), salt (I-34) to salt (I-36), salt (I-45) to salt (I-50), salt (I-59), salt (I-60), salt (I-62) to salt (I-64), salt (I-73) to salt (I-78), salt (I-87), salt (I-88), salt (I-90) to salt (I-92), salt (I-101) to salt (I-106 ), salt (I-115), salt (I-116), salt (I-118) to salt (I-120), salt ([[]] I-129) to salt (I-134), salt (I-143), salt (I-144), salt (I-14 46) to salt (I-148), salt (I-157) to salt (I-162), salt (I-171), Salt (I-172), salts (I-174) to (I-176), salts (I-185) to (I- 190), salts (I-197) to (I-238) are preferred.

[0034] <Method for producing salt (I)> In salt (I), X 1 being *-CO-O- (the salt represented by formula (I1)) can be produced, for example, by reacting the salt represented by formula (I1-a) with the compound represented by formula (I1-b) in the presence of a base in a solvent. TIFF2025102839000029.tif51142 (wherein all symbols have the same meanings as defined above).

[0035] Examples of the base include potassium carbonate, potassium iodide, pyridine, and triethylamine, etc. and the like. Examples of the solvent include chloroform and acetonitrile, etc. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours.

[0036] Examples of the salt represented by formula (I1-a) include the salts represented below, and they can be produced by the method described in JP-A-2007 -197718. TIFF2025102839000030.tif38142

[0037] Examples of the compound represented by formula (I1-b) include the compounds represented by the following formula, and they can be easily obtained from the market and can also be easily produced by known production methods. . TIFF2025102839000031.tif23158

[0038] In salt (I), X 1 being *-O-CO-O- (the salt represented by formula (I2)) can be produced, for example, by reacting a salt represented by formula (I2-a) with a compound represented by formula (I2-b) in the presence of a base in a solvent. TIFF2025102839000032.tif56158(In the formula, all the symbols have the same meanings as described above.)

[0039] Examples of the base include potassium carbonate, potassium iodide, pyridine, and triethylamine and the like. Examples of the solvent include chloroform and acetonitrile. 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 below, and it can be produced by the method described in JP-A-20 12-193170. TIFF2025102839000033.tif34140

[0040] Examples of the compound represented by formula (I2-b) include compounds represented by the following formula, and they can be easily obtained from the market and can also be easily produced by known production methods . TIFF2025102839000034.tif23161

[0041] In salt (I), a salt in which X 1 is *-O- (the salt represented by formula (I3)) can be produced, for example , by reacting a salt represented by formula (I2-a) with a compound represented by formula (I3-b) in the presence of a base in a solvent. TIFF2025102839000035.tif51158(In the formula, all the symbols have the same meanings as described above.)

[0042] Examples of the base include potassium hydroxide.​ Examples of the solvent include chloroform and acetonitrile. The reaction temperature is generally 5°C to 80°C, and the reaction time is generally 0.5 hour to 24 hours.

[0043] Examples of the compound represented by the formula (I3-b) include compounds represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods. . TIFF2025102839000036.tif1854

[0044] In the salt (I), X 1 being *-O-CO- (the salt represented by the formula (I4)) can be produced, for example, by reacting the salt represented by the formula (I2-a) with the compound represented by the formula (I4-b) in a solvent in the presence of a catalyst. TIFF2025102839000037.tif51155 (wherein all the symbols have the same meanings as described above).

[0045] Examples of the catalyst include carbonyldiimidazole, sulfuric acid, and p-toluenesulfonic acid. Examples of the solvent include chloroform and acetonitrile. The reaction temperature is generally 5°C to 80°C, and the reaction time is generally 0.5 hour to 24 hours.

[0046] Examples of the compound represented by the formula (I4-b) include compounds represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods. . TIFF2025102839000038.tif2166

[0047] In the salt (I), L 1 being an alkanediyl group having 1 to 4 carbon atoms and an alicyclic ring having 3 to 18 carbon atoms A group formed by combining with a hydrocarbon group of the formula (provided that the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and -C contained in the alicyclic hydrocarbon group H2- may be replaced by -O-, -S-, -SO2- or -CO-. The salts represented by formula (I1), formula (I2), formula (I3), and formula (I4) are synthesized. The salt represented by formula (I1-a) or the salt represented by formula (I2-a) is replaced with a salt represented by the following formula: It can also be produced by replacing TIFF2025102839000039.tif228162

[0048] <Acid generator> The acid generator of the present invention is an acid generator containing a salt (I). Alternatively, two or more types of salt (I) may be contained. In addition to the salt (I), the acid generator of the present invention may be an acid generator known in the resist field (hereinafter, “acid generator”). The acid generator (B) may be used alone. Alternatively, two or more of them may be used in combination.

[0049] The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) Salts, iodonium salts) are typical. As the anion of the onium salt, sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc. can be mentioned. As the acid generator (B), JP-A-63-26653, JP-A-55-164824,

[0050] JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, US Patent No. 3,779, , 778, US Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. Compounds that generate acid by radiation described therein can be used. Also, compounds produced by known methods may be used. The acid generator (B) may be used in combination of two or more.

[0051] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)". However, salt (I) is excluded.) TIFF2025102839000040.tif2861[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or a carbon number of 3 to 2 which may have a substituent The -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0052] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) is a trifluoromethyl group, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluorohexyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0053] L b1 The divalent saturated hydrocarbon group in the formula (I) is a straight-chain alkanediyl group, a branched alkanediyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, 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- A linear alkanediyl group such as a diyl group; An ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a branched alkanediyl group such as a 2-methylbutane-1,4-diyl group; A monocyclic divalent alicyclic saturated hydrocarbon 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; is; A polycyclic divalent alicyclic saturated hydrocarbon 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. are exemplified.

[0054] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include, for example, a group represented by any of formulas (b1-1) to (b1-3). In the groups represented by formulas (b1-1) to (b1-3) and the groups represented by formulas (b1-4) to (b1-11) which are specific examples thereof, * represents a bond with -Y. to -Y.

[0055] TIFF2025102839000041.tif26118 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 ​​​represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b2 and L b3 is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b4 and L b5 is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L b6 and L b7 is 23 or less. * and ** represent bonds, and * represents the bond with Y.]

[0056] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L b1 . L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-.

[0057] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferred. Examples of the group represented by formula (b1-1) include the groups represented by formula (b1-4) to formula (b1-8), respectively. TIFF2025102839000042.tif49120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b9 L b10 and the total number of carbon atoms of In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b11 L b12 and the total number of carbon atoms of In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b13 ~L b15 is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated carbon hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of L b16 ~L b18 is 19 or less. * and ** represent bonds, and * represents a bond with Y.] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0058] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11), respectively. are as follows. TIFF2025102839000043.tif23140 [In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, the total number of carbon atoms of L and L b19 and L b20 is 23 or less. In the formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. In the alkylcarbonyloxy group, -CH2- may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L b21 , L b22 and L b23 is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. In the alkylcarbonyloxy group, -CH2- may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L b24 , L b25 and L b26 is 21 or less. * and ** represent bonds, and * represents a bond to Y.

[0059] In the group represented by the formula (b1-9) to the group represented by the formula (b1-11), when a hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group, and the like. Examples of the group represented by the formula (b1-4) include the following.

[0060] TIFF2025102839000044.tif16150 (* and ** represent bonds, and * represents the bond to Y.)

[0061] Examples of the group represented by the formula (b1-5) include the following. TIFF2025102839000045.tif72148 (* and ** represent bonds, and * represents the bond to Y.)

[0062] Examples of the group represented by the formula (b1-6) include the following.

[0063] TIFF2025102839000046.tif29150 (* and ** represent bonds, and * represents the bond to Y.)

[0064] Examples of the group represented by the formula (b1-7) include the following. TIFF2025102839000047.tif64150 (* and ** represent bonds, and * represents the bond to Y.)

[0064] Examples of the group represented by the formula (b1-8) include the following. TIFF2025102839000048.tif23150 (* and ** represent bonds, and * represents the bond to Y.)

[0065] Examples of the group represented by formula (b1-2) include the following. TIFF2025102839000049.tif31161 (* and ** represent a bond, and * represents a bond to Y.)

[0066] Examples of the group represented by formula (b1-9) include the following. TIFF2025102839000050.tif44137 (* and ** represent a bond, and * represents a bond to Y.)

[0067] Examples of the group represented by formula (b1-10) include the following. TIFF2025102839000051.tif89157 (* and ** represent a bond, and * represents a bond to Y.)

[0068] Examples of the group represented by formula (b1-11) include the following. TIFF2025102839000052.tif82158 (* and ** represent a bond, and * represents a bond to Y.)

[0069] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to the group represented by formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S(O)2- or - CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents a bond to L b1 and is represented by. TIFF2025102839000053.tif82165 Examples of the alicyclic hydrocarbon group represented by Y preferably include the groups represented by formula (Y1) to formula (Y20), formula ( Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43) A group represented by any of them, more preferably a group represented by formula (Y11), formula (Y15), formula (Y16 ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), formula (Y40), formula (Y42) or formula (Y43), still more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) represented by. When the alicyclic hydrocarbon group represented by Y is a spiro ring having an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39) to formula (Y 40), formula (Y42) or formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. In addition, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

[0070] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 1 6 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -( CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group is a hydrogen atom ​​​​It may be replaced with a droxy group or a fluorine atom. ja represents an integer of any one of 0 to 4 are mentioned. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, and a C1-C16 alkyl group which may be substituted with a hydroxy group (in the alkyl group, -CH2- may be replaced with -O- or -CO-).), a C3-C16 alicyclic hydrocarbon group, a C6-C18 aromatic hydrocarbon group, a C7-C21 aralkyl group, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 represents a C1-C16 alkyl group, a C3-C16 alicyclic hydrocarbon group, a C6-C18 aromatic hydrocarbon group or a group combining these, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -SO2- or -CO- i2 and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced with a hydroxy group or a fluorine atom. ja represents an integer of any one of 0 to 4.). are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group and a dimethylcyclohexyl group. It may be replaced with a hydroxy group or a fluorine atom. ja represents an integer of any one of 0 to 4.). are mentioned.

[0071] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. are mentioned. Examples of the alicyclic hydrocarbon group include, for example, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group and a dimethylcyclohexyl group. and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group, a dimethylcyclohexyl group and the like. are mentioned. The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 12, more preferably from 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and the aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-adamantylphenyl group, p-cyclohexylphenyl group, etc.). The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 14, more preferably from 6 to 10. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. The number of carbon atoms in the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, still more preferably from 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group, etc. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, etc. -CH2- contained in the alkyl group is replaced by -O-, -S(O)2- or -CO-, etc. ​​​​​​​​​​​​​​​Examples of the base include an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or a group combining these groups. 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. The number of carbon atoms in the alkoxy group is preferably from 1 to 12, more preferably from 1 to 6, and still more preferably from 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the combined group include a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, and a group combining an alkoxy group and an alkylcarbonyloxy group. Examples of the group combining an alkoxy group and an alkyl group include a methoxymethyl group. Examples of the group combining an alkoxy group and an alkoxy group include a methoxyethoxy group. Examples of the group combining an alkoxy group and an alkylcarbonyl group include a methoxyacetyl group. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group. The number of carbon atoms in the combined group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the group combining an alkoxy group and an alkoxy group include a methoxyethoxy group. The number of carbon atoms in the group combining an alkoxy group and an alkoxy group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include a methoxyacetyl group. The number of carbon atoms in the group combining an alkoxy group and an alkylcarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group. The number of carbon atoms in the group combining an alkoxy group and an alkylcarbonyloxy group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the combined group include a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, and a group combining an alkoxy group and an alkylcarbonyloxy group. Examples of the group combining an alkoxy group and an alkyl group include a methoxymethyl group. Examples of the group combining an alkoxy group and an alkoxy group include a methoxyethoxy group. Examples of the group combining an alkoxy group and an alkylcarbonyl group include a methoxyacetyl group. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group. Examples of the group combining an alkoxy group and an alkyl group include a methoxymethyl group. Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group, and the like. The number of carbon atoms of the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group formed by combining an alkoxy group and an alkoxy group include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group formed by combining an alkoxy group and an alkylcarbonyl group include an alkoxyalkylcarbonyl group such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, and an ethoxypropionyl group. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group formed by combining an alkoxy group and an alkylcarbonyloxy group include an alkoxyalkylcarbonyloxy group such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxy propionyloxy group. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S(O)2-, -CO-, or the like include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0072] Examples of Y include the following. TIFF2025102839000054.tif103165

[0073] TIFF2025102839000055.tif64161

[0074] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents, even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, even more preferably an adamantyl group which may have substituents, and the -CH2- constituting the alicyclic hydrocarbon group or the adamantyl group may be replaced by -CO-, -S(O)2- or -CO- Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by formula (Y42), formula (Y100) to formula (Y114)

[0075] As the anion in the salt represented by formula (B1), an anion represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] is preferable, and an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-59) is more preferable. (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-5 9)

[0076] TIFF2025102839000056.tif143153

[0077] TIFF2025102839000057.tif66157 ​​​​​​

[0078] TIFF2025102839000058.tif100158

[0079] TIFF2025102839000059.tif121153

[0080] TIFF2025102839000060.tif57162

[0081] TIFF2025102839000061.tif185165 Here, R i2 ~R i7 are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms , preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these , more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms group. Q b1 and Q b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 4646.

[0082] Preferred examples of the anion in the salt represented by formula (B1) include anions represented by formula (B1a-1) to formula ( B1a-38), respectively. TIFF2025102839000062.tif125153

[0083] TIFF2025102839000063.tif91138

[0084] TIFF2025102839000064.tif168155

[0085] Among them, anions represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-1 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-3 8) are preferred.

[0086] Z1 + As the organic cation of Z1, organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations and the like can be mentioned. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. + As the arylsulfonium cation, those similar to the cation of Z in formula (I) can be mentioned.

[0087] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula ( B1a-19), formula (B1a-22) to formula (B1a-38) and any of the anions represented by a combination with cation (b2-1) or cation (b2-3) can be mentioned.

[0088] As the acid generator (B), preferably, those represented by formula (B1-1) to formula (B1-56) are mentioned respectively. Among them, those containing an arylsulfonium cation are preferred. Formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) ~ Formulas (B1-14), (B1-20) to (B1-26), (B1-29), Formula (B 1-31) to (B1-56) are particularly preferred. TIFF2025102839000065.tif61150

[0089] TIFF2025102839000066.tif72163

[0090] TIFF2025102839000067.tif79150

[0091] TIFF2025102839000068.tif64150

[0092] TIFF2025102839000069.tif87145

[0093] TIFF2025102839000070.tif66164

[0094] TIFF2025102839000071.tif68167

[0095] TIFF2025102839000072.tif92158

[0096] When containing salt (I) and acid generator (B) as the acid generator, the content ratio (mass ratio; salt (I): acid generator (B)) of salt (I) and acid generator (B ) is usually 1:99 to 99:1 and preferably 2:98 to 98:2, more preferably 5:95 to 95:5 and even more preferably 10:90 to 90:10, particularly preferably 15:85 to 85 :15. In the resist composition of the present invention, the total content rate of the acid generator is resin (A) 1 described later Based on 00 parts by mass, preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, still more preferably 3 parts by mass or more and 35 parts by mass or less.

[0097] <Resist composition> The resist composition of the present invention contains an acid generator containing salt (I) and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" has a leaving group, and when the leaving group is eliminated by contact with an acid, the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition of the present invention preferably contains a quencher such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator (hereinafter sometimes referred to as "quencher (C)"), and preferably contains a solvent (hereinafter sometimes referred to as "solvent (E)").

[0098] <Resin (A)> Resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). Resin (A) preferably further contains a structural unit other than structural unit (a1). Examples of the structural unit other than structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0099] ​​​​​​​​​​The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter referred to as "monomer (a1)") in some cases). The acid-labile group contained in the resin (A) 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)). TIFF2025102839000073.tif1988 [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 1 8 carbon atoms or a group combining these, or R a1 and R a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. . ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding site.] TIFF2025102839000074.tif2171 [In the formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and the -CH2- contained in the hydrocarbon group and the heterocyclic ring may be replaced by -O- or -S- . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bonding site.] * represents a bonding site.]

[0100] ​R a1 、R a2 and R a3 Examples of the alkyl group in R R a1 、R a2 and R a3 Examples of the alkenyl group in R include ethenyl group, propenyl group isopropyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl R a1 、R a2 and R a3 The alicyclic hydrocarbon group in R can be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding site). The number of carbon atoms of the alicyclic hydrocarbon group in R a1 、R a2 and R a3 is preferably 3 to 16. TIFF2025102839000075.tif10150R a1 、R a2 and R a3 Examples of the aromatic hydrocarbon group in R include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined group include the group obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbor alkylcycloalkyl group or cycloalkylalkyl group such as nyl ethyl group), benzyl aralkyl group such as group, 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.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. are mentioned. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form a non-aromatic hydrocarbon ring, -C(R a1 )(R a2 )(R a3 ) includes the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents the bonding site with -O-. TIFF2025102839000076.tif31138

[0101] R a1’ 、R a2’ and R a3’ The hydrocarbon groups in include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. are mentioned. The alkyl group and the alicyclic hydrocarbon group are the same as the groups mentioned for R a1 、R a2 and R a3 . are mentioned. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples of the aryl group include a phenanthryl group and the like. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornil group , a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbor nylethyl group and the like, such as an alkylcycloalkyl group or a cycloalkylalkyl group), a benzyl group and the like, such as an aralkyl 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 a phenylcyclohexyl group, and the like. R a2’ and R a3’ are bonded to each other, and together with the carbon atom to which they are bonded and X, form a heterocyclic ring, -C(R a1’ )(R a2’ )-X-R a3’ includes the following rings . * represents the bonding site. TIFF2025102839000077.tif18130R a1’ and R a2’ Among them, at least one is preferably a hydrogen atom. na' is preferably 0.

[0102] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and n A group where a = 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamant tyl group, R a3 is an alkyl group, ma = 0, and na = 1. In formula (1), R a1 and R a2 are each independently an alkyl group, R a3 is an adamant tyl group, ma = 0, and na = 1. Specific examples of group (1) include the following groups. * represents the bonding site. TIFF2025102839000078.tif171163

[0103] Specific examples of group (2) include the following groups. * represents the bonding site. TIFF2025102839000079.tif68162

[0104] 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 preferably mentioned. Using a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group in the resist composition

[0105] can improve the resolution of the resist pattern.

[0106]

[0106] As the structural unit derived from the (meth)acrylic monomer having group (1), a structural unit represented by formula (a1- 0) (hereinafter, may be referred to as structural unit (a1-0)), formula (a1 - 1) or a structural unit represented by the formula (hereinafter sometimes referred to as structural unit (a1 - 1)). Or a structural unit represented by the formula (a1 - 2) (hereinafter sometimes referred to as structural unit (a1 - 2)) is exemplified. Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1 - 1) and structural unit (a1 - 2). These may be used alone or in combination of two or more. In TIFF2025102839000080.tif44144 [In formula (a1 - 0), formula (a1 - 1) and formula (a1 - 2), L a01 , L L a01 a1 And L a2 a2 Are each independently, - O - or * - O - (CH2) k1 - CO - O - represents, k1 represents an integer of any one of 1 to 7, and * represents the bonding site with - CO -. Represents. R a01 a01 , R a4 And R a5 a5 R a02 a02 , R a03 And R a04 a04 Are each independently, 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. R a6 a6 , and R a7 a7 Are each independently, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or A group formed by combining these. m1 represents an integer of any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1' represents an integer of any one of 0 to 3.

[0107] R a01 、R a4 and R a5 are preferably methyl groups. L a01 、L a1 and L a2 are preferably an oxygen atom or *-O-(CH2) k01 -C O-O- (where k01 is preferably any integer from 1 to 4, more preferably 1. ), more preferably an oxygen atom. R a02 、R a03 、R a04 、R a6 and R a7 The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and the groups formed by combining these in R of group (1) a1 、R a2 and R a3 include the same groups as those exemplified for R R a02 、R a03 、and R a04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group is. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms 、more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, still more preferably an ethyl group, an isopropyl group or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms 、more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group is. R a02 、R a03 、Ra04 , R a6 and R a7 The number of carbon atoms of the alicyclic hydrocarbon group of is preferably 5 to 12, more preferably 5 to 10. a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group of is preferably 6 to 12, more preferably 6 to 10. The total number of carbon atoms of the group formed by combining an alkyl group and an alicyclic hydrocarbon group is preferably 18 or less. The total number of carbon atoms of the group formed by combining an alkyl group and an aromatic hydrocarbon group is preferably 18 or less. , R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group . , R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group . , R a6 and R a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a meth yl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphth yl group, even more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. ​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.

[0108] Examples of the structural unit (a1-0) include structural units represented by any of Formula (a1-0-1) to Formula (a1-0-18) and structural units in which the methyl group corresponding to R in the structural unit (a1-0) a01 is replaced with a hydrogen atom, and structural units represented by any of Formula (a1-0-1) to Formula (a1- 0-10), Formula (a1-0-13), and Formula (a1-0-14) are preferred.

[0109] TIFF2025102839000081.tif101164 Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, structural units represented by any of Formula (a1-1-1) to Formula (a1 -1-7) and structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced with a hydrogen atom are preferred, and structural units represented by any of Formula (a1-1-1) to Formula a4 (a1-1-4) are more preferred. (a1-1-4) are more preferred. TIFF2025102839000082.tif42169

[0110] Examples of the structural unit (a1-2) include structural units represented by any of Formula (a1-2-1) to Formula (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) a5 is replaced with a hydrogen atom, and structural units represented by Formula (a1-2-2), Formula (a1-2-5), are mentioned, and structural units in which the methyl group corresponding to R in the structural unit (a1-2) The structural unit represented by any one of formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) is preferred. is preferred. TIFF2025102839000083.tif77155

[0111] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 80 mol%, preferably 5 to 75 mol%, more preferably 10 to 70 mol% with respect to all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content of these is usually 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 75 mol%, and even more preferably 20 to 70 mol% with respect to all the structural units of the resin (A).

[0112] Examples of the structural unit having the group (2) in the structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025102839000084.tif4664[In formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 a30 represents a single bond or * ​​​​​​​-X a31 -(A a32 -X a32 ) nc - represents, and * is -R a32 is the bonding site with the carbon atom to which it binds. represents. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer of 2 or more, multiple Rs a33 may be the same as or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. The -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. may also be.]

[0113] R a32 and R a33 Examples of the halogen atom in R and R include a fluorine atom, a chlorine atom, and a bromine atom. and the like. R a32 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, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, an ethyl group, a per fluoropropyl group, 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 are mentioned. 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 are mentioned. include a pentyl group, a hexyl group and a perfluorohexyl group. R a32 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. include a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in R 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. Examples of the alkyl group in R 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. include a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. R a33 Examples of the alkoxy group in R 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 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. Examples of the alkoxy group in R 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 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. Examples of the alkoxy group in R 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 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. Examples of the alkoxy group in R 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 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. R a33 Examples of the alkoxyalkyl group in R 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 a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. Examples of the alkoxyalkyl group in R 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 a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. Examples of the alkoxyalkyl group in R 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 a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. Examples of the alkoxyalkyl group in R 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 a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. Examples of the alkoxyalkyl group in R 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 a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy group in R include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, Examples of the alkoxyalkoxy group in R include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, A methoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, a tert-butoxy methoxy group may be mentioned. The alkoxyalkoxy group is preferably an alkoxyalk oxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a33 Examples of the alkylcarbonyl group in include an acetyl group, a propionyl group, and a buty ryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in include an acetyloxy group, a propiony loxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R a33 is preferably 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 preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an eth oxymethoxy group, even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0114] *-X a31 -(A a32 -X a32 ) nc Examples of *- include *-O-, *-CO-O-, *-O-C O-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32-O-CO- include. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *- O-A a32 -CO-O- is preferred.

[0115] A a32 As the alkanediyl group in, 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-methyl propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group and 2-methylbutane-1,4-diyl group etc. are included. A a32 is preferably a methylene group or an ethylene group.

[0116] A a30 is a single bond, *-CO-O- or *-CO-O-A a32 -CO-O- and is preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O- and is more preferably a single bond or *-CO-O- and is even more preferably a single bond or *-CO-O-.

[0117] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 R a35 and R a36 As the hydrocarbon group in, alkyl group, alicyclic hydrocarbon group , aromatic hydrocarbon group, and groups combining these are included. As the alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hex yl group, heptyl group, octyl group etc. are included. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group . Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents the bonding site), etc. . TIFF2025102839000085.tif10151Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group , phenanthryl group, etc. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group , aromatic hydrocarbon groups having 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 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms a36 , an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these.

[0118] R a34 ​​​is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a It is an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 Archi The R alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 is bonded to the o- or p-position of the benzene ring It is preferred that the linker be bonded at the p-position, and more preferred that the linker be bonded at the p-position.

[0119] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers represented by the formula (a1-4-1) to (a1-4-2) are preferably included. -4-18) and R a32 The hydrogen atom corresponding to More preferably, the structural units represented by the formula (a1-4-1) to the formula (a1-4 -5), Formula (a1-4-10), Formula (a1-4-13), and Formula (a1-4-14) respectively include structural units represented thereby. TIFF2025102839000086.tif102168

[0120] When the resin (A) contains the structural unit (a1-4), its content 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 60 mol% based on the total of all structural units of the resin (A).

[0121] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) include the structural unit represented by Formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF2025102839000087.tif4558In 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 an integer of 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 an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0122] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred.​​​​​​ Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoro methyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Preferably. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one of them 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-.

[0123] Examples of the structural unit (a1-5) include structural units derived from monomers 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. ) are more preferable. TIFF2025102839000088.tif33133

[0124] When the resin (A) contains the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and still more preferably 5 to 30 mol% based on all the structural units of the resin (A). units, 5 to 40 mol% is still more preferable, and 5 to 30 mol% is still more preferably. mol%.

[0125] Examples of the structural unit (a1) also include the following structural units. TIFF2025102839000089.tif31162

[0126] When the resin (A) contains structural units such as (a1-3-1) to (a1-3-7) as described above , its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, still more preferably 20 to 70 mol% even more preferably 20 to 60 mol%, and particularly preferably 20 to 60 mol%.

[0127] In addition, examples of the structural unit (a1) also include the following structural units. TIFF2025102839000090.tif4894 When the resin (A) contains structural units such as (a1-6-1) to (a1-6-3) as described above , its content is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, still more preferably 20 to 50 mol%, still more preferably 20 to 45 mol% even more preferably 20 to 40 mol%, and particularly preferably 20 to 40 mol%.

[0128] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. When a resin having a structural unit having a hydroxy 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)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0129] 〈Structural unit (a2)〉 The hydroxy group in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using high-energy rays such as KrF excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light), etc., as the exposure light source, as the structural unit (a2), a structural unit having a phenolic hydroxy group ( a2) is preferred, and it is more preferable to use the structural unit (a2-A) described later. Further, 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 preferred, and it is more preferable to use the structural unit (a2 -1) described later. The structural unit (a2) may be included alone as one kind or may include two or more kinds. As the structural unit (a2), a structural unit having an alcoholic hydroxy group is preferred, and it is more preferable to use the structural unit (a2 -1) described later. The structural unit (a2) may be included alone as one kind or may include two or more kinds. As the structural unit (a2), a structural unit having an alcoholic hydroxy group is preferred, and it is more preferable to use the structural unit (a2

[0130] Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). are mentioned. TIFF2025102839000091.tif4551 [In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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. represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. Aa50 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bonding position of -R a50 to the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, multiple Rs a51 may be the same as or different from each other.

[0131] R a50 and R a51 Examples of the halogen atom in include a fluorine atom, a chlorine atom, and a bromine atom, etc. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, 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-nonafluoro pentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Ra51 Examples of the alkyl group in [description] 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 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in [description] include a methoxy group, an ethoxy group, a propoxy group, an iso propoxy 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 a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51 Examples of the alkoxyalkyl group in [description] include a methoxymethyl group, an ethoxyethyl group , a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxy methyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in [description] include a methoxymethoxy group, a methoxyeth oxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropo xymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butox ymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in [description] include an acetyl group, a propionyl group, and a buty Examples include a ryl group and the like. The alkylcarbonyl group is an alkylcarbonyl group having 2 to 3 carbon atoms. is preferred, and an acetyl group is more preferred. R a51 Examples of the alkylcarbonyloxy group in 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, and more preferably an acetyloxy group. is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 is preferably 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 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 even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. is preferably 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 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 even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. is preferably 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 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 even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. is preferably 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 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 even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. is preferably 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 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 even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0132] *-X a51 -(A a52 -X a52 ) nb Examples of *-O-, *-CO-O-, *-O-C O-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO-, include. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *- O-A a52 -CO-O- is preferred.

[0133] A a52 Examples of the alkanediyl group in include a methylene group, an ethylene group, a 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 - methyl propane - 1,3 - diyl group, 2 - methylpropane - 1,2 - diyl group, pentane - 1, 4 - diyl group and 2 - methylbutane - 1,4 - diyl group, etc. may be mentioned. A a52 is preferably a methylene group or an ethylene group.

[0134] A a50 is a single bond, * - CO - O - or * - CO - O - A a52 -CO - O - is preferred, and a single bond, * - CO - O - or * - CO - O - CH2 - CO - O - is more preferred, and a single bond or * - CO - O - is even more preferred.

[0135] mb is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. The hydroxy group is preferably bonded to the o - position or p - position of the benzene ring, and more preferably bonded to the p - position.

[0136] Examples of the structural unit (a2 - A) include structural units derived from the monomers described in JP - A - 2010 - 204634 and JP - A - 2012 - 12577.

[0137] Examples of the structural unit (a2 - A) include structural units represented by formula (a2 - 2 - 1) to formula (a2 - 2 - 16) and structural units obtained by replacing the methyl group corresponding to R in the structural units represented by formula (a2 - 2 - 1) to formula (a2 - 2 - 16) with a hydrogen atom. In the structural unit (a2 - A), R a50 corresponding methyl group is replaced with a hydrogen atom. Examples of the structural unit (a2 - A) include the structural unit represented by formula (a2 - 2 - 1), The structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula ( a2-2-8), and the structural units represented by formulas (a2-2-12) to (a2-2-14), and in these structural units, it is preferable that the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom. In the case where the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) a50 is preferably 5 to 80 mol%, more preferably 10 to 70 TIFF2025102839000092.tif64168

[0138] mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to is, based on all the structural units, 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 incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also it can be incorporated into the resin (A) by polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide . As the structural unit having an alcoholic hydroxy group in the structural unit (a2), there is a structural unit represented by formula ( can be.

[0139] a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). is exemplified. In formula (a2-1), TIFF2025102839000093.tif4157In formula (a2-1), L a3 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding position with -CO-.​ R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents any integer from 0 to 10.

[0140] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- wherein (the said f1 represents any integer from 1 to 4), and more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably any integer from 0 to 3, more preferably 0 or 1.

[0141] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. Structural units represented by any of formula (a2-1-1) to formula (a2-1-6 ) are preferred, structural units represented by any of formula (a2-1-1) to formula (a2-1-4) are more preferred, and structural units represented by formula (a2-1-1) or formula (a2-1- 3) are even more preferred. 3) are even more preferred. TIFF2025102839000094.tif53147

[0142] When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably is 1 to 10 mol%.

[0143] 〈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 may be a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, an adamantanone lactone ring, or a bridged ring containing a γ -butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) is exemplified.

[0144] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These may be contained alone, or two or more thereof may be contained. TIFF2025102839000095.tif50161[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4), L a4 、L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -C O-O- (where k3 represents an integer of 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 -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding position to the carbonyl group. R a18 、R​​a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents 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 a aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 , R a22 , R a2 3 and / or R a25 may be the same as or different from each other.

[0145] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert t-butyl group. R a24 Examples of the halogen atom in include fluorine atom, chlorine atom, bromine atom and iodine atom. a24 Examples of the alkyl group in Alkyl groups such as a methyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. are exemplified, preferably an alkyl group having 1 to 4 carbon atoms is exemplified, and more preferably a methyl group or an ethyl group is exemplified. R a24 Examples of the alkyl group having a halogen atom in R include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, perfluoro orobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro ropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl yl group, triiodomethyl group, etc. are exemplified.

[0146] L a8 and L a9 Examples of the alkanediyl group in include a methylene group, an ethylene group, pro pane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pen tane-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, pen tane-1,4-diyl group and 2-methylbutane-1,4-diyl group, etc. are exemplified.

[0147] In formula (a3-1) to formula (a3-3), L a4 ~L a6 are each independently, preferably -O- or, *-O-(CH2) k3 -CO-O- where k3 is an integer from 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, even more preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. Ra22 and R a23 is, independently of one another, preferably a carboxy group, a cyano group or a methyl group. p1, q1 and r1 are, independently of one another, preferably any integer from 0 to 2, more preferably 0 or 1.

[0148] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF2025102839000096.tif4455 (wherein R a24 , L a7 represent the same meaning as described above.)

[0149] Examples of the structural unit (a3) include monomers described in JP-A-2010-204646, monomers described in JP-A-2000-122294, and structural units derived from monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include 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 (a3-4-1 A structural unit represented by any one of (2), and in the said structural unit, in formula (a3-1) to formula ( a3-4), R a18 , R a19 , R a20 and R a24 The methyl group corresponding to is preferably a structural unit in which the hydrogen atom is replaced by a hydrogen atom. When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, more preferably

[0150] TIFF2025102839000097.tif118168

[0151] When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol% based on all the structural units of the resin (A), preferably 10 to 65 mol%, more preferably It is 10 to 60 mol%. Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is each 5 to 60 mol with respect to all the structural units of the resin (A). %, preferably 5 to 50 mol%, more preferably 10 to 50 mol%.

[0152] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF2025102839000098.tif3066[In formula (a4), R 41 represents a hydrogen atom or a methyl group. 41 R represents a saturated hydrocarbon group having a halogen atom having 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. 42 The saturated hydrocarbon group represented by R includes a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these. R 42 The saturated hydrocarbon group represented by includes a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these. Examples include hydrocarbon groups and the like formed by combining these.

[0153] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a he xadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group , a cycloheptyl group, and a cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding site). Examples of the group formed by the combination of TIFF2025102839000099.tif10146 include groups formed by combining one or more alkyl groups or one or more alkanedi yl groups with one or more alicyclic saturated hydrocarbon groups, and examples thereof include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0154] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4). TIFF2025102839000100.tif4551[In the formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perflu orocycloalkanediyl group having 3 to 12 carbon atoms. R 64 represents a hydrogen atom or a fluorine atom.]

[0155] L 4a Examples of the alkanediyl group in L include linear alkanediyl groups such as methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpro pane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0156] L 3a Examples of the perfluoroalkanediyl group in L include difluoromethylene group, per fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 -diyl group, perfluorooctane-4,4-diyl group, etc. L 3a Examples of the perfluorocycloalkanediyl group in L include perfluorocyclohe ​Examples include a xanthiyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, etc.

[0157] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0158] Examples of the structural unit (a4-0) include the following structural units and the structural units in the following structural units (a4-0) where the methyl group corresponding to R 54 is replaced by a hydrogen atom. TIFF2025102839000101.tif95166

[0159] TIFF2025102839000102.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g 1). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF2025102839000103.tif1487[In formula (a-g1), s represents 0 or 1. A​​​​​​​a42 and A a44 each independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. represents a saturated hydrocarbon group. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. represents. X a41 and X a42 each independently represents -O-, -CO-, -CO-O- or -O-CO -. However, the total number of carbon atoms of A a42 A a43 A a44 X a41 and X a42 is 7 or less. ] * is a bonding site, and the * on the right side is the bonding site with -O-CO-R a42 . ]

[0160] R a42 Examples of the saturated hydrocarbon group in include a chain hydrocarbon group, a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and a group formed by combining these.

[0161] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, hexa decyl group, a heptadecyl group, an octadecyl group, and the like. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group , a cycloheptyl group, a cyclooctyl group; a polycyclic alicyclic hydrocarbon group such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site). TIFF2025102839000104.tif10160 groups of combinations of groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more saturated alicyclic hydrocarbon groups are exemplified, such as -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, etc. The substituents that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom. In [Formula (a-g3), X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-.

[0162] R a42 is selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom. TIFF2025102839000105.tif855 A represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * represents the bonding site with R. a42 However, in R-X-A, when R does not have a halogen atom, A represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom. However, in R-X-A, when R does not have a halogen atom, A represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom. a42 -X a43 -A a45 In R-X-A, when R does not have a halogen atom, A represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom. a42 A a4 5 represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

[0163] A a45 Examples of the saturated hydrocarbon group in A include 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; pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups; and the like. Monocyclic alicyclic hydrocarbon groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group ; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site). Examples of the group formed by the combination of TIFF2025102839000106.tif10160 include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc. are included.

[0164] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably a saturated hydrocarbon group having an alkyl group having a halogen atom and / or a group represented by the formula (a-g3). R a42 When R is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group. R a42When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the number of carbon atoms contained in the group represented by the formula (a- g3), the total number of carbon atoms of R a42 is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0165] R a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). In the formula (a-g2), TIFF2025102839000107.tif871 A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding site with A a46 ). ). A a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A a46 A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents the bonding site with the carbonyl group.] * represents the bonding site with the carbonyl group.]

[0166] A a46 preferably has 1 to 6 carbon atoms in the saturated hydrocarbon group, more preferably 1 to 3 carbon atoms. A a47 preferably has 4 to 15 carbon atoms in the saturated hydrocarbon group, more preferably 5 to 12 carbon atoms, A a 47 ​A cyclohexyl group or an adamantyl group is more preferable.

[0167] The preferred structure of the group represented by formula (a-g2) is the following structure (* is the bonding site with the carbonyl group ). TIFF2025102839000108.tif14160

[0168] A a41 As the alkanediyl group in, a methylene group, an ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group and other linear alkanediyl groups; propane-1,2-diyl group, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups can be mentioned . A a41 As the substituent in the alkanediyl group represented by, a hydroxy group and an alkoxy group having 1 to 6 carbon atoms and the like can be mentioned. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0169] In the group represented by formula (a-g1), A a42 , A a43 and A a44 The divalent saturated hydrocarbon groups represented by are linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups , and divalent saturated hydrocarbon groups formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group and the like can be mentioned. Specifically, a methylene group, an ethylene group, a prop A propan-1,3-diyl group, a propan-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropan-1,3-diyl group, a 2-methylpropan-1,3-diyl group, 2- methylpropan-1,2-diyl group, and the like can be mentioned. A a42 、A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms and the like. s is preferably 0.

[0170] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or -O-CO-. Examples of the group include the following groups. In the following examples, * and ** each represent a bonding site, and ** is the bonding site with -O-CO-R a42 respectively. TIFF2025102839000109.tif47140

[0171] Examples of the structural unit represented by formula (a4-1) include the structural units shown below and the methyl group corresponding to R in the structural unit represented by formula (a4-1) in the following structural units wherein the methyl group is replaced by a hydrogen atom. a41 replaced structural units. can be mentioned. TIFF2025102839000110.tif97142

[0172] TIFF2025102839000111.tif135153

[0173] Examples of the structural unit represented by formula (a4-1) include the structural unit represented by formula (a4-2) and the structural unit represented by formula (a4-3). TIFF2025102839000112.tif4256[In formula (a4-2), R f5represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and the -C H2- in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. However, the upper limit of the total number of carbon atoms of L 44 and R f6 is 21.

[0174] L 44 The alkanediyl group having 1 to 6 carbon atoms of L is the same as the group exemplified by A a41 and the like can be mentioned. That's it. R f6 The saturated hydrocarbon group of R is the same as the group exemplified by R 42 and the like can be mentioned. L 44 As the alkanediyl group in L, an alkanediyl group having 2 to 4 carbon atoms is preferable. and an ethylene group is more preferable.

[0175] Examples of the structural unit represented by formula (a4-2) include, for example, the structural units represented by formulas (a4-1-1) to (a4 -1-11), respectively. In the structural unit (a4-2), R f5 The structural unit in which the methyl group corresponding to R is replaced by a hydrogen atom is also included as the structural unit represented by formula (a4-2). That's it.

[0176] TIFF2025102839000113.tif5772 [In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. That's it. Xf12 represents *-O-CO- or *-CO-O- (* represents the bonding site with A f13 ). ) A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total carbon number of L 5 , A f13 and A f14 is 20.]

[0177] L 5 As the alkanediyl group in, those exemplified as the alkanediyl group of A a41 are the same types of groups.

[0178] A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl yl group. As the divalent chain saturated hydrocarbon group which may have a fluorine atom, there are alkane diyl groups such as methylene group, ethylene group, propane diyl group, butane diyl group and pentane diyl group ; perfluoroalkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluoro fluorobutane diyl group and perfluoropentane diyl group etc. are exemplified. ; perfluoroalkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluoro fluorobutane diyl group and perfluoropentane diyl group etc. are exemplified. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. As the monocyclic group, there are cyclohexane diyl group and perfluorocyclohe xane diyl group etc. Either may be used. As the monocyclic group, there are cyclohexane diyl group and perfluorocyclohe Examples include a xylyl group and the like. Examples of the polycyclic group include an adamantyl group, a norbornyl group, a perfluoroadamantyl group, and the like. Examples of the saturated hydrocarbon group having a saturated hydrocarbon group and a fluorine atom of A which may be included are the same groups as those exemplified by R.

[0179] A f14 Among them, 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 alkyl fluoride 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 are preferable. a42 in Among them, 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 alkyl fluoride 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 are preferable. Among them, 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 alkyl fluoride 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 are preferable. ,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, 1,1,2, 2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, 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 and a per fluorooctyl group and other alkyl fluoride groups, a cyclopropylmethyl group, a cyclopropyl group , a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohe xyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbor nyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamant ylmethyl group and the like are preferable.

[0180] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of is preferably a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and a divalent chain having 2 to 3 carbon atoms is preferably a group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and a divalent chain having 2 to 3 carbon atoms An alicyclic saturated hydrocarbon group is more preferable. A f14 's saturated hydrocarbon group preferably includes a linear saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably includes a linear saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 is , preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0181] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a 4-1'-11), respectively. In the structural unit (a4-3), the methyl group corresponding to R f7 replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-3).

[0182] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-4). TIFF2025102839000114.tif4569[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 - CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.]

[0183] R f22 The saturated hydrocarbon group of R a42 includes the same ones as the saturated hydrocarbon group represented by R 。R f22 is preferably an alkyl group having 1 to 10 carbon atoms with a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms with a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms with a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms with a fluorine atom. In formula (a4-4), A is preferably -(CH2) -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0184] As the structural unit represented by formula (a4-4), for example, in the following structural units and the structural units represented by the following formulas, the methyl group corresponding to R in structural unit (a4-4) f21 is replaced by a hydrogen atom. j1 The structural units include those in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom.

[0185] When resin (A) has structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% with respect to all the structural units of resin (A). f21 〈Structural unit (a5)〉 As the non-leaving hydrocarbon group of structural unit (a5), groups having a linear, branched or cyclic hydrocarbon group can be mentioned. Among them, structural unit (a5) preferably has a group having an alicyclic hydrocarbon group.

[0186]

[0187] % is even more preferable.

[0187] 〈Structural unit (a5)〉 As the non-leaving hydrocarbon group of structural unit (a5), groups having a linear, branched or cyclic hydrocarbon group can be mentioned. Among them, structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. is preferable. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF2025102839000116.tif3656[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula (I) may be replaced with -O- or -CO-.

[0188] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentene group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, , adamantyl group and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl Examples of the alkyl group include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group.

[0189] L 55The divalent saturated hydrocarbon group in the formula (I) is a divalent chain saturated hydrocarbon group or a divalent fatty acid group. Examples of the hydrocarbon group include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediyl group. Examples of the alkyl groups include alkanediyl groups such as dialkyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the saturated hydrocarbon group include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adatomyl groups. Examples thereof include a manthanediyl group and a norbornanediyl group.

[0190] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula (I) is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF2025102839000117.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents the binding site with . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L 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. hydrogen group. 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.

[0191] 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 x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0192] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF2025102839000118.tif53136

[0193] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF2025102839000119.tif23130

[0194] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF2025102839000120.tif15145

[0195] Examples of the group represented by the formula (L1-4) include the following divalent groups. TIFF2025102839000121.tif26114

[0196] L 55is preferably a single bond or a group represented by the formula (L1-1).

[0197] Examples of the structural unit (a5-1) include the structural units shown below and the structural units in the following structural units ( a5-1), where the methyl group corresponding to R 51 in the formula is replaced by a hydrogen atom. and the like can be mentioned. TIFF2025102839000122.tif79161

[0198] When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol% based on all the structural units of the resin (A). % is even more preferred.

[0199] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and 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 sulfonyl group and an organic anion in the side chain is preferred. A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by the formula (II-2-A').

[0200] In the formula (II-2-A'), X TIFF2025102839000124.tif3295 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group contains X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group contains The -CH2- that is replaced may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.]

[0201] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 . A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group , a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group , a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group , a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group ​​​​​Examples thereof include a C1-C6 perfluoroalkyl group which may be substituted on A, such as 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, etc. ; A x1 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof. 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 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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; 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. of divalent monocyclic alicyclic saturated hydrocarbon groups; ;

[0202] X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof. 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 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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; ; 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 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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; 2-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; ,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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; 1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; Examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a 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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; 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, etc. of branched alkanediyl groups; Examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a 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, etc. of linear alkanediyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkanediyl groups; ; Examples of the divalent monocyclic alicyclic saturated hydrocarbon group include 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. ; Examples of the divalent monocyclic alicyclic saturated hydrocarbon group include 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. Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1 ,5-diyl group, adamantane-2,6-diyl group and other divalent polycyclic alicyclic saturated hydrocarbons groups and the like can be mentioned.

[0203] -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- Examples of such include divalent groups represented by formulas (X1) to (X53). However before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- the carbon number is 17 or less respectively. In the following formulas, * and ** represent bonding sites, * represents the bonding site with A x1 and represents the bonding site. TIFF2025102839000125.tif148164

[0204] 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 6 represents 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.

[0205] ZA + Examples of the organic cation represented by include organic onium cations, organic sulfonium cations thions, organic iodonium cations, organic ammonium cations, benzothiazolium cations thions and organic phosphonium cations and the like. Among these, organic sulfonium Mukation and organic iodonium cation are preferred, and arylsulfonium cation is more preferred. Specifically, the cation represented by any of the above formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number). is exemplified.

[0206] The structural unit represented by formula (II-2-A') is preferably the structural unit represented by formula (II-2-A). JPEG2025102839000126.jpg37109 [In formula (II-2-A), R III3 、X III3 and ZA + represent the same meaning as above. z represents an integer from 0 to 6. R III2 and R III4 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. When z is 2 or more, a plurality of R III2 and R II I4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.]

[0207] R III2 、R III4 、Q a and Q b The perfluoroalkyl group having 1 to 6 carbon atoms represented by is the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by the aforementioned Q b1 and the like are exemplified.

[0208] The structural unit represented by formula (II-2-A) is the structural unit represented by formula (II-2-A-1).​ is preferably in the form of bits. TIFF2025102839000127.tif5779 [In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b 、z and ZA + have the same meanings as described above. represent. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group.]

[0209] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by include linear or branched alkyl groups such as methyl group, ethyl group 、propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pent yl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. I2 Examples of the divalent saturated hydrocarbon group represented by X III3 are the same as those of the divalent saturated carbon hydrocarbon group represented by X

[0210] As the structural unit represented by formula (II-2-A-1), the structural unit represented by formula (II-2-A-2) is preferred. represented. TIFF2025102839000128.tif5287 [In formula (II-2-A-2), R III3 、R III5 and ZA + have the same meanings as described above. m and n each independently represent 1 or 2.

[0211] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 wherein the group corresponding to the methyl group of is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a C1-C6 alkyl group which may have a halogen atom (e.g., a trifluoromethyl group, etc. ) and the structural units described in WO 2012 / 050015. ZA are exemplified. + represents an organic cation. TIFF2025102839000129.tif86163

[0212] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by formula (II-1-1). In formula (II-1-1), TIFF2025102839000130.tif3587 A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may combine with each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. A - represents an organic anion. II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group. R II1 include a phenylene group and naphthylene groups and the like can be mentioned. R II2 and R II3 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 and the alicyclic hydrocarbon group are the same as those described above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group , an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphen yl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesity yl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic carbon hydrogen group (p-cyclohexylphenyl group, p-adamantyl phenyl group, etc.), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. can be mentioned. R II4 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 and can be mentioned. A II1 Examples of the divalent linking group represented by include, for example, 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-. Specifically, X ​III3 Examples thereof include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the same as that.

[0213] Examples of the structural unit containing the cation in formula (II-1-1) include a structural unit represented by the following, , R II4 a group corresponding to the methyl group of, is a hydrogen atom, a halogen atom (e.g., a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (e.g., a trifluoromethyl group, etc.) and the like, and a structural unit in which the like is replaced. TIFF2025102839000131.tif85130

[0214] A - Examples of the organic anion represented by include a sulfonate anion, a sulfonylimide anion anion, a sulfonylmethide anion, a carboxylate anion, and the like. A - represented by The organic anion is preferably a sulfonate anion. Examples of the sulfonate anion include the same ones as the anion represented by the aforementioned formula (B1).

[0215] A - Examples of the sulfonylimide anion represented by include the following. TIFF2025102839000132.tif36135

[0216] Examples of the sulfonylmethide anion include the following. TIFF2025102839000133.tif29123

[0217] Examples of the carboxylate anion include the following. TIFF2025102839000134.tif51152

[0218] Examples of the structural unit represented by the formula (II-1-1) include structural units represented below. and the like. TIFF2025102839000135.tif88149

[0219] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0220] The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well-known in the art.

[0221] The resin (A) 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), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two species, and even more preferably at least two 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 a structural unit represented by the formula (a2-1) or a structural unit represented by the formula (a2-A). The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a formula ( It is at least one selected from the group consisting of structural units represented by a3-4).

[0222] Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Using the monomers that lead to these structural units, by a known polymerization method (for example, radical polymerization method). It can be produced. The content ratio of each structural unit of the resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, even more preferably 3,000 or more), 50,000 or less (more preferably 30 ,000 or less, even more preferably 15,000 or less). In this specification, the weight average molecular weight is the value determined by gel permeation chromatography under the conditions described in the examples.

[0223] [[Resin other than resin (A)]] The resist composition of the present invention may contain a resin other than the resin (A). Examples of the resin other than the resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)).

[0224] Among them, as the resin (X), a resin containing the structural unit (a4) is preferable. In the resin (X), the content ratio of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, relative to the total of all structural units of the resin (X), and even more preferably 45 mol% or more. Examples of the structural unit that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. Among them, the resin ( ​​​​(X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), more preferably a resin composed of only the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more. Using the monomers that induce these structural units, a known polymerization method (for example, radical polymerization method) can be used for production. The content of each structural unit of the resin (X) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,00 0 or more), and 80,000 or less (more preferably 60,000 or less). The measurement means of the weight average molecular weight of the resin (X) is the same as that of the resin (A). When the resist composition contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and still more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A).

[0225] The content of the resin (A) in the resist composition is preferably 8 0 mass% or more and 99 mass% or less, more preferably 90 mass% or more and 99 mass% or less, with respect to the solid content of the resist composition. Also, when containing a resin other than the resin (A), the total content of the resin (A) and the resin other than the resin (A) is preferably 80 mass% or more and 99 mass% or less, more preferably 90 mass% or more and 99 mass% or less, with respect to the solid content of the resist composition. The solid content of the resist composition and the content of the resin with respect to this can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0226] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured, for example, by liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0227] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound and an acid generator (B). The resist composition may be a salt that generates an acid having a weaker acidity than the acid that generates the quencher. When (C) is contained, the content of the quencher (C) is based on the solid content of the resist composition. Generally, the content is about 0.01 to 15% by mass, and preferably about 0.01 to 10% by mass. It is more preferable that the content is about 0.01 to 7 mass %, and further preferably about 0.1 to 7 mass %. It is more preferable that the content is about 3% by mass. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Examples of aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropi laniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylani line, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylam ine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibut ylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohe xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triiso propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenedia mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyl diphenylmethane, 4,4'-diamino-3,3'-diethyl diphenylmeth ane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridi N, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulf ide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. may be cited, preferably diisopropyl aniline may be cited, and more preferably 2,6-diiso propyl aniline may be cited. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopro pylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimeth ylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylamm onium hydroxide, tetra-n-butylammonium salicylate, and choline, etc. may be cited.

[0228] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include the salt represented by the following formula, the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter, " ​​There may be cases of inner salts of weak acids (D).”), and Japanese Patent Application Laid-Open No. 2012-229206 , Japanese Patent Application Laid-Open No. 2012-6908, Japanese Patent Application Laid-Open No. 2012-72109, Japanese Patent Application Laid-Open No. 2011-3 9502 and salts described in Japanese Patent Application Laid-Open No. 2011-191745. Preferably is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably an inner salt of a weak acid (D). TIFF2025102839000136.tif89165

[0229] Examples of the inner salt of a weak acid (D) include the following salts. TIFF2025102839000137.tif72165

[0230] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as “other components (F)”). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used. There is no particular limitation and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used. agents, dyes, etc. can be used.

[0231] 〈Preparation of resist composition〉 The resist composition of the present invention can be prepared by mixing the salt (I), the resin (A), and the acid generator (B), and, if necessary, a resin other than the resin (A) used, the solvent (E), the quencher (C), and the other components (F). The mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40°C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40°C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. in the solvent (E), etc. The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. According to the mixing temperature, an appropriate time can be selected from 0.5 to 24 hours. Note that the mixing There are no particular restrictions on the mixing means, and stirring and mixing can be used, etc. After mixing the respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0232] 〈Method for manufacturing a resist pattern〉 The method for manufacturing a resist pattern of the present invention includes (1) a step of applying the resist composition of the present invention onto a substrate; (2) a step of drying the applied composition to form a composition layer; (3) a step of exposing the composition layer; (4) a step of heating the exposed composition layer; and (5) a step of developing the heated composition layer. To apply the resist composition onto a substrate, it can be usually performed by using a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate. By drying the applied composition, the solvent is removed to form a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during decompression drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, ultraviolet lasers such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F2 excimer laser (wavelength 157 nm) can be used. ​​​​​​​​​Those that emit user light, laser light from a solid laser light source (such as YAG or semiconductor laser), etc. Those that perform wavelength conversion to emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, electron beams, extreme ultraviolet light (EUV), etc. Various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure" in some cases. During exposure , usually, exposure is performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated (so-called post-exposure bake) to promote the deprotection reaction in the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. The composition layer after heating is usually developed using a developing solution with a developing device. The developing method includes dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When manufacturing a positive resist pattern from the resist composition of the present invention, an alkaline developing solution is used as the developing solution. The alkaline developing solution may be various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxy ethyl)trimethylammonium hydroxide (commonly known as choline), etc. can be mentioned. The alkaline developing solution may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and the pattern is removed. It is preferable to remove. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. Examples of the organic solvent contained in the organic developer include ketone solvents such as 2 - hexanone and 2 - heptanone; glycol ether esters such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N - dimethylacetamide; aromatic hydrocarbon solvents such as anisole, etc. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among them, as the organic developer, a developer containing butyl acetate and / or 2 - heptanone is preferred. In the organic developer, the total content of butyl acetate and 2 - heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2 - heptanone. The organic developer may contain a surfactant. Also, the organic developer may contain a trace amount of water. During development, development may be stopped by substituting with a solvent of a different type from the organic developer. It is preferable to wash the developed resist pattern with a rinse solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. ​​After washing, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0233] 〈Use〉 The resist composition of the present invention is a resist composition for KrF excimer laser exposure, an ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EU V exposure, particularly suitable as a resist composition for electron beam (EB) exposure or EUV exposure and is useful for microfabrication of semiconductors.

Example

[0234] The present invention will be further specifically described with reference to examples. In the examples, the content or usage amount indicated by “%” and “parts” is based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography . The analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40°C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent 1100 type, MASS is Agil ent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

[0235] Example 1: Synthesis of the salt represented by formula (I-1) 4.38 parts of the salt represented by TIFF2025102839000138.tif38150 formula (I-1-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 1.88 parts of the compound represented by formula (I-1-b ) were added, and then the mixture was further stirred at 50 °C for 2 hours. After the resulting reaction mixture was cooled to 23 °C, 100 parts of chloroform and 50 parts of 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. The obtained organic layer was added with 50 parts of ion-exchanged water and stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer . This water washing operation was repeated 4 times. After the obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 1.12 parts of the salt represented by formula (I-1).

[0236] MASS(ESI(+)Spectrum): M + 263.1 MASS(ESI(-)Spectrum): M - 309.0

[0237] Example 2: Synthesis of the salt represented by formula (I-4) 4.38 parts of the salt represented by TIFF2025102839000139.tif38157 formula (I-1-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 2.63 parts of the compound represented by formula (I-4-b ) were added, and then the mixture was further stirred at 50 °C for 2 hours. After the resulting reaction mixture was cooled to 23 °C, 100 parts of chloroform and 50 parts of 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. The obtained organic ​50 parts of ion-exchanged water was added to the layer, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 4 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant was removed and the residue was concentrated to obtain 1.28 parts of the salt represented by the formula (I-4).

[0238] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 377.0

[0239] Example 3: Synthesis of the salt represented by the formula (I-17) 6.03 parts of the salt represented by the formula (I-17-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the obtained mixed solution, 2.63 parts of the compound represented by the formula (I-4- b) was added, and then the mixture was further stirred at 50 °C for 2 hours. After cooling the obtained reaction mixture to 23 °C, 100 parts of chloroform and 50 parts of 5% aqueous oxalic acid solution were added and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. 50 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 4 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant was removed and the residue was concentrated to obtain 4.66 parts of the salt represented by the formula (I-17).

[0240] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum): M - 541.1

[0241] Example 4: Synthesis of the salt represented by formula (I-18) 6.03 parts of the salt represented by formula (I-17-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 2.81 parts of the compound represented by formula (I-18-b) was added, and then the mixture was further stirred at 50°C for 2 hours. After the resulting reaction mixture was cooled to 23°C, 100 parts of chloroform and 50 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to obtain the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to obtain the organic layer. This water washing operation was repeated 4 times. After the obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. Then, the supernatant liquid was removed and concentrated to obtain 4.38 parts of the salt represented by formula (I-18).

[0242] MASS(ESI(+)Spectrum): M + 263.1 MASS(ESI(-)Spectrum): M - 557.1

[0243] Example 5: Synthesis of the salt represented by formula (I-22) 6.19 parts of the salt represented by formula (I-22-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 2.63 parts of the compound represented by formula (I-4-b) was added, and then the mixture was further stirred at 50°C for 2 hours. ​​​​After cooling the resulting reaction mixture to 23 °C, 100 parts of chloroform and 50 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. This water washing operation was repeated 4 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 3.69 parts of the salt represented by the formula (I-22).

[0244] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 557.0

[0245] Example 6: Synthesis of the salt represented by the formula (I-197) 4.38 parts of the salt represented by the formula (I-1-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the obtained mixed solution, 3.27 parts of the compound represented by the formula (I-197-b) was added, and then the mixture was further stirred at 50 °C for 2 hours. After cooling the resulting reaction mixture to 23 °C, 100 parts of chloroform and 50 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. This water washing operation was repeated 4 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 1.44 parts of the salt represented by the formula (I-197). ​​​​​​​​

[0246] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 434.9

[0247] Example 7: Synthesis of the salt represented by formula (I-199) 6.03 parts of the salt represented by formula (I-17-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 3.27 parts of the compound represented by formula (I-19 7-b) were added, and then the mixture was further stirred at 50 °C for 2 hours. After cooling the resulting reaction mixture to 23 °C, 100 parts of chloroform and 50 parts of 5% oxalic acid aqueous solution were added and stirred at 23 °C for 30 minutes, and then the layers were separated to take out the organic layer. The obtained organic layer was added with 50 parts of ion-exchanged water and stirred at 23 °C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 4 times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether were added to the concentrated residue and stirred at 23 °C for 30 minutes, and then the supernatant liquid was removed and concentrated to obtain 4.96 parts of the salt represented by formula (I-199).

[0248] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 599.0

[0249] Example 8: Synthesis of the salt represented by formula (I-202) 6.19 parts of the salt represented by formula (I-22-a), 30 parts of acetonitrile, and triethylamine ​1.11 parts were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 3.27 parts of the compound represented by the formula (I-19 7-b) was added, and then the mixture was further stirred at 50 °C for 2 hours. After the resulting reaction mixture was cooled to 23 °C, 100 parts of chloroform and 50 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to take out the organic layer. The obtained organic layer was added with 50 parts of ion-exchanged water and stirred at 23 °C for 30 minutes. Then, liquid separation was performed to take out the organic layer. This water washing operation was repeated 4 times. After the obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 °C for 30 minutes. Then, the supernatant liquid was removed and concentrated to obtain 4.06 parts of the salt represented by the formula (I-202).

[0250] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 614.9

[0251] Example 9: Synthesis of the salt represented by the formula (I-106) 6.72 parts of the salt represented by the formula (I-106-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 2.63 parts of the compound represented by the formula (I-4 -b) was added, and then the mixture was further stirred at 50 °C for 2 hours. The obtained reaction mixture was cooled to 23 °C, 100 parts of chloroform and 50 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 °C for 30 minutes. Then, liquid separation was performed to take out the organic layer. The obtained organic layer was added with 50 parts of ion-exchanged water and stirred at 23 °C for 30 minutes. Then, liquid separation was performed to take out the organic layer. It was taken out. This washing operation was repeated 4 times. After concentrating the obtained organic layer, to the concentrated residue, 30 parts of tert-butyl methyl ether was added, and after stirring at 23 °C for 30 minutes, the supernatant liquid was removed and concentrated to obtain 3.97 parts of the salt represented by the formula (I-106).

[0252] MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 557.0

[0253] Example 10: Synthesis of the salt represented by the formula (I-220) 6.72 parts of the salt represented by the formula (I-106-a), 30 parts of acetonitrile, and 1.11 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes. To the obtained mixed solution, 3.27 parts of the compound represented by the formula (I-1 97-b) was added, and then it was further stirred at 50 °C for 2 hours. After cooling the obtained reaction mixture to 23 °C, 100 parts of chloroform and 50 parts of a 5% oxalic acid aqueous solution were added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer. The obtained organic layer was added with 50 parts of ion-exchanged water and stirred at 23 °C for 30 minutes, and then liquid separation was performed to take out the organic layer This washing operation was repeated 4 times. After concentrating the obtained organic layer, to the concentrated residue 30 parts of tert-butyl methyl ether was added, and after stirring at 23 °C for 30 minutes, the upper clear liquid was removed and concentrated to obtain 4.49 parts of the salt represented by the formula (I-220). .

[0254] MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 614.9

[0255] Synthesis of resin The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF2025102839000148.tif49153

[0256] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used, and their molar ratio [monomer (a1-4-2): monomer (a1-1 -3): monomer (a1-2-6)] was mixed so as to be 38:24:38, and further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and this was heated at 85 °C for about 5 hours to carry out polymerization. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered to obtain resin A1 (copolymer) having a weight average molecular weight of about 5.3×10 3 at a yield of 78%. This resin A1 has the following structural units and is as follows. TIFF2025102839000149.tif28125

[0257] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used, and their molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62 Mix them so as to combine, and further, to this monomer mixture, relative to the total mass of all the monomers , 1.5 times the mass of methyl isobutyl ketone was mixed. To the resulting mixture, as an initiator azobisisobutyronitrile was added so as to be 7 mol% relative to the total number of moles of all the monomers , and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution , and after stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and by filtration and recovery, a resin A2 (copolymer) having a weight average molecular weight of about 5.4×10 3 was obtained in a yield of 89%. This resin A2 has the following structural units. TIFF2025102839000150.tif2887

[0258] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( a3-4-2) and monomer (a1-4-2) were used, and the molar ratio [monomer (a1-2 -6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4- 2)] was mixed so as to be in a ratio of 53:3:12:32, and further, to this monomer mixture , 1.5 times the mass of methyl isobutyl ketone was mixed relative to the total mass of all the monomers . To the resulting mixture, azobisisobutyronitrile and azobis(2,4 -dimethylvaleronitrile) were added at 1.2 mol% and 3.6 m ol% respectively relative to the total amount of monomers, and these were heated at 73 °C for about 5 hours. Thereafter, an aqueous solution of p-toluene enesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount Pour the resin into n - heptane to precipitate it, and filter and collect it to obtain resin A3 with a weight - average molecular weight of about 5.3×10 3 in a yield of 88%. This resin A3 has the following structural units . TIFF2025102839000151.tif38127

[0259] Synthesis Example 4 [Synthesis of Resin A4] As monomers, monomer (a1 - 2 - 6), monomer (a2 - 1 - 3), monomer ( a3 - 4 - 2) and monomer (a2 - 2 - x) were used, and their molar ratio [monomer (a1 - 2 - 6): monomer (a2 - 1 - 3): monomer (a3 - 4 - 2): monomer (a2 - 2 - x)] was mixed so as to be in a ratio of 53:3:12:32. Further, 1.5 mass - times of methyl isobutyl ketone was mixed with this monomer mixture with respect to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile and azobis(2,4 - dimethylvaleronitrile) were added at 1.2 mol% and 3.6 mol% respectively with respect to the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, the polymerization reaction solution was poured into a large amount of n - heptane to precipitate the resin, and the resin was filtered and collected to obtain resin A4 with a weight - average molecular weight of about 5.1 ×10 in a yield of 79%. This resin A4 has the following structural units ×10 3 . TIFF2025102839000152.tif38127

[0260] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed, and the obtained mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0261] <Resin> A1 to A4: Resin A1 to Resin A4 <Salt (I)> I-1: Salt represented by formula (I-1) I-4: Salt represented by formula (I-4) I-17: Salt represented by formula (I-17) I-18: Salt represented by formula (I-18) I-22: Salt represented by formula (I-22) I-106: Salt represented by formula (I-106) I-197: Salt represented by formula (I-197) I-199: Salt represented by formula (I-199) I-202: Salt represented by formula (I-202) I-220: Salt represented by formula (I-220) <Acid generator> B1-X1: TIFF2025102839000154.tif2864B1-X2: TIFF2025102839000155.tif2866B1-X3: TIFF2025102839000156.tif2881<Quencher (C)> C1: Synthesized by the method described in JP-A-2011-39502 TIFF2025102839000157.tif3646<Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0262] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was applied to this silicon wafer, and the composition Spin coating was performed so that the film thickness of the layer became 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form a composition layer. On the wafer, a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithography machine ["ELS-F1 25 125 keV" manufactured by Elionix, Inc.] while changing the exposure dose step by step. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate, and further paddle development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

[0263] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0264] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The average hole diameter of the patterns formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and used as the population to calculate the standard deviation. The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm).

Table 3

[0265] (Electron Beam Exposure Evaluation of Resist Composition) A 6-inch silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90 °C for 60 seconds. A resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer became 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form a composition layer. On the composition layer formed on the wafer, an electron beam lithography machine ["ELS-F1 25 125keV" manufactured by Elionix, Inc.] was used, and the exposure dose was changed stepwise to directly draw a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm). After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer at 23 °C for 20 seconds by the dynamic dispense method to obtain a resist pattern. In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity. (hole pitch 40 nm / hole diameter 17 nm). After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate. Subsequently, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer at 23 °C for 20 seconds by the dynamic dispense method to obtain a resist pattern.

[0266] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity. (hole pitch 40 nm / hole diameter 17 nm).

[0267] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The average hole diameter of the patterns formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and used as the population to calculate the standard deviation. The results are shown in Table 4. The numerical values in the table indicate the standard deviation (nm). (hole pitch 40 nm / hole diameter 17 nm). The results are shown in Table 4. The numerical values in the table indicate the standard deviation (nm).

Table 4

Industrial Applicability

[0268] The resist composition containing the salt of the present invention can obtain a resist pattern with good CD uniformity (CDU), and thus is suitable for fine processing of semiconductors and extremely useful industrially.

Claims

1. A resist composition containing an acid generator containing a salt represented by formula (I) and a resin having an acid-labile group, wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). [In formula (I), Q １ and Q ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6, and when z is 2 or more, a plurality of R １ and R ２ may be the same as or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O- or *-O-CO-O-, where * represents a bonding site with C(R １ )(R ２ ), or C(Q １ )(Q ２ ). L 1 represents *-norbornanelactone-(C=O)O-, where * represents the bonding site with X 1 and is the bonding site with X R ３ and R ４ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar represents a phenyl group which may have a substituent. Z ＋ represents an organic cation represented by formula (b2-1). (In formula (b2-1), R b4 to R b6 each independently represents a phenyl group, and the hydrogen atom contained in the phenyl group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms. ) ] [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nｂ -, where * represents the bonding site with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

2. R of formula (I) ４ The resist composition according to claim 1, wherein R is a hydrogen atom.

3. X in formula (I) 1 is *-CO-O- or *-O-CO-O- (where * represents a bonding site with C(R １ )(R ２ ), or C(Q １ )(Q ２ ).). The resist composition according to claim 1 or 2

4. The resist composition according to any one of claims 1 to 3, wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [In formula (a1-1) and formula (a1-2), 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 a bond with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an 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 combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3. ]

5. The resist composition according to any one of claims 1 to 4, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator.

6. (1) A step of applying the resist composition according to any one of claims 1 to 5 onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern, comprising the steps.

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